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】
(式中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。)
【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】
(式中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、R5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。)
【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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(Wherein 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, and R 3 and R 4 are the same. And a hydrogen atom or an organic group having 1 to 20 carbon atoms, n is in the range of 5 to 100,000, p and q are each in the range of 0 to 4, r and s are each (The range is from 0 to 2. p + q> 0.)
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; .
Embedded image
(Wherein 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, and R 3 and R 4 are the same. A hydrogen atom or an organic group having 1 to 20 carbon atoms, R 5 is a divalent organic group, and X and Y are a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a thiol group, an unsaturated And represents an organic group having at least one substituent selected from a hydrocarbon group having 1 to 10 carbon atoms containing at least one hydrocarbon group, a nitro group, a methylol group, an ester group, and a hydroxyalkynyl group. Is in the range from 5 to 100,000, m is in the range from 0 to 10, p and q are each in the range from 0 to 4, r and s are each in the range from 0 to 2. p + q> 0. .)
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 |
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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 |
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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 |
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