JP2004054254A5 - - Google Patents
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- JP2004054254A5 JP2004054254A5 JP2003150454A JP2003150454A JP2004054254A5 JP 2004054254 A5 JP2004054254 A5 JP 2004054254A5 JP 2003150454 A JP2003150454 A JP 2003150454A JP 2003150454 A JP2003150454 A JP 2003150454A JP 2004054254 A5 JP2004054254 A5 JP 2004054254A5
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【特許請求の範囲】
【請求項１】（ａ）一般式（１）で表される構造を有する樹脂と、（ｂ）感光剤と、（ｃ）大気圧下における沸点が１００℃以上１４０℃以下の有機溶媒とを含有し、かつ、（ｃ）成分の含有量が有機溶媒全量に対して７０重量％以上１００重量％以下である感光性樹脂組成物。
【化１】
【請求項２】（ａ）一般式（２）〜（５）のいずれかで表される構造を有する樹脂から選ばれた１種以上の樹脂と、（ｂ）感光剤と、（ｃ）大気圧下における沸点が１００℃以上１４０℃以下の有機溶媒とを含有し、かつ、（ｃ）成分の含有量が有機溶媒全量に対して５０重量％以上１００重量％以下である感光性樹脂組成物。
【化２】
【請求項３】（ｂ）成分がキノンジアジド化合物である請求項１または２に記載の感光性樹脂組成物。
【請求項４】請求項１または２に記載の感光性樹脂組成物を基板上に塗布し感光性樹脂膜を形成する工程、該感光性樹脂膜を乾燥する工程、該感光性樹脂膜を露光する工程、露光された感光性樹脂膜を現像する工程、および、加熱処理をする工程を含む耐熱性樹脂膜の製造方法。
【請求項５】感光性樹脂組成物の塗布をスリットダイコート法を用いて行う請求項４記載の耐熱性樹脂膜の製造方法。
【請求項６】感光性樹脂膜の現像をアルカリ現像液を用いて行う請求項４記載の耐熱性樹脂膜の製造方法。
【請求項７】請求項１または２に記載の感光性樹脂組成物を、第一電極が形成された基板上に塗布し感光性樹脂膜を形成する工程、該感光性樹脂膜を乾燥、露光、現像および加熱処理して絶縁層を形成する工程、発光層を形成する工程、および、第二電極を形成する工程を少なくとも含む有機電界発光装置の製造方法。
【請求項８】絶縁層を第一電極のエッジを覆うように形成する請求項７に記載の有機電界発光装置の製造方法。
【請求項９】請求項４記載の製造方法により得られた耐熱性樹脂膜を有する有機電界発光装置。
【請求項１０】請求項４記載の製造方法により得られた耐熱性樹脂膜を表面保護膜または層間絶縁膜として有する電子部品。
[Claims]
(1) A resin having a structure represented by the general formula (1), (b) a photosensitizer, and (c) an organic solvent having a boiling point at atmospheric pressure of 100 ° C to 140 ° C. A photosensitive resin composition which contains the component (c) and has a content of 70 % by weight or more and 100% by weight or less based on the total amount of the organic solvent.
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2. A composition comprising: (a) at least one resin selected from resins having a structure represented by any of formulas (2) to (5); (b) a photosensitive agent; A photosensitive resin composition containing an organic solvent having a boiling point of 100 ° C. or more and 140 ° C. or less at atmospheric pressure, and having a component (c) content of 50% by weight or more and 100% by weight or less based on the total amount of the organic solvent; .
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Wherein component (b) is a photosensitive resin composition according to claim 1 or 2 is a quinonediazide compound.
4. A process of forming a photosensitive resin composition is coated on a substrate a photosensitive resin film according to claim 1 or 2, drying the photosensitive resin film, exposing the photosensitive resin film A method for producing a heat-resistant resin film including a step of performing, a step of developing the exposed photosensitive resin film, and a step of performing a heat treatment.
5. The method for producing a heat-resistant resin film according to claim 4 , wherein the application of the photosensitive resin composition is performed by a slit die coating method.
6. The method for producing a heat-resistant resin film according to claim 4, wherein the development of the photosensitive resin film is performed using an alkali developer.
7. A photosensitive resin composition according to claim 1 or 2, the step of forming a photosensitive resin film is applied on the substrate on which the first electrode is formed, drying the photosensitive resin film, exposing A method for manufacturing an organic electroluminescent device, comprising at least a step of forming an insulating layer by performing development and heat treatment, a step of forming a light emitting layer, and a step of forming a second electrode.
8. A method of manufacturing an organic electroluminescence device of claim 7 for forming the insulating layer so as to cover the edges of the first electrode.
9. The organic electroluminescent device having a heat-resistant resin film obtained by the production method according to claim 4, wherein.
10. An electronic component having a heat-resistant resin film obtained by the method according to claim 4 as a surface protective film or an interlayer insulating film.
【００１１】
【課題を解決するための手段】 本発明は、（ａ）一般式（１）で表される構造を有する樹脂と、（ｂ）感光剤と、（ｃ）大気圧下における沸点が１００℃以上１４０℃以下の有機溶媒とを含有し、かつ、（ｃ）成分の含有量が有機溶媒全量に対して７０重量％以上１００重量％以下である感光性樹脂組成物である。また、本発明は、（ａ）一般式（２）〜（５）のいずれかで表される構造を有する樹脂から選ばれた１種以上の樹脂と、（ｂ）感光剤と、（ｃ）大気圧下における沸点が１００℃以上１４０℃以下の有機溶媒とを含有し、かつ、（ｃ）成分の含有量が有機溶媒全量に対して５０重量％以上１００重量％以下である感光性樹脂組成物である。
[0011]
The present invention provides (a) a resin having a structure represented by the general formula (1), (b) a photosensitizer, and (c) a boiling point at atmospheric pressure of 100 ° C. or higher. A photosensitive resin composition containing an organic solvent having a temperature of 140 ° C. or lower and having a content of the component (c) of 70 % by weight or more and 100% by weight or less based on the total amount of the organic solvent. Further, the present invention provides (a) one or more resins selected from resins having a structure represented by any of the general formulas (2) to (5), (b) a photosensitizer, and (c) A photosensitive resin composition containing an organic solvent having a boiling point of not less than 100 ° C. and not more than 140 ° C. under atmospheric pressure, and having a component (c) content of not less than 50% by weight and not more than 100% by weight based on the total amount of the organic solvent; Things.
