JP2688698B2 - Polyimide varnish for optical material and method for producing the same - Google Patents
Polyimide varnish for optical material and method for producing the sameInfo
- Publication number
- JP2688698B2 JP2688698B2 JP1196501A JP19650189A JP2688698B2 JP 2688698 B2 JP2688698 B2 JP 2688698B2 JP 1196501 A JP1196501 A JP 1196501A JP 19650189 A JP19650189 A JP 19650189A JP 2688698 B2 JP2688698 B2 JP 2688698B2
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- Prior art keywords
- polyamic acid
- acid solution
- solvent
- polyimide
- polyimide varnish
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Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は光透過性の優れたポリイミドフィルムの作製
に用いるための光学材料用ポリイミドワニスに関する。TECHNICAL FIELD The present invention relates to a polyimide varnish for an optical material, which is used for producing a polyimide film having excellent light transmittance.
ポリイミドは耐熱性プラスチックとして使用されてい
る。ポリイミドの中でフッ素を含有するものは、ほとん
ど無色透明で、耐熱性にも優れているため、従来のポリ
メチルメタクリレートやポリカーボネートでは実現不可
能であった耐熱性光学材料として有望なプラスチックで
ある。Polyimide is used as a heat resistant plastic. Of the polyimides, those containing fluorine are almost colorless and transparent, and also have excellent heat resistance, and thus are promising plastics as heat resistant optical materials that could not be realized by conventional polymethylmethacrylate or polycarbonate.
しかし、透明の含フッ素ポリイミドであっても、光学
材料として使用するには光透過損失が大きいという欠点
があった。However, even a transparent fluorine-containing polyimide has a drawback that it has a large light transmission loss when used as an optical material.
本発明の目的は、従来のポリイミドでは実現できなか
った耐熱性に優れ、光透過損失の小さい光学材料を製造
するためのポリイミドワニスを提供することにある。An object of the present invention is to provide a polyimide varnish for producing an optical material having excellent heat resistance and small light transmission loss, which cannot be realized by conventional polyimides.
本発明を概説すれば、本発明の第１の発明は光学材料
用ポリイミドワニスに関する発明であって、2,2−ビス
−（3,4−ジカルボキシフェニル）−ヘキサフルオロプ
ロパン二無水物と2,2′−ビス（トリフルオロメチル）
−4,4′−ジアミノビフェニルを溶媒中で反応させて得
られるポリアミック酸をイミド化率20％〜98％の範囲で
イミド化したものが溶媒中に溶解していることを特徴と
する。Briefly describing the present invention, the first invention of the present invention relates to a polyimide varnish for optical materials, which comprises 2,2-bis- (3,4-dicarboxyphenyl) -hexafluoropropane dianhydride and 2 , 2'-bis (trifluoromethyl)
It is characterized in that polyamic acid obtained by reacting -4,4'-diaminobiphenyl in a solvent is imidized in a range of 20% to 98% of imidization rate and dissolved in the solvent.
そして、本発明の第２の発明は、第１の発明の光学材
料用ポリイミドワニスの製造方法に関する発明であっ
て、2,2−ビス−（3,4−ジカルボキシフェニル）−ヘキ
サフルオロプロパン二無水物と2,2′−ビス（トリフル
オロメチル）−4,4′−ジアミノビフェニルを溶媒中で
反応させて得られるポリアミック酸をイミド化後、生成
物に溶媒を添加するか、又は生成物を溶媒に加えるか、
あるいは生成したポリイミドを単離して溶媒に加えるこ
とにより、イミド化したものを溶媒に溶解することを特
徴とする。A second invention of the present invention is an invention relating to the method for producing a polyimide varnish for an optical material of the first invention, which comprises 2,2-bis- (3,4-dicarboxyphenyl) -hexafluoropropanedi After imidizing a polyamic acid obtained by reacting an anhydride with 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl in a solvent, the solvent is added to the product, or the product is added. To the solvent, or
Alternatively, it is characterized in that the imidized product is dissolved in a solvent by isolating the produced polyimide and adding it to the solvent.
