JPH05289334A - Photosensitive composition - Google Patents
Photosensitive compositionInfo
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- JPH05289334A JPH05289334A JP13745692A JP13745692A JPH05289334A JP H05289334 A JPH05289334 A JP H05289334A JP 13745692 A JP13745692 A JP 13745692A JP 13745692 A JP13745692 A JP 13745692A JP H05289334 A JPH05289334 A JP H05289334A
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- Prior art keywords
- photosensitive
- film
- composition
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- substrate
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- Formation Of Insulating Films (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明は、概略、感光性芳香族
ポリアミドまたは感光性芳香族ポリイミドなどの感光性
樹脂、光重合開始剤、ジカルボン酸化合物（Ａ）、およ
び、エポキシ基またはアミノ基を含有するアルコキシシ
ラン化合物（Ｂ）からなり、（Ａ）と（Ｂ）のモル比
（Ａ／Ｂ）が２：９〜５：２である感光性組成物に係わ
るものである。BACKGROUND OF THE INVENTION This invention relates to a photosensitive resin such as a photosensitive aromatic polyamide or a photosensitive aromatic polyimide, a photopolymerization initiator, a dicarboxylic acid compound (A), and an epoxy group or an amino group. The present invention relates to a photosensitive composition comprising an alkoxysilane compound (B) contained therein and having a molar ratio (A / B) of (A) and (B) of 2: 9 to 5: 2.
【０００２】この発明の感光性組成物は、その組成物の
塗膜（皮膜）を基材上に形成し、その塗膜上に光照射し
てパターン状に光硬化させ、最後に、現像液で該塗膜の
未露光部分（未硬化部分）を除去する現像操作を行うこ
とによって、電子部材の絶縁保護膜（オーバーコート
膜）を形成したり、透明保護膜、エッチングレジスト、
スペーサー等の微細な光硬化パターンを有する部材を製
造することができる。The photosensitive composition of the present invention comprises forming a coating film (film) of the composition on a substrate, irradiating the coating film with light to photo-cure it in a pattern, and finally, developing solution. By performing a developing operation for removing the unexposed portion (uncured portion) of the coating film, an insulating protective film (overcoat film) of an electronic member is formed, a transparent protective film, an etching resist,
It is possible to manufacture a member having a fine photo-curing pattern such as a spacer.
【０００３】[0003]
【従来技術の説明】従来、感光性組成物は、一般に、感
光性樹脂、光重合開始剤からなり、必要に応じて基材と
の密着性を高めるためにシランカップリング剤等を添加
していた。これらシランカップリング剤は、アルコキシ
シラン基と有機反応性基を持ち、アルコキシシラン基が
基材と、有機反応性基が感光性樹脂等の有機化合物とそ
れぞれ結合することにより、密着性を付与している。し
かし、この有機反応性基と反応性に乏しい感光性樹脂、
例えば感光性ポリイミドや感光性ポリアミドなどでは充
分な密着性が得られなかった。特に現像時における密着
性について充分でなく、そのため塗膜底部まで充分に光
硬化させなければ現像を効率的に行うことができず、結
局、感度が低いという問題点があった。Description of the Prior Art Conventionally, a photosensitive composition generally comprises a photosensitive resin and a photopolymerization initiator, and a silane coupling agent or the like is added as necessary to enhance the adhesion to a substrate. It was These silane coupling agents have an alkoxysilane group and an organic reactive group, and the alkoxysilane group binds to the base material and the organic reactive group to an organic compound such as a photosensitive resin to provide adhesion. ing. However, a photosensitive resin that is poorly reactive with this organic reactive group,
For example, sufficient adhesion cannot be obtained with photosensitive polyimide or photosensitive polyamide. In particular, the adhesiveness at the time of development is not sufficient, so that development cannot be efficiently performed unless the bottom of the coating film is sufficiently photocured, and there is a problem that sensitivity is low in the end.
【０００４】[0004]
【本発明が解決しようとする問題点】この発明は、塗膜
と基材との密着性に優れ、特に現像時の密着性が高く、
塗膜底部での光硬化度が低くても安定した光硬化パター
ンが得られるため、見かけ上の感度が高くなるとともに
現像の操作性を高める感光性組成物を提供することを目
的とするものである。DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The present invention has excellent adhesion between the coating film and the substrate, and particularly high adhesion during development.
Since a stable photo-curing pattern can be obtained even when the photo-curing degree at the bottom of the coating film is low, it is an object to provide a photosensitive composition which has high apparent sensitivity and enhances operability of development. is there.
【０００５】[0005]
【問題点を解決するための手段】この発明は、炭素−炭
素不飽和結合を有する感光性樹脂、光重合開始剤、ジカ
ルボン酸化合物（Ａ）、および、エポキシ基またはアミ
ノ基を含有するアルコキシシラン化合物（Ｂ）からな
り、（Ａ）と（Ｂ）のモル比（Ａ／Ｂ）が２：９〜５：
２、特に１：４〜２：１であることを特徴とする感光性
組成物に関する。This invention is directed to a photosensitive resin having a carbon-carbon unsaturated bond, a photopolymerization initiator, a dicarboxylic acid compound (A), and an alkoxysilane containing an epoxy group or an amino group. The compound (B) is used, and the molar ratio (A / B) of (A) and (B) is 2: 9 to 5 :.