（式（１）中Ｒ１は２個以上の炭素原子を有する２価から８価の有機基、Ｒ２は２個以上の炭素原子を有する２価から６価の有機基、Ｒ３およびＲ４は同じでも異なっていてもよく、水素原子または炭素数１から２０までの有機基を示す。ｎは５から１０００００までの範囲、ｐおよびｑは、それぞれ０から４までの範囲、ｒおよびｓは、それぞれ０から２までの範囲である。ｐ＋ｑ＞０である。
式（２）〜（５）中Ｒ １ は２個以上の炭素原子を有する２価から８価の有機基、Ｒ ２ は２個以上の炭素原子を有する２価から６価の有機基、Ｒ ３ およびＲ ４ は同じでも異なっていてもよく、水素原子または炭素数１から２０までの有機基、Ｒ ５ は２価の有機基、ＸおよびＹはそれぞれカルボキシル基、フェノール性水酸基、スルホン酸基、チオール基、不飽和炭化水素基を１つ以上含有する炭素数１から１０までの炭化水素基、ニトロ基、メチロール基、エステル基、ヒドロキシアルキニル基より選ばれた一つ以上の置換基を有する有機基を示す。ｎは５から１０００００までの範囲、ｍは０から１０までの範囲、ｐおよびｑは、それぞれ０から４までの範囲、ｒおよびｓは、それぞれ０から２までの範囲である。ｐ＋ｑ＞０である。）
また、本発明は、上記の感光性樹脂組成物を基板上に塗布し感光性樹脂膜を形成する工程、該感光性樹脂膜を乾燥する工程、該感光性樹脂膜を露光する工程、露光された感光性樹脂膜を現像する工程、および、加熱処理をする工程を含む耐熱性樹脂膜の製造方法である。
(In the formula (1) , R 1 is a divalent to octavalent organic group having two or more carbon atoms, R 2 is a divalent to hexavalent organic group having two or more carbon atoms, R 3 and R 4 may be the same or different and represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, n ranges from 5 to 100,000, p and q each range from 0 to 4, r and s Are each in the range from 0 to 2. p + q> 0.
In the formulas (2) to (5), R 1 is a divalent to octavalent organic group having two or more carbon atoms, R 2 is a divalent to hexavalent organic group having two or more carbon atoms, R 3 and R 4 may be the same or different; a hydrogen atom or an organic group having 1 to 20 carbon atoms; R 5 is a divalent organic group; X and Y are a carboxyl group, a phenolic hydroxyl group, and a sulfonic acid group, respectively; Having one or more substituents selected from hydrocarbon groups having 1 to 10 carbon atoms containing at least one thiol group, unsaturated hydrocarbon group, nitro group, methylol group, ester group and hydroxyalkynyl group Shows an organic group. n ranges from 5 to 100,000, m ranges from 0 to 10, p and q each range from 0 to 4, and r and s each range from 0 to 2. p + q> 0. )
Further, the present invention provides a step of applying the photosensitive resin composition on a substrate to form a photosensitive resin film, a step of drying the photosensitive resin film, a step of exposing the photosensitive resin film, This is a method for producing a heat-resistant resin film including a step of developing the photosensitive resin film that has been heated and a step of performing a heat treatment.
参考例１
乾燥窒素気流下、合成例１で得られた水酸基含有酸無水物（ａ）１２．０１ｇ（０．０２モル）をＮ−メチル−２−ピロリドン（ＮＭＰ）１００ｇに溶解させた。ここに合成例２で得られた水酸基含有ジアミン（ｂ）７．２ｇ（０．０１２モル）をＮＭＰ２５ｇとともに加えて、２０℃で１時間反応させ、次いで５０℃で２時間反応させた。末端封止剤は添加しなかった。その後、Ｎ，Ｎ−ジメチルホルムアミドジメチルアセタール７．１５ｇ（０．０６モル）をＮＭＰ１０ｇで希釈した溶液を１０分かけて滴下した。滴下後、５０℃で３時間攪拌した。反応終了後、溶液を水１ｌに投入して、沈殿した樹脂（樹脂Ａ）をろ過で集めた。樹脂Ａを８０℃の真空乾燥機で４０時間乾燥した。
Reference Example 1
In a dry nitrogen stream, 12.01 g (0.02 mol) of the hydroxyl group-containing anhydride (a) obtained in Synthesis Example 1 was dissolved in 100 g of N-methyl-2-pyrrolidone (NMP). Here, 7.2 g (0.012 mol) of the hydroxyl-containing diamine (b) obtained in Synthesis Example 2 was added together with 25 g of NMP, reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 2 hours. No endcapping agent was added. Thereafter, a solution prepared by diluting 7.15 g (0.06 mol) of N, N-dimethylformamide dimethyl acetal with 10 g of NMP was added dropwise over 10 minutes. After the dropwise addition, the mixture was stirred at 50 ° C. for 3 hours. After completion of the reaction, the solution was poured into 1 liter of water, and the precipitated resin (resin A) was collected by filtration. Resin A was dried in a vacuum dryer at 80 ° C. for 40 hours.
実施例１
乾燥窒素気流下、合成例１で得られた水酸基含有酸無水物（ａ）１２．０１ｇ（０．０２モル）をＮ−メチル−２−ピロリドン（ＮＭＰ）１００ｇに溶解させた。ここに合成例２で得られた水酸基含有ジアミン（ｂ）９．６ｇ（０．０１６モル）をＮＭＰ２５ｇとともに加えて、２０℃で１時間反応させ、次いで５０℃で２時間反応させた。次に４−アミノフェノール０．８７ｇ（０．００８モル）を加え５０℃で２時間反応させた。その後、Ｎ，Ｎ−ジメチルホルムアミドジメチルアセタール７．１５ｇ（０．０６モル）をＮＭＰ１０ｇで希釈した溶液を１０分かけて滴下した。滴下後、５０℃で３時間攪拌した。反応終了後、溶液を水１ｌに投入して、沈殿した樹脂（樹脂Ｂ）をろ過で集めた。樹脂Ｂを８０℃の真空乾燥機で４０時間乾燥した。
Example 1
In a dry nitrogen stream, 12.01 g (0.02 mol) of the hydroxyl group-containing anhydride (a) obtained in Synthesis Example 1 was dissolved in 100 g of N-methyl-2-pyrrolidone (NMP). Here, 9.6 g (0.016 mol) of the hydroxyl-containing diamine (b) obtained in Synthesis Example 2 was added together with 25 g of NMP, reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 2 hours. Next, 0.87 g (0.008 mol) of 4-aminophenol was added and reacted at 50 ° C. for 2 hours. Thereafter, a solution prepared by diluting 7.15 g (0.06 mol) of N, N-dimethylformamide dimethyl acetal with 10 g of NMP was added dropwise over 10 minutes. After the dropwise addition, the mixture was stirred at 50 ° C. for 3 hours. After completion of the reaction, the solution was poured into 1 liter of water, and the precipitated resin (resin B) was collected by filtration. Resin B was dried in a vacuum dryer at 80 ° C. for 40 hours.
