JPS6025061B2 - Photosensitive silicone resin composition - Google Patents
Photosensitive silicone resin compositionInfo
- Publication number
- JPS6025061B2 JPS6025061B2 JP19485181A JP19485181A JPS6025061B2 JP S6025061 B2 JPS6025061 B2 JP S6025061B2 JP 19485181 A JP19485181 A JP 19485181A JP 19485181 A JP19485181 A JP 19485181A JP S6025061 B2 JPS6025061 B2 JP S6025061B2
- Authority
- JP
- Japan
- Prior art keywords
- photosensitive
- silicone resin
- resin composition
- present
- photosensitive silicone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
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- Compositions Of Macromolecular Compounds (AREA)
Description
【発明の詳細な説明】
本発明は新規な感光性シリコーン樹脂組成物に関するも
のである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel photosensitive silicone resin composition.
感光性シリコーン樹脂の製造法としては
‘１｝ 水酸基を有するポリシロキサンに、メタクリル
基を有するアルコキシシランを反応させる方法（侍開昭
４９−３９２０び号公報）、（２’ 水素を有するポリ
シロキサンにアリルメタクリレート等の化合物を付加反
応させる方法（特開昭５２一３５７１ｙ号公報）などの
他、ポリシロキサンに感光基を導入する種々の方法が知
られている。Methods for producing photosensitive silicone resin include '1' A method of reacting a polysiloxane having a hydroxyl group with an alkoxysilane having a methacrylic group (Samurai Publication No. 49-3920), (2' A method of reacting a polysiloxane having a hydrogen group with an alkoxysilane having a methacrylic group); In addition to a method of addition-reacting a compound such as allyl methacrylate (Japanese Unexamined Patent Publication No. 52-3571y), various methods of introducing photosensitive groups into polysiloxane are known.
しかし、これらのポリシロキサンに感光基を導入する方
法では、その製造法が非常に煩雑であり、これを用いて
得られた感光性樹脂組成物は、光反応後の耐熱性がわる
いという欠点を有していた。本発明者らは、これらの欠
点に鑑み、上記のような感光性樹脂を用いずに容易に製
造可能であり、光反応後の耐熱性の優れた感光性シリコ
−ン樹脂組成物を得る目的で検討を重ねた結果、本発明
の感光性シリコーン樹脂組成物に至った。However, these methods of introducing photosensitive groups into polysiloxanes require very complicated manufacturing methods, and the photosensitive resin compositions obtained using these methods have the disadvantage of poor heat resistance after photoreaction. had. In view of these drawbacks, the present inventors aimed to obtain a photosensitive silicone resin composition that can be easily produced without using the above photosensitive resin and has excellent heat resistance after photoreaction. As a result of repeated studies, we have arrived at the photosensitive silicone resin composition of the present invention.
本発明は、風 一般式
（ただし、Ｒ，、Ｒ２は、一価の炭化水素基または一価
の置換炭化水素基であり、これらは同一でも相違しても
よく、ｎは正の整数である）で示される末端ヒドロキシ
ポリラダーシロキサンならびに（Ｂ）芳香族アジド化合
物および／または芳香族スルホニルアジド化合物を含有
してなる感光性シリコーン樹脂組成物に関する。The present invention is based on the general formula (where R, R2 is a monovalent hydrocarbon group or a monovalent substituted hydrocarbon group, and these may be the same or different, and n is a positive integer. ) and (B) an aromatic azide compound and/or an aromatic sulfonyl azide compound.
本発明になる感光性シリコーン樹脂組成物は、ベースレ
ジンとなる上記の末端ヒドロキシポリラダーシロキサン
と感光性化合物である芳香族アジドイヒ合物および／ま
たは芳香族スルホニルアジド化合物を適当な溶剤の存在
下で混合することにより容易に得られる。また、本発明
の感光性シリコーン樹脂組成物は、ベースレジンとして
末端ヒドロキシポリラダーシロキサンを用いているため
、光反応後の耐熱性が非常に優れている。以下、本発明
を詳細に説明する。The photosensitive silicone resin composition of the present invention is produced by combining the above-mentioned terminal hydroxypolyladder siloxane as a base resin and an aromatic azide compound and/or an aromatic sulfonyl azide compound as a photosensitive compound in the presence of an appropriate solvent. It can be easily obtained by mixing. Furthermore, since the photosensitive silicone resin composition of the present invention uses terminal hydroxypolyladder siloxane as the base resin, it has excellent heat resistance after photoreaction. The present invention will be explained in detail below.