2, in particular 1: 4 to 2: 1, relates to a photosensitive composition.
【０００６】この発明の感光性組成物は、例えば、炭
素−炭素二重結合（感光性基）を有する感光性（芳香
族）ポリアミド、感光性（芳香族）ポリイミド等の『感
光性樹脂』、ビスアジド化合物、ベンジル類、ベンゾ
インエーテル類、チオキサントン類等の『光重合開始
剤』、シュウ酸、マレイン酸、コハク酸、フタル酸等
の『ジカルボン酸化合物』及びγ−グリシドキシプロ
ピルトリメトキシシラン、γ−アミノプロピルトリエト
キシシラン等の『エポキシ基またはアミノ基を含有する
アルコキシシラン化合物』が、均一に配合、混合されて
いる感光性組成物、或いはその溶液組成物が好適であ
る。The photosensitive composition of the present invention comprises, for example, a "photosensitive resin" such as a photosensitive (aromatic) polyamide or a photosensitive (aromatic) polyimide having a carbon-carbon double bond (photosensitive group), "Photoinitiators" such as bisazide compounds, benzyls, benzoin ethers, thioxanthones, "dicarboxylic acid compounds" such as oxalic acid, maleic acid, succinic acid, phthalic acid and γ-glycidoxypropyltrimethoxysilane, A photosensitive composition in which “alkoxysilane compound containing epoxy group or amino group” such as γ-aminopropyltriethoxysilane is uniformly mixed and mixed, or a solution composition thereof is suitable.
【０００７】前記の炭素−炭素不飽和結合を有する感光
性樹脂としては、（メタ）アクリレート化されたエポキ
シ樹脂、（メタ）アクリレート化されたウレタン樹脂、
（メタ）アクリレート化されたポリエステル樹脂などの
多官能性アクリレート系樹脂、あるいは、感光性ポリア
ミド、感光性ポリイミド、感光性ポリシロキサン、感光
性ポリアルキル（メタ）アクリレート、感光性ポリビニ
ルアルコール、又は、それらの誘導体などの炭素−炭素
不飽和結合を有する感光性重合体を挙げることができ
る。As the photosensitive resin having a carbon-carbon unsaturated bond, a (meth) acrylated epoxy resin, a (meth) acrylated urethane resin,
Polyfunctional acrylate resin such as (meth) acrylated polyester resin, or photosensitive polyamide, photosensitive polyimide, photosensitive polysiloxane, photosensitive polyalkyl (meth) acrylate, photosensitive polyvinyl alcohol, or those Examples thereof include photosensitive polymers having a carbon-carbon unsaturated bond.
【０００８】前記の感光性樹脂としては、特開昭６１−
３７８０８号公報および特公平２ー３１１０３号公報な
どに記載されている炭素−炭素不飽和結合を有する可溶
性の感光性芳香族ポリアミド及び感光性芳香族ポリイミ
ドが、感光性、耐熱性などの点において、好適である。As the above-mentioned photosensitive resin, JP-A-61-161
Soluble photosensitive aromatic polyamides and photosensitive aromatic polyimides having a carbon-carbon unsaturated bond described in JP-A-37808 and JP-B-2-31103, etc. are, in terms of photosensitivity and heat resistance, It is suitable.
【０００９】又、前記感光性樹脂は平均分子量が１００
０〜１００００００、特に５０００〜５０００００程度
であることが好ましい。前記感光性樹脂は、沸点が５０
℃以上の有機溶媒に可溶性であり、該有機溶媒に１〜４
０重量％の濃度で均一に溶解させて用いることが好まし
い。The photosensitive resin has an average molecular weight of 100.
It is preferably from 0 to 1,000,000, and particularly preferably from 5,000 to 500,000. The photosensitive resin has a boiling point of 50.
It is soluble in an organic solvent having a temperature of ℃ or higher, and is 1 to 4 in the organic solvent.
It is preferable to use it by uniformly dissolving it at a concentration of 0% by weight.
【００１０】この発明の感光性組成物に配合される光重
合開始剤としては、例えば、ビスアジド化合物、ミヒラ
ーズケトン、ベンゾイン、ベンゾインメチルエーテル、
ベンゾインエチルエーテル、ベンゾインイソプロピルエ
ーテル、２−ｔ−ブチルアントラキノン、１，２−ベン
ゾ−９，１０−アントラキノン、ベンジル、アニシル、
４，４’−ビス（ジエチルアミノ）ベンゾフェノン、ア
セトフェノン、ベンゾフェノン、１，５−アセナフテ
ン、チオキサントン又はその誘導体、アントラニル酸ジ
メチルアミノベンゾエート等の光重合開始剤を挙げるこ
とができる。Examples of the photopolymerization initiator to be incorporated in the photosensitive composition of the present invention include bisazide compounds, Michler's ketone, benzoin, benzoin methyl ether,
Benzoin ethyl ether, benzoin isopropyl ether, 2-t-butylanthraquinone, 1,2-benzo-9,10-anthraquinone, benzyl, anisyl,
Examples of the photopolymerization initiator include 4,4′-bis (diethylamino) benzophenone, acetophenone, benzophenone, 1,5-acenaphthene, thioxanthone or its derivative, and anthranilic acid dimethylaminobenzoate.
