JP4434338B2 - Photosensitive polyimide - Google Patents
Photosensitive polyimide Download PDFInfo
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- JP4434338B2 JP4434338B2 JP23017098A JP23017098A JP4434338B2 JP 4434338 B2 JP4434338 B2 JP 4434338B2 JP 23017098 A JP23017098 A JP 23017098A JP 23017098 A JP23017098 A JP 23017098A JP 4434338 B2 JP4434338 B2 JP 4434338B2
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- photosensitive polyimide
- tetracarboxylic dianhydride
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- 0 CC1C(C*(N(CC=C)O)N(C(C2C)C2*2C)N2O)C1C Chemical compound CC1C(C*(N(CC=C)O)N(C(C2C)C2*2C)N2O)C1C 0.000 description 2
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- Macromonomer-Based Addition Polymer (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、感光性ポリイミドに関する。更に詳しくは、汎用低沸点有機溶媒およびアルカリ水溶液に可溶性の感光性ポリイミドに関する。
【０００２】
【従来の技術】
ポリイミド樹脂は、それ自身では有機溶媒に不溶性なので、一旦有機溶媒可溶性のポリアミック酸とした後、ポリイミド化させるという方法がとられている。ポリイミド樹脂自身が有機溶媒可溶性のものもあることはあり、例えば特開昭57-131227号公報に記載されるポリイミド樹脂、同59-145216号公報に記載されるポリアミドイミド樹脂は、有機溶媒可溶性でかつ感光性を有するとされている。しかしながら、ここでいう有機溶媒とは、ジメチルホルムアミドを始めとする非プロトン性極性溶媒であって、アセトン、ベンゼン、シクロヘキサノール等は逆に当該樹脂の析出に用いられており、即ちこれらの有機溶媒には不溶性である。
【０００３】
【発明が解決しようとする課題】
本発明の目的は、メチルエチルケトンによって代表される汎用の低沸点有機溶媒に可溶性であり、かつそれ自身感光性を有し、アルカリ水溶液で現像可能なネガ型感光性ポリイミドを提供することにある。
【０００４】
【課題を解決するための手段】
かかる本発明の目的は、ジアミノポリシロキサン20〜60モル％、ヒドロキシル基含有ジアミンまたはカルボキシル基含有ジアミン60〜20モル％および1,4-ビス[2-(3-アミノベンゾイル)エテニル]ベンゼン5〜40モル％よりなる3種類のジアミン化合物とテトラカルボン酸二無水物との共重合体よりなる炭酸ナトリウム水溶液可溶性感光性ポリイミドによって達成される。
【０００５】
【発明の実施の形態】
テトラカルボン酸二無水物と反応する３種類のジアミン化合物の一つの成分であるジアミノポリシロキサンとしては、次のような一般式で表わされる化合物が用いられる。
R1〜R4：炭素数1〜5の低級アルキル基、フェニル基
n：0〜30の整数、好ましくは4〜12の整数
【０００６】
この化合物としては、RおよびR1〜R4が次のような置換基の組合せである化合物が例示される。
実際には、市販品、例えば東芝シリコーン製品TSL9386、TSL9346、TSL9306、東レ・ダウコーニング製品BY16-853U、信越化学製品X-22-161AS、日本ユニカー製品F2-053-01等を用いることができる。