本発明は、下記の構造式I: で表される2,2−ビス（3,4−ジカルボキシフェニル）−
ヘキサフルオロプロパン二無水物と、下記の構造式II: で表される2,2′−ビス（トリフルオロメチル）−4,4′
−ジアミノビフェニルを溶媒中で反応させて得られるポ
リアミック酸を部分イミド化させたものを溶媒中に溶解
して含有するワニスであることを特徴とする。The present invention has the following structural formula I: 2,2-bis (3,4-dicarboxyphenyl)-represented by
Hexafluoropropane dianhydride and the following structural formula II: 2,2'-bis (trifluoromethyl) -4,4 'represented by
-A varnish containing a partially imidized polyamic acid obtained by reacting diaminobiphenyl in a solvent, which is dissolved and contained in the solvent.
本発明者らは、ポリイミドフィルムの光透過損失の低
減方法を種々検討した結果、ポリイミドワニスを熱処理
（乾燥・硬化）することによりポリアミック酸から直接
作製したポリイミドフィルムは光透過損失が大きいが、
ポリイミドワニスのポリアミック酸をある程度イミド化
した後、一旦、溶媒に溶解し、この溶液を塗布してから
熱処理（乾燥・硬化）を行って作製したポリイミドフィ
ルムは光透過損失が顕著に小さくなることを見出した。The present inventors have variously studied the method of reducing the light transmission loss of the polyimide film, the polyimide film directly produced from polyamic acid by heat treatment (drying / curing) of the polyimide varnish has a large light transmission loss,
The polyimide film produced by imidizing the polyamic acid of the polyimide varnish to some extent, once dissolving it in a solvent, applying this solution, and then performing heat treatment (drying / curing) has a significantly reduced light transmission loss. I found it.
本発明において、溶媒に溶解している樹脂量は５〜40
重量％が適当である。それは５％未満ではフィルムの厚
さが薄くなりすぎ、厚くできない。他方40重量％を超え
ると、粘度が高くなりすぎ作業性が悪くなるからであ
る。In the present invention, the amount of resin dissolved in the solvent is 5-40
% By weight is appropriate. If it is less than 5%, the thickness of the film becomes too thin and cannot be made too thick. On the other hand, if it exceeds 40% by weight, the viscosity becomes too high and the workability deteriorates.
本発明においては、ポリイミドワニスとして2,2−ビ
ス（3,4−ジカルボキシフェニル）−ヘキサフルオロプ
ロパン二無水物と2,2′−ビス（トリフルオロメチル）
−4,4′−ジアミノビフェニルを溶媒中で反応させて得
られるポリアミック酸を用いているため、イミド化後に
おいても、Ｎ−メチル−２−ピロリドン、N,N−ジメチ
ルアセトアミド、N,N−ジメチルホルムアミドなどの極
性有機溶媒やアセトン、メチルエチルケトン、テトラヒ
ドロフランなどの低沸点有機溶媒に可溶である。また、
イミド化の手法としては、加熱処理、無水酢酸を用いる
化学的処理が挙げられる。In the present invention, the polyimide varnish is 2,2-bis (3,4-dicarboxyphenyl) -hexafluoropropane dianhydride and 2,2'-bis (trifluoromethyl).
Since polyamic acid obtained by reacting -4,4'-diaminobiphenyl in a solvent is used, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N- It is soluble in polar organic solvents such as dimethylformamide and low boiling organic solvents such as acetone, methyl ethyl ketone, and tetrahydrofuran. Also,
Examples of the imidization method include heat treatment and chemical treatment using acetic anhydride.
以下、実施例により本発明の光学材料用ポリイミドワ
ニスについて、詳細に説明するが、本発明はこれらの実
施例に限定されるものではない。Hereinafter, the polyimide varnish for optical materials of the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples.
ポリイミドの比率は、ポリアミック酸とポリイミドの
分子構造の違いによる分子中プロトン数の違いに基づい
て核磁気共鳴装置で1Ｈ核測定を行い、試料の７〜8.5pp
m及び11ppm付近のプロトン積分強度により定量的に評価
した。光透過損失の測定は波長633nmのHe-Neレーザ光を
用い、導波路に沿う導波ストリーク光の強度変化から計
算する電子情報通信学会論文誌Ｃ、第J71−Ｃ巻、第543
〜460頁（1988）記載の方法により行った。The ratio of polyimide was measured by 1 H nuclear measurement with a nuclear magnetic resonance apparatus based on the difference in the number of protons in the molecule due to the difference in the molecular structure of polyamic acid and polyimide.