実施例２
乾燥窒素気流下、合成例１で得られた水酸基含有酸無水物（ａ）１２．０１ｇ（０．０２モル）をＮ−メチル−２−ピロリドン（ＮＭＰ）１００ｇに溶解させた。ここに合成例３で得られた水酸基含有ジアミン（ｃ）４．８４ｇ（０．００８モル）と合成例４で得られた水酸基含有ジアミン（ｄ）１．９４ｇ（０．００８モル）をＮＭＰ２５ｇとともに加えて、２０℃で１時間反応させ、次いで５０℃で２時間反応させた。次に４−エチニルアニリン０．９４ｇ（０．００８モル）を加え５０℃で２時間反応させた。その後、Ｎ，Ｎ−ジメチルホルムアミドジメチルアセタール７．１５ｇ（０．０６モル）をＮＭＰ５ｇで希釈した溶液を１０分かけて滴下した。滴下後、５０℃で３時間攪拌した。反応終了後、溶液を水１ｌに投入して、沈殿した樹脂（樹脂Ｃ）をろ過で集めた。樹脂Ｃを８０℃の真
空乾燥機で４０時間乾燥した。
Example 2
In a dry nitrogen stream, 12.01 g (0.02 mol) of the hydroxyl group-containing anhydride (a) obtained in Synthesis Example 1 was dissolved in 100 g of N-methyl-2-pyrrolidone (NMP). Here, 4.84 g (0.008 mol) of the hydroxyl-containing diamine (c) obtained in Synthesis Example 3 and 1.94 g (0.008 mol) of the hydroxyl-containing diamine (d) obtained in Synthesis Example 4 were added together with 25 g of NMP. In addition, the reaction was carried out at 20 ° C. for 1 hour and then at 50 ° C. for 2 hours. Next, 0.94 g (0.008 mol) of 4-ethynylaniline was added and reacted at 50 ° C. for 2 hours. Thereafter, a solution prepared by diluting 7.15 g (0.06 mol) of N, N-dimethylformamide dimethyl acetal with 5 g of NMP was added dropwise over 10 minutes. After the dropwise addition, the mixture was stirred at 50 ° C. for 3 hours. After completion of the reaction, the solution was poured into 1 liter of water, and the precipitated resin (Resin C) was collected by filtration. Resin C was dried in a vacuum dryer at 80 ° C. for 40 hours.
実施例３
乾燥窒素気流下、合成例１で得られた水酸基含有酸無水物（ａ）１２．０１ｇ（０．０２モル）をＮ−メチル−２−ピロリドン（ＮＭＰ）１００ｇに溶解させた。ここに合成例２で得られた水酸基含有ジアミン（ｂ）９．６ｇ（０．０１６モル）をＮＭＰ２５ｇとともに加えて、２０℃で１時間反応させ、次いで５０℃で２時間反応させた。次に４−アミノフェノール０．４４ｇ（０．００４モル）および４−エチニルアニリン０．４７ｇ（０．００４モル）を加え５０℃で２時間反応させた。その後、Ｎ，Ｎ−ジメチルホルムアミドジメチルアセタール７．１５ｇ（０．０６モル）をＮＭＰ１０ｇで希釈した溶液を１０分かけて滴下した。滴下後、５０℃で３時間攪拌した。反応終了後、溶液を水１ｌに投入して、沈殿した樹脂（樹脂Ｄ）をろ過で集めた。樹脂Ｄを８０℃の真空乾燥機で４０時間乾燥した。
Example 3
In a dry nitrogen stream, 12.01 g (0.02 mol) of the hydroxyl group-containing anhydride (a) obtained in Synthesis Example 1 was dissolved in 100 g of N-methyl-2-pyrrolidone (NMP). Here, 9.6 g (0.016 mol) of the hydroxyl-containing diamine (b) obtained in Synthesis Example 2 was added together with 25 g of NMP, reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 2 hours. Next, 0.44 g (0.004 mol) of 4-aminophenol and 0.47 g (0.004 mol) of 4-ethynylaniline were added and reacted at 50 ° C. for 2 hours. Thereafter, a solution prepared by diluting 7.15 g (0.06 mol) of N, N-dimethylformamide dimethyl acetal with 10 g of NMP was added dropwise over 10 minutes. After the dropwise addition, the mixture was stirred at 50 ° C. for 3 hours. After completion of the reaction, the solution was poured into 1 liter of water, and the precipitated resin (Resin D) was collected by filtration. Resin D was dried in a vacuum dryer at 80 ° C. for 40 hours.
実施例４
乾燥窒素気流下、４，４’−ジアミノジフェニルエーテル９．０８ｇ（０．０４５モル）、１，３−ビス（３−アミノプロピル）テトラメチルジシロキサン１．２４ｇ（０．００５モル）をＮ−メチル−２−ピロリドン（ＮＭＰ）２０ｇに溶解させた。ここに合成例１で得られた水酸基含有酸二無水物（ａ）２４．０２ｇ（０．０４モル）をＮＭＰ１５ｇとともに加えて、２０℃で１時間反応させ、次いで５０℃で２時間反応させた。反応後、末端封止剤として無水マレイン酸１．９６ｇ（０．０２モル）を加えさらに５０℃で２時間反応させた。その後、Ｎ，Ｎ−ジメチルホルムアミドジメチルアセタール１５．１９ｇ（０．１２７モル）をＮＭＰ４ｇで希釈した溶液を１０分かけて滴下した。滴下後、５０℃で３時間攪拌した。反応終了後、溶液を水１ｌに投入して、沈殿した樹脂（樹脂Ｅ）をろ過で集めた。樹脂Ｅを７０℃の真空乾燥機で６０時間乾燥した。
Example 4
Under a stream of dry nitrogen, 9.04 g (0.045 mol) of 4,4'-diaminodiphenyl ether and 1.24 g (0.005 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane were added to N-methyl. -2-Pyrrolidone (NMP) was dissolved in 20 g. Here, 24.02 g (0.04 mol) of the hydroxyl group-containing dianhydride (a) obtained in Synthesis Example 1 was added together with 15 g of NMP, reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 2 hours. . After the reaction, 1.96 g (0.02 mol) of maleic anhydride was added as a terminal blocking agent, and the mixture was further reacted at 50 ° C. for 2 hours. Thereafter, a solution prepared by diluting 15.19 g (0.127 mol) of N, N-dimethylformamide dimethyl acetal with 4 g of NMP was added dropwise over 10 minutes. After the dropwise addition, the mixture was stirred at 50 ° C. for 3 hours. After completion of the reaction, the solution was poured into 1 liter of water, and the precipitated resin (Resin E) was collected by filtration. Resin E was dried in a vacuum dryer at 70 ° C. for 60 hours.
実施例５
乾燥窒素気流下、合成例３で得られた水酸基含有ジアミン化合物（ｃ）９．６７（０．０１６モル）、１，３−ビス（３−アミノプロピル）テトラメチルジシロキサン０．５０ｇ（０．００２モル）、末端封止剤として３−アミノフェノール０．４４ｇ（０．００４モル）をＮ−メチル−２−ピロリドン（ＮＭＰ）５０ｇに溶解させた。ここにビス（３，４−ジカルボキシフェニル）エーテル二無水物６．２ｇ（０．０２モル）をＮＭＰ１４ｇとともに加えて、２０℃で１時間反応させ、次いで５０℃で４時間反応させた。その後、Ｎ，Ｎ−ジメチルホルムアミドジメチルアセタール７．１５ｇ（０．０６モル）をＮＭＰ５ｇで希釈した溶液を１０分かけて滴下した。滴下後、５０℃で３時間攪拌した。反応終了後、溶液を水１ｌに投入して、沈殿した樹脂（樹脂Ｆ）をろ過で集めた。樹脂Ｆを７０℃の真空乾燥機で６０時間乾燥した。
Example 5
9.67 (0.016 mol) of the hydroxyl group-containing diamine compound (c) obtained in Synthesis Example 3 and 0.50 g of 1,3-bis (3-aminopropyl) tetramethyldisiloxane (0. 002 mol) and 0.44 g (0.004 mol) of 3-aminophenol as a terminal blocking agent were dissolved in 50 g of N-methyl-2-pyrrolidone (NMP). Here, 6.2 g (0.02 mol) of bis (3,4-dicarboxyphenyl) ether dianhydride was added together with 14 g of NMP, and the mixture was reacted at 20 ° C. for 1 hour and then at 50 ° C. for 4 hours. Thereafter, a solution prepared by diluting 7.15 g (0.06 mol) of N, N-dimethylformamide dimethyl acetal with 5 g of NMP was added dropwise over 10 minutes. After the dropwise addition, the mixture was stirred at 50 ° C. for 3 hours. After completion of the reaction, the solution was poured into 1 L of water, and the precipitated resin (Resin F) was collected by filtration. Resin F was dried in a vacuum dryer at 70 ° C. for 60 hours.