【００１１】前記の光重合開始剤として使用されるビス
アジド化合物としては、４，４’−ジアジドカルコン、
４，４’−ジアジドベンザルアセトン、２，６−ジ−
（４’−アジドベンザル）メチルシクロヘキサノン、
４，４’−ジアジドスチルベン等を好適に挙げることが
できる。また、光重合開始剤として使用される前記のチ
オキサントン類としては、２，４−ジエチルチオキサン
トン、２−クロルチオキサントン等を挙げることができ
る。The bisazide compound used as the photopolymerization initiator is 4,4'-diazidochalcone,
4,4'-diazidobenzalacetone, 2,6-di-
(4'-azidobenzal) methylcyclohexanone,
Suitable examples include 4,4'-diazidostilbene. Examples of the thioxanthones used as the photopolymerization initiator include 2,4-diethylthioxanthone and 2-chlorothioxanthone.
【００１２】上記光重合開始剤の配合量は、前記感光性
ポリアミドなどの感光性樹脂１００重量部に対して、
０．２〜４０重量部、特に０．５〜３０重量部の割合と
なる量とすることが好ましい。前記の配合量が少なすぎ
ると、得られる組成物の感度が低くなり、また、多くな
り過ぎると得られる組成物により形成される膜の耐熱性
が低下するので好ましくない。The amount of the photopolymerization initiator blended is 100 parts by weight of the photosensitive resin such as the photosensitive polyamide.
The amount is preferably 0.2 to 40 parts by weight, particularly 0.5 to 30 parts by weight. If the blending amount is too small, the sensitivity of the resulting composition will be low, and if it is too high, the heat resistance of the film formed by the composition will be unfavorable.
【００１３】この発明の感光性組成物において使用され
るジカルボン酸化合物は、分子量が３００以下であり、
高い酸性度（ｐＫａ＜５）を有すると共に、有機極性溶
媒に対して２重量％以上の可溶性であると、そのジカル
ボン酸化合物の配合量を少なくすることができたり、加
熱処理後にパターン部から昇華、蒸発、分解などで実質
的に除去されるので好ましい。上記ジカルボン酸の配合
量は、前記感光性樹脂１００重量部に対して、０．１〜
１５重量部、特に０．２〜１０重量部であることが好ま
しい。The dicarboxylic acid compound used in the photosensitive composition of the present invention has a molecular weight of 300 or less,
When it has a high acidity (pKa <5) and is soluble in an organic polar solvent in an amount of 2% by weight or more, the compounding amount of the dicarboxylic acid compound can be reduced, or it can be sublimated from the pattern portion after heat treatment. It is preferably removed by evaporation, decomposition, etc. The compounding amount of the dicarboxylic acid is 0.1 to 100 parts by weight of the photosensitive resin.
It is preferably 15 parts by weight, particularly 0.2 to 10 parts by weight.
【００１４】この発明の感光性組成物において使用され
るエポキシ基またはアミノ基を含有するアルコキシシラ
ン化合物としては、例えば、β−（３，４−エポキシシ
クロヘキシル）エチルトリメトキシシラン、γ−グリシ
ドキシプロピルトリメトキシシラン、γ−グリシドキシ
プロピルメチルジエトキシシラン、Ｎ−β（アミノエチ
ル）γ−アミノプロピルトリメトキシシラン、Ｎ−β
（アミノエチル）γ−アミノプロピルメチルジメトキシ
シラン、γ−アミノプロピルトリエトキシシラン、Ｎ−
フェニル−γ−アミノプロピルトリメトキシシラン等を
挙げることができる。上記アルコキシシラン化合物の配
合量は、前記感光性樹脂１００重量部に対して、１〜２
５重量部、特に２〜２０重量部であることが好ましい。Examples of the epoxysilane- or amino-group-containing alkoxysilane compound used in the photosensitive composition of the present invention include β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and γ-glycidoxy. Propyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β
(Aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-
Examples thereof include phenyl-γ-aminopropyltrimethoxysilane. The compounding amount of the alkoxysilane compound is 1 to 2 with respect to 100 parts by weight of the photosensitive resin.
It is preferably 5 parts by weight, particularly preferably 2 to 20 parts by weight.
【００１５】この発明では、前記ジカルボン酸化合物と
エポキシ基又はアミノ基を含有するアルコキシシラン化
合物とが併用されており、さらにそのモル比が２：９〜
５：２であることが、特に特徴的な要件である。In the present invention, the dicarboxylic acid compound and an alkoxysilane compound containing an epoxy group or an amino group are used in combination, and the molar ratio is 2: 9 to.
5: 2 is a particularly characteristic requirement.