Quantitative evaluation was performed by the proton integrated intensity around m and 11 ppm. The light transmission loss is measured using He-Ne laser light with a wavelength of 633 nm, and is calculated from the intensity change of the guided streak light along the waveguide. IEICE Transactions C, Volumes J71-C, 543.
Up to 460 (1988).
実施例１ 三角フラスコに、前記の構造式Ｉで表される2,2−ビ
ス（3,4−ジカルボキシフェニル）−ヘキサフルオロプ
ロパン二無水物2.225g（5.0×10-3モル）と、前記の構
造式IIで表される2,2′−ビス（トリフルオロメチル）
−4,4′−ジアミノビフェニル1.601g（5.0×10-3モル）
を21.662gのN,N−ジメチルアセトアミド中、窒素雰囲気
下で混合・かくはんし、室温で24時間反応を進め、濃度
15重量％のポリアミック酸溶液（ポリイミドワニス）を
得た。次に、このポリアミック酸溶液約3gを開栓した広
口びんに量り取り、70℃で12時間風乾した後、200℃で
１時間熱処理し、N,N−ジメチルアセトアミドを加えて
溶解し、濃度20重量％のポリアミック酸溶液を得た。こ
のポリアミック酸溶液の一部をシリコンウエハ上にスピ
ンコートし、70℃で２時間風乾した後、シリコンウエハ
からはく離し、重水素化ジメチルスルホキシドに溶解し
て核磁気共鳴装置で分析を行ったところ、98％イミド化
していることが確認できた。次に、残りのポリアミック
酸溶液を石英板上にスピンコートし、70℃×２時間、20
0℃×１時間、300℃×１時間の熱処理を行い、厚さ約18
μｍのポリイミドフィルムを形成した。このポリイミド
フィルムの光透過損失は、後記表１に他の例と共に示す
ように、0.3dB/cmであった。Example 1 In an Erlenmeyer flask, 2.225 g (5.0 × 10 −3 mol) of 2,2-bis (3,4-dicarboxyphenyl) -hexafluoropropane dianhydride represented by the above structural formula I, and 2,2'-bis (trifluoromethyl) represented by the structural formula II of
-4,4'-Diaminobiphenyl 1.601 g (5.0 x 10 -3 mol)
Was mixed and stirred in 21.662 g of N, N-dimethylacetamide under a nitrogen atmosphere, the reaction was allowed to proceed at room temperature for 24 hours, and the concentration was
A 15% by weight polyamic acid solution (polyimide varnish) was obtained. Next, about 3 g of this polyamic acid solution was weighed into an open wide-mouthed bottle, air-dried at 70 ° C for 12 hours, then heat-treated at 200 ° C for 1 hour, dissolved by adding N, N-dimethylacetamide to a concentration of 20 A weight% polyamic acid solution was obtained. A part of this polyamic acid solution was spin-coated on a silicon wafer, air-dried at 70 ° C for 2 hours, peeled from the silicon wafer, dissolved in deuterated dimethyl sulfoxide, and analyzed by a nuclear magnetic resonance apparatus. , 98% imidation was confirmed. Next, spin coat the remaining polyamic acid solution on a quartz plate, and leave at 70 ℃ for 2 hours.
Heat treatment at 0 ℃ x 1 hour, 300 ℃ x 1 hour, thickness about 18
A μm polyimide film was formed. The light transmission loss of this polyimide film was 0.3 dB / cm, as shown in Table 1 below together with other examples.
実施例２ 実施例１で作製した濃度15重量％のポリアミック酸溶
液（ポリイミドワニス）約3gを開栓した広口びんに量り
取り、70℃で12時間風乾した後、130℃で１時間熱処理
し、N,N−ジメチルアセトアミドを加えて溶解し、濃度2
0重量％のポリアミック酸溶液を得た。このポリアミッ
ク酸溶液の一部を用い、実施例１と同様に核磁気共鳴分
析を行ったところ、60％イミド化していることが確認で
きた。次に、残りのポリアミック酸溶液を石英板上にス
ピンコートし、70℃×２時間、200℃×１時間、300℃×
１時間の熱処理を行い、厚さ約８μｍのポリイミドフィ
ルムを形成した。このポリイミドフィルムの光透過損失
は表１に示すように、0.3dB/cmであった。Example 2 About 3 g of the polyamic acid solution (polyimide varnish) having a concentration of 15% by weight prepared in Example 1 was weighed into a wide-mouthed bottle which was opened, air-dried at 70 ° C. for 12 hours, and then heat-treated at 130 ° C. for 1 hour, Add N, N-dimethylacetamide and dissolve to a concentration of 2
A 0% by weight polyamic acid solution was obtained. When a nuclear magnetic resonance analysis was performed in the same manner as in Example 1 using a part of this polyamic acid solution, it was confirmed that the polyamic acid solution was imidized to 60%. Next, spin coat the remaining polyamic acid solution on a quartz plate, 70 ° C x 2 hours, 200 ° C x 1 hour, 300 ° C x
Heat treatment was performed for 1 hour to form a polyimide film having a thickness of about 8 μm. The light transmission loss of this polyimide film was 0.3 dB / cm as shown in Table 1.