実施例６
乾燥窒素気流下、合成例３で得られた水酸基含有ジアミン化合物（ｃ）９．６７（０．０１６モル）、１，３−ビス（３−アミノプロピル）テトラメチルジシロキサン０．５０ｇ（０．００２モル）をＮ−メチル−２−ピロリドン（ＮＭＰ）５０ｇに溶解させた。ここにビス（３，４−ジカルボキシフェニル）エーテル二無水物６．２ｇ（０．０２モル）をＮＭＰ１４ｇとともに加えて、２０℃で１時間反応させ、次いで５０℃で２時間反応させた。次に末端封止剤として４−エチニルアニリン０．４７ｇ（０．００４モル）を加えさらに５０℃で２時間反応させた。その後、Ｎ，Ｎ−ジメチルホルムアミドジメチルアセタール４．７７ｇ（０．０４モル）をＮＭＰ５ｇで希釈した溶液を１０分かけて滴下した。滴下後、５０℃で３時間攪拌した。反応終了後、溶液を水１ｌに投入して、沈殿した樹脂（樹脂Ｇ）をろ過で集めた。樹脂Ｇを７０℃の真空乾燥機で６０時間乾燥した。
Example 6
9.67 (0.016 mol) of the hydroxyl group-containing diamine compound (c) obtained in Synthesis Example 3 and 0.50 g of 1,3-bis (3-aminopropyl) tetramethyldisiloxane (0. 002 mol) was dissolved in 50 g of N-methyl-2-pyrrolidone (NMP). Here, 6.2 g (0.02 mol) of bis (3,4-dicarboxyphenyl) ether dianhydride was added together with 14 g of NMP, and the mixture was reacted at 20 ° C. for 1 hour and then at 50 ° C. for 2 hours. Next, 0.47 g (0.004 mol) of 4-ethynylaniline was added as a terminal blocking agent, and the mixture was further reacted at 50 ° C. for 2 hours. Thereafter, a solution obtained by diluting 4.77 g (0.04 mol) of N, N-dimethylformamide dimethyl acetal with 5 g of NMP was added dropwise over 10 minutes. After the dropwise addition, the mixture was stirred at 50 ° C. for 3 hours. After completion of the reaction, the solution was poured into 1 liter of water, and the precipitated resin (Resin G) was collected by filtration. Resin G was dried in a vacuum dryer at 70 ° C. for 60 hours.
実施例７
乾燥窒素気流下、ビス（３，４−ジカルボキシフェニル）エーテル二無水物６．２ｇ（０．０２モル）をＮ−メチル−２−ピロリドン（ＮＭＰ）５０ｇに溶解させた。ここに末端封止剤として３−アミノフェノール１．０９ｇ（０．０１モル）を加えて、４０℃で１時間反応させた。次いで合成例３で得られた水酸基含有ジアミン化合物（ｃ）６．０４ｇ（０．０１モル）、４，４’−ジアミノジフェニルエーテル１ｇ（０．００５モル）をＮＭＰ１０ｇと加えてさらに４０℃で２時間反応させた。その後、Ｎ，Ｎ−ジメチルホルムアミドジメチルアセタール５．９６ｇ（０．０５モル）をＮＭＰ５ｇで希釈した溶液を１０分かけて滴下した。滴下後、５０℃で３時間攪拌した。反応終了後、溶液を水１ｌに投入して、沈殿した樹脂（樹脂Ｈ）をろ過で集めた。樹脂Ｈを７０℃の真空乾燥機で６０時間乾燥した。
Example 7
Under a stream of dry nitrogen, 6.2 g (0.02 mol) of bis (3,4-dicarboxyphenyl) ether dianhydride was dissolved in 50 g of N-methyl-2-pyrrolidone (NMP). To this, 1.09 g (0.01 mol) of 3-aminophenol was added as a terminal blocking agent, and the mixture was reacted at 40 ° C. for 1 hour. Next, 6.04 g (0.01 mol) of the hydroxyl group-containing diamine compound (c) obtained in Synthesis Example 3 and 1 g (0.005 mol) of 4,4′-diaminodiphenyl ether were added to 10 g of NMP, and further added at 40 ° C. for 2 hours. Reacted. Thereafter, a solution obtained by diluting 5.96 g (0.05 mol) of N, N-dimethylformamide dimethyl acetal with 5 g of NMP was added dropwise over 10 minutes. After the dropwise addition, the mixture was stirred at 50 ° C. for 3 hours. After completion of the reaction, the solution was poured into 1 liter of water, and the precipitated resin (Resin H) was collected by filtration. Resin H was dried in a vacuum dryer at 70 ° C. for 60 hours.
実施例８
乾燥窒素気流下、２，２−ビス（３−アミノ−４−ヒドロキシフェニル）ヘキサフルオロプロパン２７．４７ｇ（０．０７５モル）、１，３−ビス（３−アミノプロピル）テトラメチルジシロキサン１．２４ｇ（０．００５モル）、末端封止剤として活性エステル化合物（ｊ）５．６６ｇ（０．０２モル）ピリジン１１．９３ｇ（０．１５１モル）をＮ−メチル−２−ピロリドン（ＮＭＰ）５０ｇに溶解させた。ここに、３，３’，４，４’−ジフェニルエーテルテトラカルボン酸ジｎ−ブチルエステルジクロリド溶液（ｅ）２３９．６ｇ（０．０８モル）を、系内が１０℃以上にならないように滴下した。滴下後、室温で６時間攪拌した。反応終了後、溶液を水２ｌに投入して、沈殿した樹脂（樹脂Ｉ）をろ過で集めた。樹脂Ｉを８０℃の真空乾燥機で２０時間乾燥した。
Example 8
Under a stream of dry nitrogen, 27.47 g (0.075 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 1,3-bis (3-aminopropyl) tetramethyldisiloxane 24 g (0.005 mol), 5.66 g (0.02 mol) of active ester compound (j) as a terminal blocking agent, 11.93 g (0.151 mol) of pyridine, and 50 g of N-methyl-2-pyrrolidone (NMP) Was dissolved. Here, 239.6 g (0.08 mol) of 3,3 ′, 4,4′-diphenylethertetracarboxylic acid di-n-butyl ester dichloride solution (e) was added dropwise so that the temperature inside the system did not become 10 ° C. or more. . After the addition, the mixture was stirred at room temperature for 6 hours. After completion of the reaction, the solution was poured into 2 l of water, and the precipitated resin (resin I) was collected by filtration. Resin I was dried in a vacuum dryer at 80 ° C. for 20 hours.