【０００８】
また、2番目のジアミン化合物であるヒドロキシル基含有ジアミンまたはカルボキシル基含有ジアミンとしては、例えば4,4′-ジアミノ-4″-ヒドロキシトリフェニルメタン、ビス(4-アミノ-3-ヒドロキシフェニル)メタン、2,2-ビス(3-アミノ-4-ヒドロキシフェニル)プロパン、3,5-ジアミノ安息香酸等が用いられる。
【０００９】
更に、3番目のジアミン化合物としては、1,4-ビス[2-(3-アミノベンゾイル)エテニル]ベンゼンが用いられ、この化合物は得られる共重合体に感光性を付与する。
これら3種類のジアミン化合物の内、ジアミノポリシロキサンは約20〜60モル%、好ましくは約30〜50モル%の割合で、ヒドロキシル基含有ジアミンまたはカルボキシル基含有ジアミンは約20〜60モル%、好ましくは約30〜50モル%の割合で、また1,4-ビス[2-(3-アミノベンゾイル)エテニル]ベンゼンは約5〜40モル%、好ましくは約10〜30モル%の割合でそれぞれ用いられる。ジアミノポリシロキサンの割合がこれより少ないと、フィルムが形成されず、一方これより多く用いられると、アルカリ水溶液による現像ができなくなる。ヒドロキシル基含有ジアミンまたはカルボキシル基含有ジアミンの割合がこれより少ないと、未露光部がアルカリ水溶液に溶解できなくなり、一方これより多く用いられると、露光部でもアルカリ水溶液に溶解するものの、露光部と未露光部との溶解速度の差が小さくなる。また、1,4-ビス[2-(3-アミノベンゾイル)エテニル]ベンゼンの割合がこれより少ないと、十分なる感光性が得られず、一方これより多く用いられると、透明性に劣るようになる。
【００１１】
これらのジアミン化合物混合物と反応するテトラカルボン酸二無水物としては、3,3´,4,4´-ベンゾフェノンテトラカルボン酸二無水物、3,3´,4,4´-ジフェニルスルホンテトラカルボン酸二無水物、4,4´-オキシジフタル酸二無水物、4,4´-ビフタル酸二無水物、2,2´-ジフタル酸二無水物プロパン、ジフタル酸二無水物メタン、ピロメリット酸二無水物、2,2´-(ヘキサフルオロイソプロピリデン)ジフタル酸二無水物等の芳香族テトラカルボン酸二無水物または5-(2,5-ジオキソテトラヒドロフリル)-3-メチル-3-シクロヘキセン-1,2-ジカルボン酸無水物
【００１２】
ジアミン化合物混合物とテトラカルボン酸二無水物との反応は、好ましくはジメチルホルムアミド、ジメチルアセトアミド、N-メチルピロリドン等の非プロトン性極性溶媒中で行われるが、この他にクレゾール、ピリジン等の極性溶媒中でも行われる。実際には、ジアミン化合物混合物の極性溶媒溶液中に、約0〜10℃でテトラカルボン酸二無水物を滴下し、その後約50〜200℃、好ましくは約100〜150℃で約2〜8時間反応させることによって行われる。
【００１３】
この反応生成物は、ポリイミド前駆体であるポリアミック酸であるので、それをポリイミド化するための脱水反応が行われる。脱水反応は、必要に応じて更に極性有機溶媒を加えてその濃度を約10〜20重量%に調整した後、好ましくは無水酢酸等の脱水剤を用い、約100〜180℃で約2〜6時間、好ましくは約2〜4時間反応させることによって行われる。
【００１４】
ポリイミド化反応の生成物であるシロキサンポリイミドは、例えばヒドロキシル基含有ジアミンが4,4′-ジアミノ-4″-ヒドロキシトリフェニルメタンである場合、次のような一般式で表わされる繰返し単位(a)、(b)および(c)を有するブロック共重合体とも考えられ、それの重量平均分子量Mw(GPCによる測定；ポリスチレン換算)は約10000〜100000、好ましくは約15000〜30000程度である。
【００１５】
このようにして得られる共重合体は、アセトン、メチルエチルケトン、メチルイソブチルケトン、テトラヒドロフラン、シクロヘキサノン等の低沸点有機溶媒に可溶性であるので、これらの有機溶媒中に約20〜40重量%、好ましくは約30〜35重量%の濃度で溶解させた溶液として用いられる。このような溶液を、石英ガラス板、銅等の耐アルカリ性基質上に滴下し、スピンコーティングを行った後、約60〜80℃で約5〜10分間程度プリベークすることにより、溶媒を除去する。