実施例３ 実施例１で作製した濃度15重量％のポリアミック酸溶
液（ポリイミドワニス）約3gを開栓した広口びんに量り
取り、70℃で12時間風乾した後、100℃で10時間熱処理
し、N,N−ジメチルアセトアミドを加えて溶解し、濃度3
3重量％のポリアミック酸溶液を得た。このポリアミッ
ク酸溶液の一部を用い、実施例１と同様に核磁気共鳴分
析を行ったところ、22％イミド化していることが確認で
きた。次に、残りのポリアミック酸溶液を石英板上にス
ピンコートし、70℃×２時間、200℃×１時間、300℃×
１時間の熱処理を行い、厚さ約47μｍのポリイミドフィ
ルムを形成した。このポリイミドフィルムの光透過損失
は表１に示すように、0.1dB/cmであった。Example 3 About 3 g of the polyamic acid solution (polyimide varnish) having a concentration of 15% by weight prepared in Example 1 was weighed into a wide-mouthed bottle that had been opened, air-dried at 70 ° C for 12 hours, and then heat-treated at 100 ° C for 10 hours, Add N, N-dimethylacetamide and dissolve to a concentration of 3
A 3% by weight polyamic acid solution was obtained. When a nuclear magnetic resonance analysis was performed in the same manner as in Example 1 using a part of this polyamic acid solution, it was confirmed that 22% imidization was carried out. Next, spin coat the remaining polyamic acid solution on a quartz plate, 70 ° C x 2 hours, 200 ° C x 1 hour, 300 ° C x
A heat treatment was performed for 1 hour to form a polyimide film having a thickness of about 47 μm. The light transmission loss of this polyimide film was 0.1 dB / cm as shown in Table 1.
比較例１ 実施例１で作製した濃度15重量％のポリアミック酸溶
液（ポリイミドワニス）の一部を用い、実施例１と同様
に核磁気共鳴分析を行い、ポリアミック酸がほとんどイ
ミド化していない（イミド化率２％以下）ことを確認し
た。次に、残りのポリアミック酸溶液を石英板上にスピ
ンコートし、70℃×２時間、200℃×１時間、300℃×１
時間の熱処理を行い、厚さ約18μｍのポリイミドフィル
ムを形成した。このポリイミドフィルムの光透過損失
は、表１に示すように、1.7dB/cmであった。Comparative Example 1 Using a portion of the polyamic acid solution (polyimide varnish) having a concentration of 15% by weight prepared in Example 1, a nuclear magnetic resonance analysis was performed in the same manner as in Example 1, and the polyamic acid was hardly imidized (imide. It was confirmed that the conversion rate was 2% or less). Next, spin coat the remaining polyamic acid solution on a quartz plate, 70 ℃ × 2 hours, 200 ℃ × 1 hour, 300 ℃ × 1
Heat treatment was performed for a time to form a polyimide film having a thickness of about 18 μm. The light transmission loss of this polyimide film was 1.7 dB / cm as shown in Table 1.