実施例９
乾燥窒素気流下、３，５−ジアミノ安息香酸７．７５ｇ（０．０５１モル）、４，４’−ジアミノジフェニルエーテル４ｇ（０．０２モル）、末端封止剤として３−アミノフェノール１．９６ｇ（０．０１８モル）、ピリジン１２．６６ｇ（０．１６モル）をＮ−メチル−２−ピロリドン（ＮＭＰ）５０ｇに溶解させた。ここに、合成例１で得られた水酸基含有酸無水物（ａ）４８．０４ｇ（０．０８モル）をＮＭＰ５０ｇとともに加えて４０℃で２時間反応させた。その後Ｎ，Ｎ−ジメチルホルムアミドジメチルアセタール１１．９２ｇ（０．１モル）をＮＭＰ１０ｇで希釈した溶液を１０分かけて滴下した。滴下後、５０℃で３時間撹拌した。反応終了後、溶液を水２ｌに投入して、沈殿した樹脂（樹脂Ｊ）をろ過で集めた。樹脂Ｊを８０℃の真空乾燥機で２０時間乾燥した。
Example 9
Under a stream of dry nitrogen, 7.75 g (0.051 mol) of 3,5-diaminobenzoic acid, 4 g (0.02 mol) of 4,4′-diaminodiphenyl ether, and 1.96 g of 3-aminophenol as a terminal blocking agent ( 0.018 mol) and 12.66 g (0.16 mol) of pyridine were dissolved in 50 g of N-methyl-2-pyrrolidone (NMP). Here, 48.04 g (0.08 mol) of the hydroxyl group-containing acid anhydride (a) obtained in Synthesis Example 1 was added together with 50 g of NMP, and reacted at 40 ° C. for 2 hours. Thereafter, a solution obtained by diluting 11.92 g (0.1 mol) of N, N-dimethylformamide dimethyl acetal with 10 g of NMP was added dropwise over 10 minutes. After the addition, the mixture was stirred at 50 ° C. for 3 hours. After completion of the reaction, the solution was poured into 2 l of water, and the precipitated resin (Resin J) was collected by filtration. Resin J was dried in a vacuum dryer at 80 ° C. for 20 hours.
実施例１０
乾燥窒素気流下、３，５−ジアミノ安息香酸７．７５ｇ（０．０５１モル）、２，２−ビス（３−アミノ−４−ヒドロキシフェニル）ヘキサフルオロプロパン７．３ｇ（０．０２モル）、末端封止剤として３−アミノフェノール１．９６ｇ（０．０１８モル）、ピリジン１２．６６ｇ（０．１６モル）をＮ−メチル−２−ピロリドン（ＮＭＰ）５０ｇに溶解させた。ここに、３，３’，４，４’−ジフェニルエーテルテトラカルボン酸ジｎ−ブチルエステルジクロリド溶液（ｅ）２３９．６ｇ（０．０８モル）を、系内が１０℃以上にならないように滴下した。滴下後、室温で６時間攪拌した。反応終了後、溶液を水２ｌに投入して、沈殿した樹脂（樹脂Ｋ）をろ過で集めた。樹脂Ｋを８０℃の真空乾燥機で２０時間乾
燥した。
Example 10
Under a stream of dry nitrogen, 7.75 g (0.051 mol) of 3,5-diaminobenzoic acid, 7.3 g (0.02 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 1.96 g (0.018 mol) of 3-aminophenol and 12.66 g (0.16 mol) of pyridine were dissolved in 50 g of N-methyl-2-pyrrolidone (NMP) as a terminal blocking agent. Here, 239.6 g (0.08 mol) of 3,3 ′, 4,4′-diphenylethertetracarboxylic acid di-n-butyl ester dichloride solution (e) was added dropwise so that the temperature inside the system did not become 10 ° C. or more. . After the addition, the mixture was stirred at room temperature for 6 hours. After completion of the reaction, the solution was poured into 2 l of water, and the precipitated resin (resin K) was collected by filtration. Resin K was dried in a vacuum dryer at 80 ° C. for 20 hours.
実施例１１
乾燥窒素流下、ビス（３，４−ジカルボキシフェニル）エーテル二無水物１２４ｇ（０．４モル）、２−ヒドロキシエチルメタクリレート５２ｇ（０．４モル）、エタノール１８．４ｇ（０．４モル）、γ−ＢＬ３２０ｇを入れ、氷冷下、かきまぜながらピリジン６４．２ｇを加えた。発熱終了後室温まで放冷し１６時間放置した後、ジシクロヘキシルカルボジイミド１６６ｇをγ−ＢＬ１２０ｇに溶かした溶液を氷冷下、かきまぜながら４０分間で加え、続いて合成例３で得られた水酸基含有ジアミン化合物（ｃ）１８１ｇ（０．３モル）をγ−ＢＬ１５０ｇに懸濁したものを氷冷下、かきまぜながら６０分間で加えた。室温で２時間かきまぜた後、エタノール３０ｇを加えて１時間かきまぜ、Ｎ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ）２５０ｇとテトラヒドロフラン４００ｇを加えた後、沈殿を濾過により除いて得られた反応液を１５リットルのエタノールに加え、生成した沈殿（樹脂Ｌ）を濾別した後、真空乾燥した。
Example 11
Under a stream of dry nitrogen, 124 g (0.4 mol) of bis (3,4-dicarboxyphenyl) ether dianhydride, 52 g (0.4 mol) of 2-hydroxyethyl methacrylate, 18.4 g (0.4 mol) of ethanol, 320 g of γ-BL was added, and 64.2 g of pyridine was added while stirring under ice cooling. After completion of the heat generation, the mixture was allowed to cool to room temperature and left for 16 hours, and then a solution of 166 g of dicyclohexylcarbodiimide dissolved in 120 g of γ-BL was added thereto with stirring under ice-cooling for 40 minutes. (C) A suspension of 181 g (0.3 mol) in 150 g of γ-BL was added thereto under ice cooling with stirring for 60 minutes. After stirring at room temperature for 2 hours, 30 g of ethanol was added and the mixture was stirred for 1 hour, 250 g of N, N-dimethylacetamide (DMAc) and 400 g of tetrahydrofuran were added, and the precipitate was removed by filtration. In addition to ethanol, the resulting precipitate (resin L) was filtered off and dried in vacuum.