本発明の感光性シリコーン樹脂組成物に用いられる末端
ヒドロキシポＩＪラダーシロキサンは特関昭５３−磯０
９少号公報等に示され、既に知られた化合物である。The terminal hydroxypolyte IJ ladder siloxane used in the photosensitive silicone resin composition of the present invention is
It is an already known compound as disclosed in Publication No. 9, etc.
本発明における上記の末端ヒドロキシポリラダーシロキ
サンを示す上記の式において、Ｒ，およびＲ２は一価の
炭化水素基または一価の置換炭化水素基であり、これら
は同一であっても相違してもよく、例えばメチル基、エ
チル基、プロピル基等のアルキル基、フェニル基、置換
フェニル基等の芳香族炭化水素基、これらのハロゲン置
換体などがあるが、光反応後の耐熱性を高めるためには
芳香族炭化水素基が好ましい。上式においてｎは正の整
数であるが通常５０より大なる整数である。In the above formula showing the terminal hydroxy polyladder siloxane of the present invention, R and R2 are monovalent hydrocarbon groups or monovalent substituted hydrocarbon groups, and they may be the same or different. Common examples include alkyl groups such as methyl groups, ethyl groups, and propyl groups, aromatic hydrocarbon groups such as phenyl groups and substituted phenyl groups, and halogen-substituted products of these groups. is preferably an aromatic hydrocarbon group. In the above formula, n is a positive integer, but is usually an integer greater than 50.
また、本発明の感光性シリコーン樹脂組成物に用いられ
る感光性化合物である芳香族アジド化合物および芳香族
スルホニルァジド化合物は光照射により活性種ナイトレ
ンを生成し、この活性種は二量化、二重結合への付加、
水素引き抜き反応などを起こすことが知られている。Furthermore, the aromatic azide compound and the aromatic sulfonylazide compound, which are the photosensitive compounds used in the photosensitive silicone resin composition of the present invention, produce an active species nitrene upon irradiation with light, and this active species undergoes dimerization and duplication. addition to the bond,
It is known to cause hydrogen abstraction reactions.
従って末端ヒドロキシポリラダーシ。キサン中に添加さ
れたこれらの感光性化合物は上記反応を経由して、その
光照射部と未照射部に現像液に対する溶解性の差異をも
たらし、パターン形成が可能となる。本発明に用いられ
る芳香族アジド化合物としては例えば等のモノアジド化
合物、等のビスアジド化合物などがある。Therefore, terminal hydroxypolyradashi. These photosensitive compounds added to xane cause a difference in solubility in a developing solution between the irradiated area and the non-irradiated area through the above reaction, thereby making it possible to form a pattern. Examples of the aromatic azide compound used in the present invention include monoazide compounds such as , and bisazide compounds such as .
また、芳香族スルホニルアジド化合物としては、例えば
等のモノスルホニルアジド化合物
等のビススルホニルアジド化合物などがある。Examples of aromatic sulfonyl azide compounds include bissulfonyl azide compounds such as monosulfonyl azide compounds.
これらの感光性化合物は単独でまたは二種以上を併用し
て用いることができる。本発明の感光性シリコーン樹脂
組成物は通常末端ヒドロキシポリラダーシロキサンと感
光性化合物を適当な有機溶媒に溶解した状態で使用され
るが、この場合に用いる溶媒としては、末端ヒドロキシ
ポリラダーシロキサンと感光性化合物のいずれをも熔解
することが望ましく、例えば、ベンゼン、トルェン、キ
シレン等の芳香族炭化水素、アセトン、メチルエチルケ
トン等のケトン系溶媒などが用いられる。These photosensitive compounds can be used alone or in combination of two or more. The photosensitive silicone resin composition of the present invention is usually used in a state in which the terminal hydroxypolyladder siloxane and the photosensitive compound are dissolved in a suitable organic solvent. For example, aromatic hydrocarbons such as benzene, toluene, and xylene, and ketone solvents such as acetone and methyl ethyl ketone are used.
これらは単独で用いても良いし混合して用いることも可
能である。また本発明の感光性シリコーン樹脂組成物に
は種々の増感剤を併用することが可能である。These may be used alone or in combination. Further, various sensitizers can be used in combination with the photosensitive silicone resin composition of the present invention.