比較例２ 実施例１で作製した濃度15重量％のポリアミック酸溶
液（ポリイミドワニス）約3gを開栓した広口びんに量り
取り、70℃で12時間風乾した後、100℃で１時間熱処理
し、N,N−ジメチルアセトアミドを加えて溶解し、濃度3
0重量％のポリアミック酸溶液を得た。このポリアミッ
ク酸溶液の一部を用い、実施例１と同様に核磁気共鳴分
析を行ったところ、18％イミド化していることが確認で
きた。次に、残りのポリアミック酸溶液を石英板上にス
ピンコートし、70℃×２時間、200℃×１時間、300℃×
１時間の熱処理を行い、厚さ約23μｍのポリイミドフィ
ルムを形成した。このポリイミドフィルムの光透過損失
は表１に示すように、2.9dB/cmであった。Comparative Example 2 About 3 g of the polyamic acid solution (polyimide varnish) having a concentration of 15% by weight prepared in Example 1 was weighed into a wide-mouthed bottle having been opened, air-dried at 70 ° C. for 12 hours, and then heat-treated at 100 ° C. for 1 hour, Add N, N-dimethylacetamide and dissolve to a concentration of 3
A 0% by weight polyamic acid solution was obtained. When a nuclear magnetic resonance analysis was carried out in the same manner as in Example 1 using a part of the polyamic acid solution, it was confirmed that the polyamic acid solution was 18% imidized. Next, spin coat the remaining polyamic acid solution on a quartz plate, 70 ° C x 2 hours, 200 ° C x 1 hour, 300 ° C x
Heat treatment was performed for 1 hour to form a polyimide film having a thickness of about 23 μm. The light transmission loss of this polyimide film was 2.9 dB / cm as shown in Table 1.
比較例３ 実施例１で作製した濃度15重量％のポリアミック酸溶
液（ポリイミドワニス）約3gを開栓した広口びんに量り
取り、70℃で24時間風乾した後、250℃で１時間熱処理
し、N,N−ジメチルアセトアミドを加えて溶解し、濃度2
0重量％のポリアミック酸溶液を得た。このポリアミッ
ク酸溶液の一部を用い、実施例１と同様に核磁気共鳴分
析を行ったところ、99％イミド化していることが確認で
きた。次に、残りのポリアミック酸溶液を石英板上にス
ピンコートし、70℃×２時間、200℃×１時間、300℃×
１時間の熱処理を行い、厚さ約14μｍのポリイミドフィ
ルムを形成した。このポリイミドフィルムの光透過損失
は表１に示すように、1.2dB/cmであった。Comparative Example 3 About 3 g of a polyamic acid solution (polyimide varnish) having a concentration of 15% by weight prepared in Example 1 was weighed into a wide-mouthed bottle, which was air-dried at 70 ° C. for 24 hours, and then heat-treated at 250 ° C. for 1 hour, Add N, N-dimethylacetamide and dissolve to a concentration of 2
A 0% by weight polyamic acid solution was obtained. When a nuclear magnetic resonance analysis was carried out in the same manner as in Example 1 using a part of this polyamic acid solution, it was confirmed that the polyamic acid solution was 99% imidized. Next, spin coat the remaining polyamic acid solution on a quartz plate, 70 ° C x 2 hours, 200 ° C x 1 hour, 300 ° C x
Heat treatment was performed for 1 hour to form a polyimide film having a thickness of about 14 μm. The light transmission loss of this polyimide film was 1.2 dB / cm as shown in Table 1.
比較例４ 実施例１で作製した濃度15重量％のポリアミック酸溶
液（ポリイミドワニス）約3gを開栓した広口びんに量り
取り、70℃で24時間風乾した後、300℃で１時間熱処理
し、N,N−ジメチルアセトアミドを加えて溶解し、濃度2
0重量％のポリアミック酸溶液を得た。このポリアミッ
ク酸溶液の一部を用い、実施例１と同様に核磁気共鳴分
析を行ったところ、99％イミド化していることが確認で
きた。次に、残りのポリアミック酸溶液を石英板上にス
ピンコートし、70℃×２時間、200℃×１時間、300℃×
１時間の熱処理を行い、厚さ約15μｍのポリイミドフィ
ルムを形成した。このポリイミドフィルムの光透過損失
は表１に示すように、2.0dB/cmであった。Comparative Example 4 About 3 g of the polyamic acid solution (polyimide varnish) with a concentration of 15% by weight prepared in Example 1 was weighed into a wide-mouthed bottle that was opened, air-dried at 70 ° C. for 24 hours, and then heat-treated at 300 ° C. for 1 hour, Add N, N-dimethylacetamide and dissolve to a concentration of 2
A 0% by weight polyamic acid solution was obtained. When a nuclear magnetic resonance analysis was carried out in the same manner as in Example 1 using a part of this polyamic acid solution, it was confirmed that the polyamic acid solution was 99% imidized. Next, spin coat the remaining polyamic acid solution on a quartz plate, 70 ° C x 2 hours, 200 ° C x 1 hour, 300 ° C x
Heat treatment was performed for 1 hour to form a polyimide film having a thickness of about 15 μm. The light transmission loss of this polyimide film was 2.0 dB / cm as shown in Table 1.