参考例２
参考例１で得られたワニスＷ１を、前記の感光性樹脂膜の作製方法にしたがって、ＩＴＯをパターニングしたガラス基板上にスピンコートコート法により塗布した。回転数は１０００ｒｐｍで１０秒間行った。次いでホットプレートを用いて乾燥し、転写痕の有無およびスジ引きの有無について評価した。
Reference Example 2
The varnish W1 obtained in Reference Example 1 was applied to a glass substrate on which ITO was patterned by a spin coat method according to the above-described method for producing a photosensitive resin film. The rotation was performed at 1000 rpm for 10 seconds. Then, drying was performed using a hot plate, and the presence or absence of transfer marks and the presence or absence of streaking were evaluated.
実施例１２
実施例６で得られたワニスＷ７を、前記の感光性樹脂膜の作製方法にしたがって、ＩＴＯをパターニングしたガラス基板上にスリットダイコート法により塗布し、続けてスピンコート法により回転させた。回転数は１２００ｒｐｍで６秒間行った。次いでホットプレートを用いて乾燥し、転写痕の有無およびスジ引きの有無について評価した。
Example 12
The varnish W7 obtained in Example 6 was applied by a slit die coating method on a glass substrate on which ITO was patterned in accordance with the above-described method of forming a photosensitive resin film, and subsequently rotated by a spin coating method. The rotation was performed at 1200 rpm for 6 seconds. Then, drying was performed using a hot plate, and the presence or absence of transfer marks and the presence or absence of streaking were evaluated.
参考例３
参考例１で得られた感光性ポリイミド前駆体樹脂膜を、第一電極のエッジを覆う形状のフォトマスクを介してＵＶ露光した。露光後、２．３８％ＴＭＡＨ水溶液で露光部分のみを溶解させることで現像し、純水でリンスした。つづいて、クリーンオーブン中の窒素雰囲気下で２３０℃で３０分間加熱して、感光性ポリイミド前駆体樹脂膜をキュアし、ポリイミド絶縁層を得た。絶縁層の厚さは約１μｍであった。絶縁層は、第一電極のエッジを覆うように形成され、中央部には幅７０μｍ、長さ２５０μｍの開口部が設けられて第一電極が露出している。絶縁層の断面は、なだらかな順テーパーになっていた。
Reference Example 3
The photosensitive polyimide precursor resin film obtained in Reference Example 1 was exposed to UV through a photomask having a shape covering the edge of the first electrode. After the exposure, development was performed by dissolving only the exposed portion with a 2.38% TMAH aqueous solution, followed by rinsing with pure water. Subsequently, the photosensitive polyimide precursor resin film was cured by heating at 230 ° C. for 30 minutes in a nitrogen atmosphere in a clean oven to obtain a polyimide insulating layer. The thickness of the insulating layer was about 1 μm. The insulating layer is formed so as to cover the edge of the first electrode, and an opening having a width of 70 μm and a length of 250 μm is provided at the center to expose the first electrode. The cross section of the insulating layer had a gentle forward taper.
実施例１３
実施例１で得られた感光性ポリイミド前駆体樹脂膜を用い、キュア条件を２３０℃で６０分にした他は、参考例３と同様にして、単純マトリクス型カラー有機電界発光装置を作製した。本表示装置を線順次駆動したところ、輝度ムラも認められず良好な表示特性を得ることができた。
Example 13
A simple matrix color organic electroluminescent device was produced in the same manner as in Reference Example 3 , except that the photosensitive polyimide precursor resin film obtained in Example 1 was used and the curing conditions were changed to 230 ° C. for 60 minutes. When this display device was driven line-sequentially, good display characteristics could be obtained without any uneven luminance.
実施例１４
実施例２で得られた感光性ポリイミド前駆体樹脂膜を用い、キュア条件を２３０℃で３０分にした他は、参考例３と同様にして、単純マトリクス型カラー有機電界発光装置を作製した。本表示装置を線順次駆動したところ、輝度ムラも認められず良好な表示特性を得ることができた。
Example 14
A simple matrix color organic electroluminescent device was produced in the same manner as in Reference Example 3 , except that the photosensitive polyimide precursor resin film obtained in Example 2 was used and the curing conditions were changed to 230 ° C. for 30 minutes. When this display device was driven line-sequentially, good display characteristics could be obtained without any uneven luminance.
実施例１５
実施例３で得られた感光性ポリイミド前駆体樹脂膜を用い、キュア条件を２５０℃で３０分にした他は、参考例３と同様にして、単純マトリクス型カラー有機電界発光装置を作製した。本表示装置を線順次駆動したところ、輝度ムラも認められず良好な表示特性を得ることができた。
Example 15
A simple matrix color organic electroluminescent device was produced in the same manner as in Reference Example 3 , except that the photosensitive polyimide precursor resin film obtained in Example 3 was used and the curing conditions were changed to 250 ° C. for 30 minutes. When this display device was driven line-sequentially, good display characteristics could be obtained without any uneven luminance.
実施例１６
実施例４で得られた感光性ポリイミド前駆体樹脂膜を用い、キュア条件を２３０℃で３０分にした他は、参考例３と同様にして、単純マトリクス型カラー有機電界発光装置を作製した。本表示装置を線順次駆動したところ、輝度ムラも認められず良好な表示特性を得ることができた。
Example 16
A simple matrix color organic electroluminescent device was produced in the same manner as in Reference Example 3 , except that the photosensitive polyimide precursor resin film obtained in Example 4 was used and the curing conditions were changed to 230 ° C. for 30 minutes. When this display device was driven line-sequentially, good display characteristics could be obtained without any uneven luminance.
実施例１７
実施例５で得られた感光性ポリイミド前駆体樹脂膜を用い、キュア条件を２００℃で６０分にした他は、参考例３と同様にして、単純マトリクス型カラー有機電界発光装置を作製した。本表示装置を線順次駆動したところ、輝度ムラも認められず良好な表示特性を得ることができた。
Example 17
A simple matrix type color organic electroluminescent device was produced in the same manner as in Reference Example 3 , except that the photosensitive polyimide precursor resin film obtained in Example 5 was used and the curing conditions were set at 200 ° C. for 60 minutes. When this display device was driven line-sequentially, good display characteristics could be obtained without any uneven luminance.
実施例１８
実施例６で得られた感光性ポリイミド前駆体樹脂膜を用い、キュア条件を３５０℃で３０分にした他は、参考例３と同様にして、単純マトリクス型カラー有機電界発光装置を作製した。本表示装置を線順次駆動したところ、輝度ムラも認められず良好な表示特性を得ることができた。
Example 18
A simple matrix color organic electroluminescent device was produced in the same manner as in Reference Example 3 , except that the photosensitive polyimide precursor resin film obtained in Example 6 was used and the curing conditions were changed to 350 ° C. for 30 minutes. When this display device was driven line-sequentially, good display characteristics could be obtained without any uneven luminance.
実施例１９
実施例７で得られた感光性ポリイミド前駆体樹脂膜を用い、キュア条件を２００℃で３０分にした他は、参考例３と同様にして、単純マトリクス型カラー有機電界発光装置を作製した。本表示装置を線順次駆動したところ、輝度ムラも認められず良好な表示特性を得ることができた。
Example 19
A simple matrix color organic electroluminescent device was produced in the same manner as in Reference Example 3 , except that the photosensitive polyimide precursor resin film obtained in Example 7 was used and the curing conditions were set at 200 ° C. for 30 minutes. When this display device was driven line-sequentially, good display characteristics could be obtained without any uneven luminance.