【００１６】両者が併用された感光性組成物では、ジカ
ルボン酸の片方のカルボキシル基と、アルコキシシラン
化合物のエポキシ基又はアミノ基とが反応し、両者の反
応物を生成し、感光性組成物の塗膜と基材界面では、ア
ルコキシシラン基が基材と結合しジカルボン酸の未反応
のカルボキシル基が感光性樹脂と水素結合を形成し塗膜
と基材の密着性を高めていると推定され、現像時に現像
液が塗膜と基材の界面に浸透しにくくなり光硬化部のパ
ターンの剥がれが起こらなくなるとともに、感光性組成
物の塗膜底部の光硬化度が低くても高い密着力によりパ
ターンが維持され見かけ上感度が高くなった状態になる
ため、現像の操作性が飛躍的に向上し、微細なパターン
を効果的に形成することができるのである。In the photosensitive composition in which both are used in combination, one carboxyl group of the dicarboxylic acid and the epoxy group or amino group of the alkoxysilane compound react with each other to form a reaction product of the two, and the photosensitive composition of the photosensitive composition is obtained. It is presumed that at the interface between the coating film and the base material, the alkoxysilane group binds to the base material and the unreacted carboxyl group of the dicarboxylic acid forms a hydrogen bond with the photosensitive resin, increasing the adhesion between the coating film and the base material. , The developing solution hardly penetrates into the interface between the coating film and the base material during development, and the peeling of the pattern of the photocured part does not occur, and even if the photocurable degree of the bottom part of the photosensitive composition coating film is low, the high adhesion Since the pattern is maintained and the sensitivity is apparently increased, the operability of development is dramatically improved, and a fine pattern can be effectively formed.
【００１７】上記ジカルボン酸とアルコキシシラン化合
物のモル比が２：９より小さくなってアルコキシシラン
化合物の使用量が多くなると、アルコキシシラン基同志
の縮重合が起きやすくなり、未露光部の現像性が低下し
てパターンの解像度が悪くなる。また、モル比が５：２
より大きくなってジカルボン酸の使用量が多くなると、
現像後の最終パターンの機械的密着力が悪くなる。更
に、この発明の感光性組成物の溶液を長期間保存する場
合には、上記モル比が１：２〜３：２、特に２：３〜
３：２程度であることが好ましい。When the molar ratio of the dicarboxylic acid to the alkoxysilane compound is smaller than 2: 9 and the amount of the alkoxysilane compound used is large, polycondensation of the alkoxysilane groups is likely to occur and the developability of the unexposed area is increased. And the resolution of the pattern deteriorates. Also, the molar ratio is 5: 2.
The larger the amount of dicarboxylic acid used, the more
The mechanical adhesion of the final pattern after development becomes poor. Furthermore, when the solution of the photosensitive composition of the present invention is stored for a long period of time, the above molar ratio is 1: 2 to 3: 2, particularly 2: 3 to.
It is preferably about 3: 2.
【００１８】また、この発明の感光性組成物の溶液は、
種々の配合手順で調製することができ、その溶液の調製
方法が特に限定されることはないが、例えば、感光性樹
脂を前記の有機溶媒に均一に溶解した溶液を調製し、そ
の溶液にジカルボン酸化合物及びアルコキシシラン化合
物を添加して、最後に、光重合開始剤を添加することが
好ましい。ただし、ジカルボン酸とアルコキシシラン化
合物の添加方法については、それぞれ単独で添加して
も、あらかじめ両者の混合溶液を調製してから添加して
も良い。Further, the solution of the photosensitive composition of the present invention is
It can be prepared by various compounding procedures, and the method for preparing the solution is not particularly limited. For example, a solution in which the photosensitive resin is uniformly dissolved in the organic solvent is prepared, and the solution is diluted with dicarboxylic acid. It is preferable to add the acid compound and the alkoxysilane compound, and finally add the photopolymerization initiator. However, regarding the method of adding the dicarboxylic acid and the alkoxysilane compound, they may be added individually, or may be added after preparing a mixed solution of the two in advance.
【００１９】この発明の感光性組成物の溶液は、該組成
物の濃度が２〜４０重量％、特に３〜３０重量％程度で
あり、そして、その溶液の溶液粘度（回転粘度、２５
℃）が０．１〜１０００ポイズ、特に０．２〜５００ポ
イズであることが好ましい。また、この発明の感光性組
成物（の溶液）には、ハイドロキノン、２，６−ジ−ｔ
−ブチル−４−メチルフェノール（ＢＨＴ）、メチルエ
ーテルハイドロキノン、フェノチアジン等の熱重合防止
剤が配合されてもよい。The solution of the photosensitive composition of the present invention has a concentration of about 2 to 40% by weight, particularly about 3 to 30% by weight, and the solution viscosity (rotational viscosity, 25
C.) is preferably 0.1 to 1000 poises, particularly 0.2 to 500 poises. Further, (the solution of) the photosensitive composition of the present invention contains hydroquinone and 2,6-di-t.
A thermal polymerization inhibitor such as -butyl-4-methylphenol (BHT), methyl ether hydroquinone or phenothiazine may be blended.
【００２０】この発明の感光性組成物は、例えば、その
溶液を基材上に０〜６０℃の温度で塗布し１８０℃以下
の温度で乾燥して、感光性薄膜（乾燥塗膜）を形成し、
次いで、その感光性薄膜上にパターンマスクを介して超
高圧水銀灯の平行光線を照射して、該感光性薄膜を各パ
ターン状に光硬化し、その後、現像溶液に浸漬させて、
該塗膜の未露光部分（未硬化部分）を溶出させ除去する
現像を行って、光硬化膜を基材上に形成させることがで
きる。The photosensitive composition of the present invention is formed, for example, by coating the solution on a substrate at a temperature of 0 to 60 ° C. and drying it at a temperature of 180 ° C. or less to form a photosensitive thin film (dry coating film). Then
Then, a parallel light beam of an ultra-high pressure mercury lamp is radiated on the photosensitive thin film through a pattern mask, and the photosensitive thin film is photocured in each pattern, and then immersed in a developing solution,
The photo-cured film can be formed on the substrate by performing development to elute and remove the unexposed portion (uncured portion) of the coating film.