これらの結果から、本発明の光学材料用ポリイミドワ
ニスを用いて作製したポリイミドフィルムは光透過損失
が小さいことが明らかになった。From these results, it was revealed that the polyimide film produced by using the polyimide varnish for optical materials of the present invention has a small light transmission loss.
〔発明の効果〕 以上説明したように、本発明の光学材料用ポリイミド
ワニスは、従来のポリアミック酸溶液に比べ、ポリイミ
ドフィルムにしたときの光透過性が優れているという利
点があるため、耐熱性に優れ、光透過損失の小さい光学
材料を製造することができる。 [Effects of the Invention] As described above, the polyimide varnish for optical materials of the present invention has an advantage that the light transmittance when formed into a polyimide film is superior to that of a conventional polyamic acid solution, and thus has heat resistance. It is possible to manufacture an optical material having excellent light transmission loss and small light transmission loss.
Claims (2)
ル）−ヘキサフルオロプロパン二無水物と2,2′−ビス
（トリフルオロメチル）−4,4′−ジアミノビフェニル
を溶媒中で反応させて得られるポリアミック酸をイミド
化率20％〜98％の範囲でイミド化したものが溶媒中に溶
解していることを特徴とする光学材料用ポリイミドワニ
ス。1. 2,2-Bis- (3,4-dicarboxyphenyl) -hexafluoropropane dianhydride and 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl in a solvent A polyimide varnish for optical materials, characterized in that a polyamic acid obtained by reacting with the above is imidized in a range of 20% to 98% in imidization and dissolved in a solvent.
ル）−ヘキサフルオロプロパン二無水物と2,2′−ビス
（トリフルオロメチル）−4,4′−ジアミノビフェニル
を溶媒中で反応させて得られるポリアミック酸をイミド
化後、生成物に溶媒を添加するか、又は生成物を溶媒に
加えるか、あるいは生成したポリイミドを単離して溶媒
に加えることにより、イミド化したものを溶媒に溶解す
ることを特徴とする請求項１記載の光学材料用ポリイミ
ドワニスの製造方法。2. 2,2-Bis- (3,4-dicarboxyphenyl) -hexafluoropropane dianhydride and 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl in a solvent After imidizing the polyamic acid obtained by reacting with, the solvent is added to the product, or the product is added to the solvent, or the resulting polyimide is isolated and added to the solvent to give an imidized product. It dissolves in a solvent, The manufacturing method of the polyimide varnish for optical materials of Claim 1 characterized by the above-mentioned.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1196501A JP2688698B2 (en) | 1989-07-31 | 1989-07-31 | Polyimide varnish for optical material and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1196501A JP2688698B2 (en) | 1989-07-31 | 1989-07-31 | Polyimide varnish for optical material and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0362868A JPH0362868A (en) | 1991-03-18 |
| JP2688698B2 true JP2688698B2 (en) | 1997-12-10 |
Family
ID=16358806
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1196501A Expired - Lifetime JP2688698B2 (en) | 1989-07-31 | 1989-07-31 | Polyimide varnish for optical material and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2688698B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2041133C (en) * | 1990-04-27 | 1995-01-03 | Toru Matsuura | Polymide optical waveguide |
| US20050221023A1 (en) * | 2003-01-10 | 2005-10-06 | Michie Sakamoto | Polyimide film and process for producing the same |
| TW200635982A (en) | 2005-03-11 | 2006-10-16 | Nippon Catalytic Chem Ind | Production method of polyimide solution and fluorinated polyimide solution |
| KR101328838B1 (en) * | 2010-03-30 | 2013-11-13 | 코오롱인더스트리 주식회사 | Polyimide film |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62127827A (en) * | 1985-11-29 | 1987-06-10 | Hitachi Chem Co Ltd | Composition for oriented film for liquid crystal |
-
1989
- 1989-07-31 JP JP1196501A patent/JP2688698B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62127827A (en) * | 1985-11-29 | 1987-06-10 | Hitachi Chem Co Ltd | Composition for oriented film for liquid crystal |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0362868A (en) | 1991-03-18 |
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