実施例２０
実施例８で得られた感光性ポリイミド前駆体樹脂膜を用い、キュア条件を３２０℃で３０分にした他は、参考例３と同様にして、単純マトリクス型カラー有機電界発光装置を作製した。本表示装置を線順次駆動したところ、輝度ムラも認められず良好な表示特性を得ることができた。
Example 20
A simple matrix type color organic electroluminescent device was produced in the same manner as in Reference Example 3 , except that the photosensitive polyimide precursor resin film obtained in Example 8 was used and the curing conditions were set at 320 ° C. for 30 minutes. When this display device was driven line-sequentially, good display characteristics could be obtained without any uneven luminance.
比較例１
ワニスを作成する際の溶媒をプロピレングリコールモノメチルエーテル（沸点１１８−１１９℃）１５ｇとγ−ブチロラクトン（沸点２０４℃）３５ｇの混合溶液に変更した他は、参考例１と同様に行い、ＩＴＯをパターニングしたガラス基板上に感光性ポリイミド前駆体樹脂膜を形成し、転写痕の有無およびスジ引きの有無について評価した。
Comparative Example 1
ITO was patterned in the same manner as in Reference Example 1 except that the solvent used for preparing the varnish was changed to a mixed solution of 15 g of propylene glycol monomethyl ether (boiling point 118-119 ° C) and 35 g of γ-butyrolactone (boiling point 204 ° C). A photosensitive polyimide precursor resin film was formed on the glass substrate thus prepared, and the presence or absence of transfer traces and the presence or absence of streaks were evaluated.
比較例２
ワニスを作成する際の溶媒をプロピレングリコールモノメチルエーテル（沸点１１８−１１９℃）１０ｇとγ−ブチロラクトン（沸点２０４℃）４０ｇの混合溶液に変更した他は、実施例１と同様に行い、ＩＴＯをパターニングしたガラス基板上に感光性ポリイミド前駆体樹脂膜を形成し、転写痕の有無およびスジ引きの有無について評価した。
Comparative Example 2
ITO was patterned in the same manner as in Example 1 , except that the solvent used for preparing the varnish was changed to a mixed solution of 10 g of propylene glycol monomethyl ether (boiling point 118-119 ° C) and 40 g of γ-butyrolactone (boiling point 204 ° C). A photosensitive polyimide precursor resin film was formed on the glass substrate thus prepared, and the presence or absence of transfer traces and the presence or absence of streaks were evaluated.
比較例３
ワニスを作成する際の溶媒をエチレングリコールモノエチルエーテル（沸点１３５℃）２０ｇとＮＭＰ（沸点２０２℃）３０ｇの混合溶液に変更した他は、実施例２と同様に行い、ＩＴＯをパターニングしたガラス基板上に感光性ポリイミド前駆体樹脂膜を形成し、転写痕の有無およびスジ引きの有無について評価した。
Comparative Example 3
Glass substrate on which ITO was patterned in the same manner as in Example 2 except that the solvent used for preparing the varnish was changed to a mixed solution of 20 g of ethylene glycol monoethyl ether (boiling point: 135 ° C.) and 30 g of NMP (boiling point: 202 ° C.) A photosensitive polyimide precursor resin film was formed thereon, and the presence or absence of transfer marks and the presence or absence of streaking were evaluated.
比較例４
ワニスを作成する際の溶媒をブチルアセテート（沸点１２６℃）１５ｇとγ−ブチロラクトン（沸点２０４℃）３５ｇの混合溶媒に変更した他は、実施例４と同様に行い、ＩＴＯをパターニングしたガラス基板上に感光性ポリイミド前駆体樹脂膜を形成し、転写痕の有無およびスジ引きの有無について評価した。
Comparative Example 4
A varnish was prepared in the same manner as in Example 4 except that the solvent used was a mixed solvent of 15 g of butyl acetate (boiling point: 126 ° C.) and 35 g of γ-butyrolactone (boiling point: 204 ° C.). Then, a photosensitive polyimide precursor resin film was formed thereon, and the presence or absence of transfer traces and the presence or absence of streaking were evaluated.
比較例５
ワニスを作成する際の溶媒をプロピレングリコールモノメチルエーテル（沸点１１８−１１９℃）１５ｇとγ−ブチロラクトン３０ｇと乳酸エチル（沸点１５４℃）５ｇの混合溶媒に変更した他は、実施例５と同様に行い、ＩＴＯをパターニングしたガラス基板上に感光性ポリイミド前駆体樹脂膜を形成し、転写痕の有無およびスジ引きの有無について評価した。
Comparative Example 5
A varnish was prepared in the same manner as in Example 5 except that the solvent used was 15 g of propylene glycol monomethyl ether (boiling point 118-119 ° C), 30 g of γ-butyrolactone, and 5 g of ethyl lactate (boiling point 154 ° C). Then, a photosensitive polyimide precursor resin film was formed on a glass substrate on which ITO was patterned, and the presence or absence of transfer traces and the presence or absence of streaking were evaluated.
比較例６
ワニスを作成する際の溶媒を乳酸ブチル（沸点１８５−１８７℃）１７ｇとγ−ブチロラクトン３３ｇの混合溶媒に変更した他は、実施例６と同様に行い、ＩＴＯをパターニングしたガラス基板上に感光性ポリイミド前駆体樹脂膜を形成し、転写痕の有無およびスジ引きの有無について評価した。
Comparative Example 6
A varnish was prepared in the same manner as in Example 6 , except that the solvent used was 17 g of butyl lactate (boiling point: 185 to 187 ° C.) and 33 g of γ-butyrolactone. A polyimide precursor resin film was formed, and the presence or absence of transfer traces and the presence or absence of streaks were evaluated.
比較例７
ワニスを作成する際の溶媒をプロピレングリコールモノメチルエーテル（沸点１１８−１１９℃）５ｇと乳酸エチル（沸点１５４℃）４５ｇの混合溶媒に変更した他は、実施例７と同様に行い、ＩＴＯをパターニングしたガラス基板上に感光性ポリイミド前駆体樹脂膜を形成し、転写痕の有無およびスジ引きの有無について評価した。
Comparative Example 7
ITO was patterned in the same manner as in Example 7 , except that the solvent used when preparing the varnish was changed to a mixed solvent of 5 g of propylene glycol monomethyl ether (boiling point 118-119 ° C) and 45 g of ethyl lactate (boiling point 154 ° C). A photosensitive polyimide precursor resin film was formed on a glass substrate, and the presence or absence of transfer marks and the presence or absence of streaks were evaluated.
比較例８
ワニスを作成する際の溶媒を乳酸エチル（沸点１５４℃）１０ｇとＮＭＰ（沸点２０２℃）４０ｇの混合溶媒に変更した他は、実施例８と同様に行い、ＩＴＯをパターニングしたガラス基板上に感光性ポリイミド前駆体樹脂膜を形成し、転写痕の有無およびスジ引きの有無について評価した。
Comparative Example 8
A varnish was prepared in the same manner as in Example 8 , except that the solvent used was 10 g of ethyl lactate (boiling point: 154 ° C.) and 40 g of NMP (boiling point: 202 ° C.). A conductive polyimide precursor resin film was formed, and the presence or absence of transfer traces and the presence or absence of streaking were evaluated.