【００２１】その感光性組成物の溶液を基材の表面へ塗
布するには、例えば、回転塗布法、ロールコート法、浸
漬法、スプレー法等の方法により行うことができる。前
記の塗布膜の乾燥は、熱風乾燥器、ホットプレートなど
により、１８０℃以下、特に５０〜１５０℃の温度で１
〜６０分間、特に２〜３０分間程度行って、有機溶媒を
実質的に除去して感光性薄膜を形成することが好まし
い。この乾燥の際には減圧状態で行ってもよい。また、
前記の感光性薄膜（乾燥後の塗膜）の厚さは、通常約
０．１〜２０．０μｍ、特に０．２〜１０．０μｍ程度
であることが好ましい。The solution of the photosensitive composition can be applied to the surface of the substrate by spin coating, roll coating, dipping, spraying or the like. The coating film is dried by a hot air drier, a hot plate or the like at a temperature of 180 ° C. or less, particularly 50 to 150 ° C.
It is preferable to perform the treatment for about 60 minutes, particularly about 2 to 30 minutes to substantially remove the organic solvent to form a photosensitive thin film. The drying may be performed under reduced pressure. Also,
The thickness of the photosensitive thin film (dried coating film) is usually about 0.1 to 20.0 μm, preferably about 0.2 to 10.0 μm.
【００２２】前述のように、パターン状マスクを介して
光照射されて光硬化した薄膜（光硬化膜）が形成された
基材を現像液に浸漬させて、感光性薄膜の未硬化部分を
除去する『現像』を行う場合には、該未硬化部分に超音
波を作用させてもよい。上記の現像液としては、「感光
性樹脂を溶解させることができる有機溶媒Ａ」からなる
現像液、或いは、それらの有機溶媒Ａと「感光性樹脂を
溶解しない有機溶媒Ｂ」との混合系の現像液を用いるこ
とができる。As described above, the uncured portion of the photosensitive thin film is removed by immersing the base material on which the thin film (photo-cured film) photo-cured by being irradiated with light through the patterned mask is formed in the developing solution. When performing "development", ultrasonic waves may be applied to the uncured portion. As the above-mentioned developing solution, a developing solution composed of "organic solvent A capable of dissolving the photosensitive resin" or a mixed system of the organic solvent A and "organic solvent B not dissolving the photosensitive resin" A developer can be used.
【００２３】前述の現像後、パターン状に光硬化した光
硬化膜が形成された基材を、感光性樹脂を溶解しない有
機溶媒、或いは、水などによりリンスし、次いで、熱風
乾燥器、ホットプレート等により、約２５０℃以下、特
に２３０℃以下の温度で、１〜６０分間、特に２〜３０
分間、熱処理（ポストベーク）することが好ましい。After the above-mentioned development, the substrate on which the photocured film which is photocured in a pattern is formed is rinsed with an organic solvent which does not dissolve the photosensitive resin, or water, and then hot air dryer and hot plate. And the like, at a temperature of about 250 ° C or lower, particularly 230 ° C or lower, for 1 to 60 minutes, especially 2 to 30 minutes.
It is preferable to perform heat treatment (post-baking) for minutes.
【００２４】この発明の光硬化膜の形成法においては、
例えば、洗剤等で充分に脱脂し乾燥した方形のガラスな
どの基板（一辺の長さ：約１０〜５０ｃｍ）上に、塗布
膜を乾燥した後の感光性薄膜（塗膜）の厚さが０．１〜
１０μｍ、特に０．５〜５μｍとなるように、感光性組
成物（溶液組成物）をスピンコートで塗布して（コート
して）塗布膜を形成し、約５０〜１５０℃、特に６０〜
１００℃の温度で、０．１〜５０分間、特に１〜３０分
間、乾燥させて、有機溶媒を実質的に除去して、乾燥さ
れた感光性薄膜（塗膜）を形成することが好ましい。In the method for forming a photocured film of the present invention,
For example, the thickness of the photosensitive thin film (coating film) after drying the coating film is 0 on a substrate (length of one side: about 10 to 50 cm) such as a rectangular glass which has been thoroughly degreased with a detergent or the like and dried. 1 ~
The photosensitive composition (solution composition) is applied (coated) by spin coating so as to have a thickness of 10 μm, particularly 0.5 to 5 μm to form a coating film, and the coating film is formed at about 50 to 150 ° C., particularly 60 to
It is preferable to dry at a temperature of 100 ° C. for 0.1 to 50 minutes, particularly 1 to 30 minutes to substantially remove the organic solvent to form a dried photosensitive thin film (coating film).