【００１６】
得られた感光性ポリイミド塗布基質上に必要なマスクを載せ、紫外線を約200〜450mJ/cm2、好ましくは約300〜450mJ/cm2の露光量で照射し、その後約120〜140℃で約5〜10分間程度のポスト暴露ベークを行ない、炭酸ナトリウム、テトラメチルアンモニウムハイドロオキサイド等のアルカリ性物質の水溶液で現像すると、そこに鮮明なネガ型パターンが得られる。ここで用いられる現像液の濃度は、約1〜5重量%、好ましくは約1〜3重量%であり、その現像時間は約1分間以内であることが好ましい。
【００１７】
【発明の効果】
本発明により、汎用の低沸点有機溶媒に対し可溶性であり、かつそれ自身感光性を有し、炭酸ナトリウム水溶液等で現像可能なネガ型感光性ポリイミドが提供される。
【００１８】
【実施例】
次に、実施例について本発明を説明する。
【００１９】
実施例１Ａ
容量300mlのセパラブルフラスコに、ジアミノポリシロキサン(BY 16-853U)7.04g(8ミリモル)、4,4′-ジアミノ-4″-ヒドロキシトリフェニルメタン[DHTM]2.90g(10ミリモル)、1,4-ビス[2-(3-アミノベンゾイル)エテニル]ベンゼン[BABEB]0.736g(2ミリモル)およびN-メチル-2-ピロリドン30gを仕込み、その溶液を氷冷した。そこに、5-(2,5-ジオキソテトラヒドロフリル)-3-メチル-3-シクロヘキセン-1,2-ジカルボン酸無水物5.28g(20ミリモル)を添加した後、120℃に昇温し、4時間撹拌しながら反応を行った。反応終了後、反応混合物を室温迄放冷した後、N-メチル-2-ピロリドン30gを追加し、ポリアミック酸濃度を希釈した。
【００２０】
更に、ピリジン5gおよび無水酢酸10gを添加し、50℃で3時間加熱してポリイミド化反応を行ない、反応終了後反応混合物を水中に再沈させることによって、感光性ポリイミドを得た。
【００２１】
実施例２Ａ
実施例1Ａにおいて、DHTMの代りに2,2-ビス(3-アミノ-4-ヒドロキシ)プロパン2.112g(8ミリモル)を用い、またBABEB量を1.472g(4ミリモル)に変更した。
【００２２】
実施例３Ａ
実施例1Ａにおいて、DHTMの代りに3,5-ジアミノ安息香酸1.216g(8ミリモル)を用い、またBABEB量を1.472g(4ミリモル)に変更した。
【００２３】
実施例１Ｂ
実施例1Ａで得られた感光性ポリイミドの35重量%メチルエチルケトン溶液約2gを、石英ガラス板(7×7cm)上に滴下し、750rpm、10秒間のスピンコーティングを行った。その後、80℃で10分間プリベークして溶媒を除去した。この感光性ポリイミド塗布石英ガラス上にマスク(日立化成製品PHOTEC)を載せ、350〜450nmに主たる吸収を有するUV光源(ウシオ電気製)を、300mJ/cm2の露光量で照射した。露光後、120℃で10分間のポスト暴露ベークを行ない、3重量%炭酸ナトリウム水溶液を現像液として、40℃で約60秒間現像し、蒸留水で洗浄して、鮮明なネガ型パターンを得た。
【００２４】
実施例２Ｂ
実施例1Ｂにおいて、実施例1Ａで得られた感光性ポリイミドの代りに、実施例2Ａで得られた感光性ポリイミドが用いられ、また露光量が475mJ/cm2に変更された。同様に、鮮明なネガ型パターンが得られた。
【００２５】
実施例３Ｂ
実施例1Ｂにおいて、実施例1Ａで得られた感光性ポリイミドの代りに、実施例3Ａで得られた感光性ポリイミドが用いられた。同様に、鮮明なネガ型パターンが得られた。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a photosensitive polyimide. More specifically, the present invention relates to a photosensitive polyimide soluble in a general-purpose low-boiling organic solvent and an aqueous alkali solution.