比較例９
ワニスを作成する際の溶媒をγ−ブチロラクトン（沸点２０４℃）５０ｇに変更した他は、実施例９と同様に行い、ＩＴＯをパターニングしたガラス基板上に感光性ポリイミド前駆体樹脂膜を形成し、転写痕の有無およびスジ引きの有無について評価した。
Comparative Example 9
Except that the solvent was changed when creating varnish γ- butyrolactone (boiling point 204 ° C.) 50 g are Examples 9 and performed in the same manner, ITO and the glass substrate to form a photosensitive polyimide precursor resin film is patterned, The presence or absence of transfer marks and the presence or absence of streaking were evaluated.
比較例１０
ワニスを作成する際の溶媒をプロピレングリコールモノメチルエーテル（沸点１１８−１１９℃）３０ｇとエチレングリコールジメチルエーテル（沸点８５℃）２０ｇの混合溶液に変更した他は、参考例１と同様に行い、ＩＴＯをパターニングしたガラス基板上に感光性ポリイミド前駆体樹脂膜を形成し、転写痕の有無およびスジ引きの有無について評価した。
Comparative Example 10
Performed in the same manner as in Reference Example 1 , except that the solvent used for preparing the varnish was changed to a mixed solution of 30 g of propylene glycol monomethyl ether (boiling point: 118 to 119 ° C.) and 20 g of ethylene glycol dimethyl ether (boiling point: 85 ° C.). A photosensitive polyimide precursor resin film was formed on the glass substrate thus prepared, and the presence or absence of transfer traces and the presence or absence of streaks were evaluated.
比較例１１
ワニスを作成する際の溶媒をメチルエチルケトン（沸点８０℃）３５ｇとγ−ブチロラクトン（沸点２０４℃）１５ｇの混合溶媒に変更した他は、実施例４と同様に行い、ＩＴＯをパターニングしたガラス基板上に感光性ポリイミド前駆体樹脂膜を形成し、転写痕の有無およびスジ引きの有無について評価した。
Comparative Example 11
A varnish was prepared in the same manner as in Example 4 , except that the solvent used was 35 g of methyl ethyl ketone (boiling point: 80 ° C.) and 15 g of γ-butyrolactone (boiling point: 204 ° C.). A photosensitive polyimide precursor resin film was formed, and the presence or absence of transfer traces and the presence or absence of streaking were evaluated.
樹脂Ａ〜Ｌのモノマー組成については表１〜４に、実施例１〜１２、参考例１〜２、比較例１〜１１の評価結果については表５〜６に示した。表２、４において、複数の成分を用いているものについては、ｐ、ｑ、ｒ、ｓを平均値で示した。 Tables 1 to 4 show the monomer compositions of the resins A to L, and Tables 5 and 6 show the evaluation results of Examples 1 to 12, Reference Examples 1 and 2 , and Comparative Examples 1 to 11. In Tables 2 and 4, p, q, r, and s are shown as average values for those using a plurality of components.
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| EP1491952B1 (en) * | 2003-06-23 | 2015-10-07 | Sumitomo Bakelite Co., Ltd. | Positive-working photosensitive resin composition, method for producing pattern-formed resin film, semiconductor device, display device, and method for producing the semiconductor device and the display device |
| JP4556616B2 (en) * | 2003-10-28 | 2010-10-06 | 住友ベークライト株式会社 | Positive photosensitive resin composition, semiconductor device and display element using the positive photosensitive resin composition, and method for manufacturing semiconductor device and display element |
| JP4494061B2 (en) * | 2004-03-30 | 2010-06-30 | 東京応化工業株式会社 | Positive resist composition |
| JP2005309032A (en) * | 2004-04-21 | 2005-11-04 | Toray Ind Inc | Positive photosensitive resin composition |
| JP4698356B2 (en) * | 2005-09-20 | 2011-06-08 | 旭化成イーマテリアルズ株式会社 | Photosensitive resin composition |
| CN101495919B (en) * | 2006-08-15 | 2015-05-06 | 旭化成电子材料株式会社 | Positive photosensitive resin composition, method for preparing cured relief pattern, semiconductor device |
| JP4929982B2 (en) * | 2006-10-30 | 2012-05-09 | 住友ベークライト株式会社 | Photosensitive resin composition, insulating film, protective film and electronic device |
| JP4400695B2 (en) * | 2007-02-19 | 2010-01-20 | 住友ベークライト株式会社 | Photosensitive resin composition, cured film, protective film, insulating film, and semiconductor device and display device using the same |
| US20100193971A1 (en) * | 2007-07-26 | 2010-08-05 | Toshio Banba | Positive photosensitive resin composition for spray coating, method for forming cured film using the same, cured film, and semiconductor device |
| WO2009064026A1 (en) * | 2007-11-16 | 2009-05-22 | Sumitomo Chemical Company, Limited | Coating liquid used in coating method for discharging coating liquid through slit-shaped discharge outlet |
| JP5292799B2 (en) * | 2007-12-19 | 2013-09-18 | 凸版印刷株式会社 | Support pin for substrate |
| JP5434027B2 (en) * | 2008-09-24 | 2014-03-05 | 住友化学株式会社 | Organic photoelectric conversion element |
| WO2010047264A1 (en) * | 2008-10-20 | 2010-04-29 | 住友ベークライト株式会社 | Positive photosensitive resin composition for spray coating and method for producing through electrode using same |
| CN102549497B (en) * | 2009-09-10 | 2013-07-31 | 东丽株式会社 | Photosensitive resin composition and method for producing photosensitive resin film |
| KR101333704B1 (en) * | 2009-12-29 | 2013-11-27 | 제일모직주식회사 | Positive type photosensitive resin composition |
| KR101728820B1 (en) | 2013-12-12 | 2017-04-20 | 제일모직 주식회사 | Positive photosensitive resin composition, photosensitive resin film prepared by using the same, and display device |
| US10199548B2 (en) * | 2015-03-27 | 2019-02-05 | Toray Industries, Inc. | Photosensitive resin composition for thin film transistors, cured film, thin film transistor, liquid crystal display device or organic electroluminescent display device, method for producing cured film, method for manufacturing thin film transistor, and method for manufacturing liquid crystal display device or organic electroluminescent display device |
| JP7487518B2 (en) | 2020-03-27 | 2024-05-21 | 住友ベークライト株式会社 | Photosensitive resin composition, cured film, panel level package including the cured film, and method for manufacturing the same |
| JP7443970B2 (en) | 2020-07-22 | 2024-03-06 | Ｈｄマイクロシステムズ株式会社 | Photosensitive resin composition, cured product, method for producing patterned cured product, and electronic components |
| CN111825348B (en) * | 2020-08-13 | 2021-09-17 | 乐清市川嘉电气科技有限公司 | Porous electrochromic glass and preparation method thereof |
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