【００２５】次いで、前述のようにして形成された感光
性の塗膜に、４〜１００μｍまでのストライプパターン
を有するパターンを介して高圧水銀灯（５ｍＷ／ｃ
ｍ２）で露光して、光硬化膜を形成し、その基板を前述
のように、現像溶液に浸漬すると共に、高い周波数の超
音波を作用させる現像操作を行って、未露光部分を実質
的に除去して、パターン状光硬化膜が形成されている基
板を得ることができる。Next, a high pressure mercury lamp (5 mW / c) was formed on the photosensitive coating film formed as described above through a pattern having a stripe pattern of 4 to 100 μm.
m 2 ) to form a photo-cured film, the substrate is immersed in a developing solution as described above, and a developing operation in which a high frequency ultrasonic wave is applied is performed to substantially expose the unexposed portion. Then, the substrate having the patterned photo-cured film formed thereon can be obtained.
【００２６】[0026]
【実施例】以下、感光性樹脂として、炭素−炭素不飽和
結合を有する感光性芳香族ポリアミドの製造に関する参
考例、並びに、この発明の感光性ポリアミド組成物の調
製、及び光硬化膜の形成法に関する実施例を例示して、
この発明をさらに詳しく説明する。EXAMPLES Reference examples relating to the production of a photosensitive aromatic polyamide having a carbon-carbon unsaturated bond as a photosensitive resin, the preparation of the photosensitive polyamide composition of the present invention, and the method for forming a photocured film are described below. As an example,
The present invention will be described in more detail.
【００２７】参考例１ 〔感光性芳香族ポリアミドの製造〕三ッ口フラスコに乾
燥した空気を通してフラスコ内のガスを置換した後、
３，５−ジアミノ安息香酸エチルメタクリル酸エステル
１１９．９８ｇを入れ、次いで、これにＮ−メチル−２
−ピロリドン（ＮＭＰ）７２０ミリリットルを加えて溶
解させた。この溶液を冷却後、０℃に冷却し攪拌しなが
ら、テレフタル酸ジクロライド９１．１６ｇを少しずつ
加えた。この際に発熱があり、反応溶液の温度が上昇す
る傾向があるが、約１０℃以下に維持した。この反応溶
液を、さらに、氷水中で、２時間攪拌し、重合反応を行
った。Reference Example 1 [Production of Photosensitive Aromatic Polyamide] Dry air was passed through a three-necked flask to replace the gas in the flask.
119.98 g of 3,5-diaminobenzoic acid ethyl methacrylic acid ester was added, and then N-methyl-2 was added thereto.
-720 ml of pyrrolidone (NMP) was added and dissolved. After cooling this solution, it was cooled to 0 ° C. and 91.16 g of terephthalic acid dichloride was added little by little while stirring. At this time, heat was generated and the temperature of the reaction solution tended to rise, but the temperature was maintained at about 10 ° C or lower. This reaction solution was further stirred in ice water for 2 hours to carry out a polymerization reaction.
【００２８】次いで、反応溶液にＮＭＰ５００ミリリッ
トルを加え希釈した後、この溶液をＮＭＰ１リットルと
水１０リットルとの混合液に加え芳香族ポリアミドを析
出させ、その析出物を濾過・回収し乾燥して芳香族ポリ
アミド白色粉末１６７．８ｇを得た。得られた感光性芳
香族ポリアミドの粉末は、対数粘度（濃度；０．５ｇ／
１００ミリリットル溶媒、溶媒；ＮＭＰ、測定温度；３
０℃）は０．８８であった。Then, 500 ml of NMP was added to the reaction solution to dilute it, and then this solution was added to a mixed solution of 1 liter of NMP and 10 liters of water to precipitate an aromatic polyamide. 167.8 g of a white powder of group polyamide was obtained. The obtained photosensitive aromatic polyamide powder had an inherent viscosity (concentration: 0.5 g /
100 ml solvent, solvent; NMP, measurement temperature; 3
(0 ° C.) was 0.88.
【００２９】実施例１ 〔感光性ポリアミド組成物（溶液組成物）の調製〕有機
溶媒としてのＮ−メチル−２−ピロリドン（ＮＭＰ）９
０ｇに、熱重合防止剤としてハイドロキノンモノメチル
エーテル（ＭＥＨＱ）１２０ｍｇを加えて、均一に溶解
させた溶液を調製し、次いで、その溶液に、参考例１で
製造した感光性芳香族ポリアミド（対数粘度：０．８
８）１０ｇを加えて、充分に攪拌して、均一に溶解させ
て粘稠な溶液を調製した。Example 1 [Preparation of photosensitive polyamide composition (solution composition)] N-methyl-2-pyrrolidone (NMP) 9 as an organic solvent
To 0 g, 120 mg of hydroquinone monomethyl ether (MEHQ) as a thermal polymerization inhibitor was added to prepare a uniformly dissolved solution, and then the photosensitive aromatic polyamide produced in Reference Example 1 (logarithmic viscosity: 0.8
8) 10 g was added, and the mixture was sufficiently stirred to be uniformly dissolved to prepare a viscous solution.