[0002]
[Prior art]
Since the polyimide resin itself is insoluble in an organic solvent, a method is used in which a polyamic acid that is soluble in an organic solvent is first converted into a polyimide. In some cases, the polyimide resin itself is soluble in an organic solvent. For example, the polyimide resin described in JP-A-57-131227 and the polyamideimide resin described in JP-A-59-145216 are soluble in an organic solvent. And it is supposed to have photosensitivity. However, the organic solvent here is an aprotic polar solvent such as dimethylformamide, and acetone, benzene, cyclohexanol, etc. are used for precipitation of the resin, that is, these organic solvents. Is insoluble.
[0003]
[Problems to be solved by the invention]
An object of the present invention is to provide a negative photosensitive polyimide that is soluble in a general-purpose low-boiling organic solvent typified by methyl ethyl ketone, has its own photosensitivity, and can be developed with an alkaline aqueous solution.
[0004]
[Means for Solving the Problems]
Such an object of the present invention is to provide 20 to 60 mol% of diaminopolysiloxane, 60 to 20 mol% of a hydroxyl group-containing diamine or carboxyl group-containing diamine and 1,4-bis [2- (3-aminobenzoyl) ethenyl] benzene 5 to This is achieved by an aqueous sodium carbonate soluble photosensitive polyimide comprising a copolymer of three kinds of diamine compounds comprising 40 mol% and tetracarboxylic dianhydride.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
As diaminopolysiloxane which is one component of three kinds of diamine compounds which react with tetracarboxylic dianhydride, compounds represented by the following general formula are used.
R 1 to R 4 : lower alkyl group having 1 to 5 carbon atoms, phenyl group
n: an integer from 0 to 30, preferably an integer from 4 to 12
Examples of this compound include compounds in which R and R 1 to R 4 are combinations of the following substituents.
Actually, commercially available products such as TOSHIBA silicone products TSL9386, TSL9346, TSL9306, Toray Dow Corning products BY16-853U, Shin-Etsu Chemical products X-22-161AS, Nippon Unicar products F2-053-01, etc. can be used.
[0008]
Examples of the hydroxyl group-containing diamine or carboxyl group-containing diamine as the second diamine compound include 4,4′-diamino-4 ″ -hydroxytriphenylmethane, bis (4-amino-3-hydroxyphenyl) methane, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 3,5-diaminobenzoic acid and the like are used.
[0009]
Further, 1,4-bis [2- (3-aminobenzoyl) ethenyl] benzene is used as the third diamine compound, and this compound imparts photosensitivity to the resulting copolymer.
Of these three types of diamine compounds, diaminopolysiloxane is about 20 to 60 mol%, preferably about 30 to 50 mol%, and hydroxyl group-containing diamine or carboxyl group-containing diamine is about 20 to 60 mol%, preferably Is about 30-50 mol%, and 1,4-bis [2- (3-aminobenzoyl) ethenyl] benzene is about 5-40 mol%, preferably about 10-30 mol%. It is done. When the proportion of diaminopolysiloxane is less than this, a film is not formed. On the other hand, when it is used more than this, development with an alkaline aqueous solution becomes impossible. If the proportion of the hydroxyl group-containing diamine or carboxyl group-containing diamine is less than this, the unexposed area cannot be dissolved in the alkaline aqueous solution.On the other hand, if it is used more than this, the exposed area also dissolves in the alkaline aqueous solution. The difference in dissolution rate from the exposed part is reduced. Also, if the proportion of 1,4-bis [2- (3-aminobenzoyl) ethenyl] benzene is less than this, sufficient photosensitivity cannot be obtained, while if it is used more than this, transparency is inferior. Become.