増感剤は感光性化合物の感光波長域をひろげたり、感光
性化合物へ光エネルギーを効率良く与えるなどして感光
感度の向上をはかるものであり、本発明においては、例
えばペンゾィン又はその誘導体、ペンゾィンメチルェー
テル等のペンゾインェーナル類、ベンジルとその誘導体
、アリールジアゾニウム塩、アントラキノンとその誘導
体、アセトフェノン又はその誘導体、ジフェニルスルフ
イド等のィオウ化合物、ベンゾフヱノン又はその譲導体
などが使用可能であり、これらは一種または二種以上の
混合物として用いられる。本発明における感光性シリコ
ーン樹脂組成物の組成としては、末端ヒドロキシポリラ
ダーシロキサン１０町重量部に対して感光性化合物は、
好ましくは１〜５の重量部、より好ましくは５〜３の重
量部の範囲で用いられる。Sensitizers aim to improve photosensitivity by expanding the sensitive wavelength range of photosensitive compounds and efficiently imparting light energy to photosensitive compounds. In the present invention, for example, penzoin or its derivatives, pen Penzoinenals such as zoin methyl ether, benzyl and its derivatives, aryl diazonium salts, anthraquinone and its derivatives, acetophenone or its derivatives, sulfur compounds such as diphenyl sulfide, benzophenone or its derivatives These can be used alone or as a mixture of two or more. The composition of the photosensitive silicone resin composition in the present invention is as follows: 10 parts by weight of the terminal hydroxy polyladder siloxane and the photosensitive compound:
It is preferably used in a range of 1 to 5 parts by weight, more preferably 5 to 3 parts by weight.
感光性化合物が多すぎると保存中に感光性化合物が析出
したり、光反応後の耐熱性が低下し、感光性化合物が少
なすぎると光反応後、光照射部を未照射部との現像液に
対する溶解性の差が小さくなりパターン形成能が低下す
る額向がある。本発明になる感光性シリコーン樹脂組成
物は、上記した様な組成で前述の有機溶媒溶液にし、適
当な方法で基材に塗布した後、溶媒を乾燥し光照射を行
なう。If there is too much photosensitive compound, the photosensitive compound will precipitate during storage or the heat resistance after photoreaction will decrease, and if there is too little photosensitive compound, after photoreaction, the developing solution will separate the light-exposed area from the unexposed area. In some cases, the difference in solubility between the two materials becomes smaller and the ability to form patterns decreases. The photosensitive silicone resin composition of the present invention is prepared by preparing a solution in the above-mentioned organic solvent with the above-described composition, applying it to a substrate by an appropriate method, drying the solvent, and irradiating it with light.
その後、前述した有機溶媒、希アルカリ溶液等の適当な
現像液を用いてパターンを形成することができる。以下
、本発明の実施例を説明する。Thereafter, a pattern can be formed using an appropriate developer such as the above-mentioned organic solvent or dilute alkaline solution. Examples of the present invention will be described below.
実施例 １
メチルトリクロルシランを用いて侍関昭５３−滋０９叫
号公報の実施例１、３に準じて製造された末端ヒドロキ
シポリメチルラダーシロキサン（重量平均分子量２万）
１０のこパラアジド安息香酸２一（ジメチルアミノ）エ
チル３夕を添加し、トルェン１５０夕に溶解して感光性
シリコーン樹脂組成物を作成した。Example 1 Terminal hydroxypolymethyl ladder siloxane (weight average molecular weight: 20,000) produced using methyltrichlorosilane according to Examples 1 and 3 of Samurai Seki Sho 53-Shi No. 09 Publication
A photosensitive silicone resin composition was prepared by adding 10 parts of 2-(dimethylamino)ethyl paraazidobenzoate and 3 parts of it and dissolving it in 150 parts of toluene.
この組成物を５肌×５ｃｍのガラス板に膜厚１仏のに塗
布し、塗布後８０ｏｏで２０分間トルェンを乾燥し、石
英マスクを介してＸｅ−Ｈｇ灯により５仇ｈＷ／めで光
照射を行なった。This composition was applied to a glass plate measuring 5 skins x 5 cm to a film thickness of 1 inch, dried with toluene at 80 ooohes after application for 20 minutes, and irradiated with light at 5 hW/hW using a Xe-Hg lamp through a quartz mask. I did it.