【００３０】そして、前述のようにして調製した溶液
に、光重合開始剤としてジエチルチオキサントン４００
ｍｇ、ベンジル１５０ｍｇ、ジエチルアミノ安息香酸エ
チルエステル３００ｍｇを加え、さらに、密着促進剤と
してγ−グリシドキシプロピルトリメトキシシラン３９
０ｍｇ（１．６５×１０−３モル）、及び、ジカルボン
酸としてしゅう酸１５０ｍｇ（１．６６×１０−３モ
ル）を加えて攪拌し、最後に、その溶液を１μｍのフッ
素樹脂製のフィルター（テフロンフィルター）を用いて
加圧濾過し、感光製芳香族ポリアミド組成物（溶液組成
物）を調製した。Then, diethylthioxanthone 400 was added as a photopolymerization initiator to the solution prepared as described above.
mg, benzyl 150 mg, and diethylaminobenzoic acid ethyl ester 300 mg were added, and γ-glycidoxypropyltrimethoxysilane 39 was further used as an adhesion promoter.
0 mg (1.65 × 10 −3 mol) and 150 mg (1.66 × 10 −3 mol) of oxalic acid as a dicarboxylic acid were added and stirred, and finally, the solution was mixed with a 1 μm fluororesin filter ( Pressure filtration was performed using a Teflon filter) to prepare a photosensitive aromatic polyamide composition (solution composition).
【００３１】〔パターン状光硬化膜の形成〕感光性芳香
族ポリアミド組成物（溶液組成物）を、ガラス基板上で
の乾燥膜の膜厚が２．０μｍになるように、該基板上に
回転塗布（スピンコート）して塗布膜を形成し、そし
て、その塗布膜を８０℃で１０分間乾燥して有機溶媒を
実質的に除去し、ガラス基板上に膜厚２．０μｍの感光
性薄膜（乾燥膜、塗膜）を形成した。[Formation of Patterned Photocured Film] A photosensitive aromatic polyamide composition (solution composition) was spun on a glass substrate so that the dry film thickness was 2.0 μm. A coating film is formed by coating (spin coating), and the coating film is dried at 80 ° C. for 10 minutes to substantially remove the organic solvent, and a photosensitive thin film (2.0 μm thick) is formed on the glass substrate. Dry film, coating film) was formed.
【００３２】次いで、該感光性薄膜（塗膜）に対して、
４〜１００μｍのストライプ状のパターンマスクを介し
て、超高圧水銀灯の光源で２０秒間で１００ｍＪ／ｃｍ
２の露光量による光照射を行い、該感光性薄膜をパター
ン状に光硬化した。Next, with respect to the photosensitive thin film (coating film),
100 mJ / cm for 20 seconds with a light source of an ultra-high pressure mercury lamp through a stripe-shaped pattern mask of 4 to 100 μm
Light irradiation with an exposure amount of 2 was performed to photo-cure the photosensitive thin film in a pattern.
【００３３】次いで、パターン状に光硬化された薄膜
（光硬化膜）が形成されている基板を、γ−ブチロラク
トン及びエチルセロソルブの混合液（γ−ブチロラクト
ンとエチルセロソルブとの容量比が３０：７０である）
からなる現像液に常温で浸漬すると同時に、１５Ｗの超
音波（２７ＫＨｚの周波数）を作用させながら、９０〜
２４０秒間、現像操作を行ってパターン状光硬化膜付き
基板を作成した。なお、前記感光性薄膜の未硬化部分
は、現像開始後６０秒で現像液に溶解し除去され、パタ
ーン状光硬化膜の剥がれはまったくなく、良好なパター
ン状光硬化膜が形成されていた。Next, the substrate on which the thin film (photo-cured film) photo-cured in a pattern is formed is subjected to a mixed liquid of γ-butyrolactone and ethyl cellosolve (the volume ratio of γ-butyrolactone and ethyl cellosolve is 30:70). Is)
While being immersed in a developing solution consisting of 10 at room temperature, ultrasonic waves of 15 W (frequency of 27 KHz) are applied,
A development operation was performed for 240 seconds to prepare a substrate with a patterned photocurable film. The uncured portion of the photosensitive thin film was dissolved and removed in a developing solution 60 seconds after the start of development, and the patterned photocured film was not peeled off at all, and a good patterned photocured film was formed.
【００３４】その基板について、最後に、エチルセロソ
ルブでリンスし、その後、その基板を２００℃で３０分
間熱処理して、４〜１００μｍのストライプ状のパター
ンからなる光硬化膜（厚さ２．０μｍ）が形成された基
板を製造した。上述のようにして得られたパターン状光
硬化膜を有する基板について、密着性試験を行った結
果、光硬化膜の剥がれはまったく無かった。Finally, the substrate was rinsed with ethyl cellosolve, and then the substrate was heat-treated at 200 ° C. for 30 minutes to form a photo-cured film having a stripe pattern of 4 to 100 μm (thickness: 2.0 μm). A substrate on which was formed was manufactured. The substrate having the patterned photo-cured film obtained as described above was subjected to an adhesion test, and as a result, the photo-cured film was not peeled at all.
【００３５】実施例２〜５及び比較例１〜４ 〔感光性ポリアミド組成物（溶液組成物）の調製〕ジカ
ルボン酸及びアルコキシシラン化合物の種類及び添加量
およびモル比を第１表のようにしたほかは、実施例１と
同様にして、感光性芳香族ポリアミド組成物（溶液組成
物）を調製した。Examples 2 to 5 and Comparative Examples 1 to 4 [Preparation of Photosensitive Polyamide Composition (Solution Composition)] The kind, addition amount and molar ratio of the dicarboxylic acid and the alkoxysilane compound are as shown in Table 1. A photosensitive aromatic polyamide composition (solution composition) was prepared in the same manner as in Example 1 except for the above.