[0011]
Tetracarboxylic dianhydrides that react with these diamine compound mixtures include 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic acid Dianhydride, 4,4'-oxydiphthalic dianhydride, 4,4'-biphthalic dianhydride, 2,2'-diphthalic dianhydride propane, diphthalic dianhydride methane, pyromellitic dianhydride , Aromatic tetracarboxylic dianhydrides such as 2,2 '-(hexafluoroisopropylidene) diphthalic dianhydride or 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene- 1,2 dicarboxylic acid anhydride
[0012]
The reaction between the diamine compound mixture and tetracarboxylic dianhydride is preferably carried out in an aprotic polar solvent such as dimethylformamide, dimethylacetamide or N-methylpyrrolidone, but in addition to this, a polar solvent such as cresol or pyridine. Among other things is done. In practice, tetracarboxylic dianhydride is dropped into a polar solvent solution of the diamine compound mixture at about 0 to 10 ° C., and then about 50 to 200 ° C., preferably about 100 to 150 ° C. for about 2 to 8 hours. This is done by reacting.
[0013]
Since this reaction product is a polyamic acid which is a polyimide precursor, a dehydration reaction is performed to polyimidize it. In the dehydration reaction, a polar organic solvent is further added as necessary to adjust the concentration to about 10 to 20% by weight, and then a dehydrating agent such as acetic anhydride is preferably used, and about 2 to 6 at about 100 to 180 ° C. It is carried out by reacting for a time, preferably about 2 to 4 hours.
[0014]
For example, when the hydroxyl group-containing diamine is 4,4′-diamino-4 ″ -hydroxytriphenylmethane, the siloxane polyimide that is a product of the polyimidation reaction is a repeating unit (a) represented by the following general formula: , (B) and (c) are also considered, and the weight average molecular weight Mw (measured by GPC; converted to polystyrene) is about 10,000 to 100,000, preferably about 15,000 to 30,000.
The copolymer thus obtained is soluble in low boiling organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, cyclohexanone and the like, and therefore, about 20 to 40% by weight in these organic solvents, preferably about Used as a solution dissolved at a concentration of 30 to 35% by weight. Such a solution is dropped on an alkali-resistant substrate such as quartz glass plate and copper, spin-coated, and then pre-baked at about 60 to 80 ° C. for about 5 to 10 minutes to remove the solvent.
[0016]
A necessary mask is placed on the obtained photosensitive polyimide coating substrate, and ultraviolet rays are irradiated at an exposure dose of about 200 to 450 mJ / cm 2 , preferably about 300 to 450 mJ / cm 2 , and then about 120 to 140 ° C. When post-exposure baking is performed for about 5 to 10 minutes and development is performed with an aqueous solution of an alkaline substance such as sodium carbonate or tetramethylammonium hydroxide, a clear negative pattern is obtained there. The concentration of the developer used here is about 1 to 5% by weight, preferably about 1 to 3% by weight, and the development time is preferably within about 1 minute.
[0017]
【The invention's effect】
According to the present invention, there is provided a negative photosensitive polyimide that is soluble in a general-purpose low-boiling-point organic solvent, has its own photosensitivity, and can be developed with an aqueous sodium carbonate solution or the like .
[0018]
【Example】
Next, the present invention will be described with reference to examples.
[0019]
Example 1A
The separable flask 300 ml, diamino polysiloxane (BY 16-853U) 7.04g (8 mmol), 4,4'-diamino-4 "- hydroxy triphenylmethane [DHTM] 2.90g (10 mmol), 1, 4-Bis [2- (3-aminobenzoyl) ethenyl] benzene [BABEB] 0.736 g (2 mmol) and N-methyl-2-pyrrolidone 30 g were charged, and the solution was ice-cooled, and 5- (2 , 5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride 5.28 g (20 mmol) was added, the temperature was raised to 120 ° C., and the reaction was conducted with stirring for 4 hours. After completion of the reaction, the reaction mixture was allowed to cool to room temperature, and 30 g of N-methyl-2-pyrrolidone was added to dilute the polyamic acid concentration.