ついで希アルカリ溶液で２分間現像して良好なパターン
を得た。このパタ−ンは３００つＣで６粉劫０熱後も何
ら変化が認められなかった。本発明によれば、末端ヒド
ロキシポリラダーシロキサンと感光性化合物を混合する
だけで容易に感光性シリコーン樹脂組成物を製作するこ
とができる。It was then developed with a dilute alkaline solution for 2 minutes to obtain a good pattern. No change was observed in this pattern even after heating at 300 degrees Celsius for 6 cycles. According to the present invention, a photosensitive silicone resin composition can be easily produced simply by mixing terminal hydroxy polyladder siloxane and a photosensitive compound.
Claims (1)
一価の置換炭化水素基であり、これらは同一でも相違し
てもよく、ｍは整数である）で示される末端ヒドロキシ
ポリラダーシロキサンならびに （Ｂ） 芳香族アジド化合物および／または芳香族スル
ホニルアジド化合物を有してなる感光性シリコーン樹脂
組成物。[Claims] 1 (A) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, R_1 and R_2 are a monovalent hydrocarbon group or a monovalent substituted hydrocarbon group, and these are the same A photosensitive silicone resin composition comprising (B) an aromatic azide compound and/or an aromatic sulfonyl azide compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19485181A JPS6025061B2 (en) | 1981-12-02 | 1981-12-02 | Photosensitive silicone resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19485181A JPS6025061B2 (en) | 1981-12-02 | 1981-12-02 | Photosensitive silicone resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5896654A JPS5896654A (en) | 1983-06-08 |
| JPS6025061B2 true JPS6025061B2 (en) | 1985-06-15 |
Family
ID=16331331
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19485181A Expired JPS6025061B2 (en) | 1981-12-02 | 1981-12-02 | Photosensitive silicone resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6025061B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0426929Y2 (en) * | 1988-06-06 | 1992-06-29 |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0656491B2 (en) * | 1983-07-20 | 1994-07-27 | 日立化成工業株式会社 | Photosensitive silicone resin composition |
| JPS60117242A (en) * | 1983-11-29 | 1985-06-24 | Fujitsu Ltd | Micropattern forming material |
| JPS61188539A (en) * | 1985-02-18 | 1986-08-22 | Nippon Telegr & Teleph Corp <Ntt> | Formation of pattern |
| JPS60238827A (en) * | 1984-05-14 | 1985-11-27 | Nippon Telegr & Teleph Corp <Ntt> | Photosensitive resin composition |
| JPS60254036A (en) * | 1984-05-30 | 1985-12-14 | Fujitsu Ltd | Formation of pattern |
| JPS61144639A (en) * | 1984-12-19 | 1986-07-02 | Hitachi Ltd | Radiation sensitive composition and pattern forming method using its composition |
| DE3678652D1 (en) * | 1985-03-07 | 1991-05-16 | Hughes Aircraft Co | POLYSILOXANE PROTECTIVE LACQUER FOR ION AND ELECTRON BEAM LITHOGRAPHY. |
| US4786569A (en) * | 1985-09-04 | 1988-11-22 | Ciba-Geigy Corporation | Adhesively bonded photostructurable polyimide film |
| JP4270708B2 (en) | 1999-04-23 | 2009-06-03 | 富士通株式会社 | Silicon-containing polymer, method for producing the same, resist composition using the same, pattern forming method, and method for producing electronic device |
| US6731857B2 (en) | 2001-03-29 | 2004-05-04 | Shipley Company, L.L.C. | Photodefinable composition, method of manufacturing an optical waveguide with the photodefinable composition, and optical waveguide formed therefrom |
| JP2004185000A (en) | 2002-12-02 | 2004-07-02 | Rohm & Haas Electronic Materials Llc | Method for forming waveguide and waveguide formed thereby |
| US6842577B2 (en) | 2002-12-02 | 2005-01-11 | Shipley Company L.L.C. | Photoimageable waveguide composition and waveguide formed therefrom |
| US7072564B2 (en) | 2003-11-25 | 2006-07-04 | Rohm And Haas Electronic Materials Llc | Waveguide compositions and waveguides formed therefrom |
| JP5102428B2 (en) | 2003-11-25 | 2012-12-19 | ローム・アンド・ハース・エレクトロニック・マテリアルズ，エル．エル．シー． | Waveguide composition and waveguide formed therefrom |
| DE602005014984D1 (en) | 2004-04-14 | 2009-07-30 | Rohm & Haas Elect Mat | Waveguide compositions and waveguides made therefrom |
-
1981
- 1981-12-02 JP JP19485181A patent/JPS6025061B2/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0426929Y2 (en) * | 1988-06-06 | 1992-06-29 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5896654A (en) | 1983-06-08 |
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