【００３６】〔パターン状光硬化膜の形成〕各感光性芳
香族ポリアミド組成物（溶液組成物）を使用したほか
は、実施例１と同様にして、光硬化膜（パターン状）を
基板上に形成した。上述のようにして形成した各基板に
ついて、現像直後のパターン状態、および、ポストベイ
ク後の光硬化膜の密着性試験の結果をそれぞれ第１表に
示す。[Formation of Patterned Photocured Film] A photocured film (patterned) was formed on a substrate in the same manner as in Example 1 except that each photosensitive aromatic polyamide composition (solution composition) was used. Formed. For each substrate formed as described above, Table 1 shows the pattern state immediately after development and the result of the adhesion test of the photo-cured film after post-baking.
【００３７】[0037]
【表１】 [Table 1]
【００３８】[0038]
【発明の作用効果】この発明は、概略、感光性芳香族ポ
リアミドなどの感光性樹脂と光重合開始剤とジカルボン
酸化合物（Ａ）とエポキシ基またはアミノ基を含有する
アルコキシシラン化合物（Ｂ）からなり、前記（Ａ）と
（Ｂ）のモル比が２：９〜５：２である感光性組成物に
係わるものであり、該感光性組成物中の（Ａ）と（Ｂ）
との反応により、ガラスなどの基材上に形成された塗膜
（感光性樹脂）の密着性が極めて向上し、その結果、こ
の発明の感光性組成物の塗膜がパターン状に露光され、
現像される際に、光硬化されたパターン部分が剥がれた
りせず、極めて現像操作が容易となり、さらに、前述の
現像後に充分な後熱処理（ポストベイク）を充分に行え
ば、最終的に形成される光硬化膜と基材との間の密着性
が極めて高くすることができるという優れた作用効果を
有しているのである。The present invention generally comprises a photosensitive resin such as a photosensitive aromatic polyamide, a photopolymerization initiator, a dicarboxylic acid compound (A) and an alkoxysilane compound (B) containing an epoxy group or an amino group. The present invention relates to a photosensitive composition in which the molar ratio of (A) and (B) is 2: 9 to 5: 2, wherein (A) and (B) in the photosensitive composition are
By the reaction with, the adhesion of the coating film (photosensitive resin) formed on a substrate such as glass is extremely improved, and as a result, the coating film of the photosensitive composition of the present invention is exposed in a pattern,
When developed, the photo-cured pattern portion does not peel off and the developing operation becomes extremely easy. Further, after the above-mentioned development, sufficient post-heat treatment (post-baking) is sufficiently performed to finally form the film. It has an excellent effect that the adhesion between the photo-cured film and the substrate can be made extremely high.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｈ０１Ｌ 21/027 21/312 Ａ 8518−4Ｍ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Office reference number FI technical display location H01L 21/027 21/312 A 8518-4M
Claims (1)
脂、光重合開始剤、ジカルボン酸化合物（Ａ）、およ
び、エポキシ基またはアミノ基を含有するアルコキシシ
ラン化合物（Ｂ）からなり、（Ａ）と（Ｂ）とのモル比
（Ａ／Ｂ）が２：９〜５：２であることを特徴とする感
光性組成物。1. A photosensitive resin having a carbon-carbon unsaturated bond, a photopolymerization initiator, a dicarboxylic acid compound (A), and an alkoxysilane compound (B) having an epoxy group or an amino group. And the molar ratio (A / B) of (B) is from 2: 9 to 5: 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4137456A JP2823104B2 (en) | 1992-04-14 | 1992-04-14 | Photosensitive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4137456A JP2823104B2 (en) | 1992-04-14 | 1992-04-14 | Photosensitive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05289334A true JPH05289334A (en) | 1993-11-05 |
| JP2823104B2 JP2823104B2 (en) | 1998-11-11 |
Family
ID=15199035
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4137456A Expired - Fee Related JP2823104B2 (en) | 1992-04-14 | 1992-04-14 | Photosensitive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2823104B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009186780A (en) * | 2008-02-06 | 2009-08-20 | Hitachi Chem Co Ltd | Photosensitive element, resist pattern forming method using the same, and method for manufacturing printed wiring board |
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| JPS6327834A (en) * | 1986-07-22 | 1988-02-05 | Asahi Chem Ind Co Ltd | Heat resistant photoresist film |
| JPS63284213A (en) * | 1987-04-14 | 1988-11-21 | チバ−ガイギー アクチエンゲゼルシヤフト | Photopolymerizable material composition |
| JPH0268A (en) * | 1987-11-13 | 1990-01-05 | Toshiba Corp | Solder resist composition |
| JPH025062A (en) * | 1988-02-16 | 1990-01-09 | Basf Ag | Negative type photosensitive recording layer |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009186780A (en) * | 2008-02-06 | 2009-08-20 | Hitachi Chem Co Ltd | Photosensitive element, resist pattern forming method using the same, and method for manufacturing printed wiring board |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2823104B2 (en) | 1998-11-11 |
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