[0020]
Furthermore, 5 g of pyridine and 10 g of acetic anhydride were added, the mixture was heated at 50 ° C. for 3 hours to conduct a polyimide reaction, and after completion of the reaction, the reaction mixture was reprecipitated in water to obtain a photosensitive polyimide.
[0021]
Example 2A
In Example 1A , 2.12 g (8 mmol) of 2,2-bis (3-amino-4-hydroxy) propane was used in place of DHTM, and the amount of BABEB was changed to 1.472 g (4 mmol).
[0022]
Example 3A
In Example 1A , 1.216 g (8 mmol) of 3,5-diaminobenzoic acid was used instead of DHTM, and the amount of BABEB was changed to 1.472 g (4 mmol).
[0023]
Example 1B
About 2 g of a 35 wt% methyl ethyl ketone solution of the photosensitive polyimide obtained in Example 1A was dropped on a quartz glass plate (7 × 7 cm), and spin coating was performed at 750 rpm for 10 seconds. Thereafter, the solvent was removed by pre-baking at 80 ° C. for 10 minutes. A mask (Hitachi Chemical Product PHOTEC) was placed on this photosensitive polyimide coated quartz glass, and a UV light source (manufactured by Ushio Electric) having main absorption at 350 to 450 nm was irradiated at an exposure dose of 300 mJ / cm 2 . After exposure, post-exposure baking at 120 ° C for 10 minutes was performed, and a 3 wt% sodium carbonate aqueous solution was used as a developer, developed at 40 ° C for about 60 seconds, and washed with distilled water to obtain a clear negative pattern .
[0024]
Example 2B
In Example 1B , the photosensitive polyimide obtained in Example 2A was used in place of the photosensitive polyimide obtained in Example 1A , and the exposure amount was changed to 475 mJ / cm 2 . Similarly, a clear negative pattern was obtained.
[0025]
Example 3B
In Example 1B , the photosensitive polyimide obtained in Example 3A was used in place of the photosensitive polyimide obtained in Example 1A . Similarly, a clear negative pattern was obtained.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23017098A JP4434338B2 (en) | 1997-09-26 | 1998-07-31 | Photosensitive polyimide |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9-279959 | 1997-09-26 | ||
| JP27995997 | 1997-09-26 | ||
| JP23017098A JP4434338B2 (en) | 1997-09-26 | 1998-07-31 | Photosensitive polyimide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11158278A JPH11158278A (en) | 1999-06-15 |
| JP4434338B2 true JP4434338B2 (en) | 2010-03-17 |
Family
ID=26529183
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23017098A Expired - Fee Related JP4434338B2 (en) | 1997-09-26 | 1998-07-31 | Photosensitive polyimide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4434338B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4811158B2 (en) * | 1998-05-01 | 2011-11-09 | 日本メクトロン株式会社 | Polyimide and process for producing the same |
| JP4811162B2 (en) * | 1998-05-14 | 2011-11-09 | 日本メクトロン株式会社 | Polyimide and process for producing the same |
| JP3968886B2 (en) | 1998-05-14 | 2007-08-29 | 日本メクトロン株式会社 | Photosensitive composition |
| WO2007125817A1 (en) * | 2006-04-24 | 2007-11-08 | Jsr Corporation | Photosensitive resin composition |
| JP5030743B2 (en) * | 2007-11-22 | 2012-09-19 | 旭化成イーマテリアルズ株式会社 | Polymer and positive photosensitive resin composition |
| US9791745B2 (en) * | 2012-09-07 | 2017-10-17 | Lg Chem, Ltd. | Photoalignment polyimide copolymer and liquid crystal alignment layer |
| CN114524938B (en) * | 2021-10-28 | 2024-02-09 | 江苏三月科技股份有限公司 | Polymer, photosensitive resin composition, cured film prepared from polymer and photosensitive resin composition, and electronic element |
-
1998
- 1998-07-31 JP JP23017098A patent/JP4434338B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH11158278A (en) | 1999-06-15 |
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