JPH0820568A - Addition polyermizable type monomer containing azide group - Google Patents
Addition polyermizable type monomer containing azide groupInfo
- Publication number
- JPH0820568A JPH0820568A JP7109093A JP7109093A JPH0820568A JP H0820568 A JPH0820568 A JP H0820568A JP 7109093 A JP7109093 A JP 7109093A JP 7109093 A JP7109093 A JP 7109093A JP H0820568 A JPH0820568 A JP H0820568A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- formula
- photosensitive resin
- type monomer
- azide group
- 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.)
- Pending
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は分子内にアジド基を含む
付加重合型モノマーに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an addition polymerization type monomer having an azido group in its molecule.
【０００２】[0002]
【従来の技術】同一分子内にアジド基を含む付加重合型
モノマーとしては、メタクリル酸 ２−（ｐ−アジドベ
ンゾイルオキシ）エチルが知られている（高分子論文
集，３５（５），ＰＰ３３１〜３３７，（１９７
８））。2. Description of the Related Art 2- (p-Azidobenzoyloxy) ethyl methacrylate is known as an addition polymerization type monomer having an azido group in the same molecule (Polymer Papers, 35 (5), PP331-). 337, (197
8)).
【０００３】[0003]
【発明が解決しようとする課題】しかしこの化合物は、
紫外線吸収域が３００ｎｍ以下にあるため、この波長域
を遮断する工業的に安価なソーダガラス製フォトマスク
あるいは乳剤被覆製のフォトマスクを使用するにあたっ
ては低感度であり、実用的ではないという課題がある。However, this compound is
Since the ultraviolet absorption region is 300 nm or less, there is a problem in that it is not practical when using an industrially inexpensive photomask made of soda glass or a photomask made of emulsion coating that blocks this wavelength region, which is not practical. is there.
【０００４】[0004]
【課題を解決するための手段】本発明者らは３００ｎｍ
以上に紫外線吸収域を持つアジド基含有付加重合型モノ
マーを得ることを目的に鋭意検討した結果本発明に到達
した。即ち本発明は、一般式Means for Solving the Problems The present inventors
The present invention has been accomplished as a result of intensive studies aimed at obtaining an azide group-containing addition polymerization type monomer having an ultraviolet absorption region. That is, the present invention has the general formula
【０００５】[0005]
【化２】 Embedded image
【０００６】（式中、Ｘはメチル基または水素原子）で
表されるアジド基含有付加重合型モノマーである。(Wherein X is a methyl group or a hydrogen atom) is an azido group-containing addition polymerization type monomer.
【０００７】本発明の化合物中に含まれる末端の（メ
タ）アクリル基は、単独重合、あるいは通常の付加重合
型モノマーと共重合することにより、アジド基をポリマ
ーに導入する役割を担っている。アジド基は、紫外線や
可視光線などの電磁波や電子線等の粒子線に感光して活
性種であるナイトレンを発生し、ナイトレン同士の二量
化反応、二重結合への付加反応、水素引き抜き反応等を
起こし、ポリマー分子間の架橋をもたらして陽画形成を
可能とする。また本発明の化合物中に含まれるアジド基
は、カルコン基と共役の位置にあるため、その紫外線吸
収域が３００ｎｍ以上となっている。The terminal (meth) acrylic group contained in the compound of the present invention plays a role of introducing an azide group into the polymer by homopolymerization or copolymerization with a usual addition polymerization type monomer. The azido group is exposed to electromagnetic waves such as ultraviolet rays and visible rays and particle beams such as electron beams to generate nitrene which is an active species, and is a dimerization reaction between nitrenes, an addition reaction to a double bond, a hydrogen abstraction reaction, etc. And cause cross-linking between polymer molecules to enable positive image formation. Further, the azide group contained in the compound of the present invention is in a conjugated position with the chalcone group, and thus has an ultraviolet absorption region of 300 nm or more.
【０００８】本発明の化合物は、例えば次に示す工程を
経て合成できる（式中、Ｘは、メチThe compound of the present invention can be synthesized, for example, through the steps shown below (wherein X is a methyl group).
【０００９】[0009]
【化３】 Embedded image
【００１０】ル基または水素原子）。即ち、アルコール
溶媒中に、４−アジド−４’−グリシドキシカルコンと
（メタ）アクリル酸とベンジルトリメチルアンモニウム
クロライドとを溶解し加熱反応させることにより得るこ
とができる。Group or hydrogen atom). That is, it can be obtained by dissolving 4-azido-4′-glycidoxychalcone, (meth) acrylic acid, and benzyltrimethylammonium chloride in an alcohol solvent and reacting with heating.
【００１１】本発明の化合物は、単独重合、あるいは通
常の付加重合型モノマーと共重合させることによってポ
リマー中にアジド基を導入することができる。その結果
得られたポリマーは、３００ｎｍ以上に紫外線吸収域を
持つアジド基を持つため高感度な感光性樹脂となる。The compound of the present invention can be introduced with an azide group into the polymer by homopolymerization or copolymerization with a usual addition polymerization type monomer. The polymer obtained as a result has azide groups having an ultraviolet absorption region of 300 nm or more, and thus becomes a highly sensitive photosensitive resin.
【００１２】[0012]
【実施例】以下実施例により本発明を更に説明するが本
発明はこれに限定されるものではない。 実施例 本発明の化合物の合成例 １ ４−アジド−４’−グリシドキシカルコン10.0g(31.3mm
ol)とアクリル酸2.5g(34.7mmol)とベンジルトリメチル
アンモニウムクロライド0.86g(4.6mmol)とをメチルセロ
ソルブ160mlに溶解する。これを７０℃まで昇温して５
時間攪拌する。これをアルカリ水洗したのち、得られた
褐色のペースト状物質を乾燥して本発明の化合物（Ａ）
を得た。化合物（Ａ）の構造は、ＮＭＲ（核磁気共鳴ス
ペクトル分析）、ＩＲ（赤外吸収スペクトル分析）およ
び元素分析により確認した。 NMR(ppm) 4.07(d,2H) 4.16(d,2H) 4.52(m,1H) 5.69(s,1H) 6.02(s,1H) 6.28(m,1H) 7.11(d,2H) 7.17(d,2H) 7.70(d,1H) 7.90(d,1H) 7.94(d,2H) 8.18(d,2H) IR(cm-1) 3422.0 3059.0 3003.0 2930.0 2122.0 1640.0 1605.0 1566.0 1505.0 1423.0 1342.0 1299.0 1256.0 1220.0 1171.0 1126.0 1006.0 985.0 912.0 また、本化合物（Ａ）のＵＶ（紫外線吸収スペクトル）
のチャートを図１に示す。The present invention will be further described with reference to the following examples, but the present invention is not limited thereto. Example Synthesis Example of Compound of the Present Invention 1 4-azido-4′-glycidoxychalcone 10.0 g (31.3 mm
ol), 2.5 g (34.7 mmol) of acrylic acid and 0.86 g (4.6 mmol) of benzyltrimethylammonium chloride are dissolved in 160 ml of methyl cellosolve. Raise it to 70 ° C and
Stir for hours. After washing this with alkaline water, the obtained brown paste-like substance is dried to obtain the compound (A) of the present invention.
I got The structure of the compound (A) was confirmed by NMR (nuclear magnetic resonance spectrum analysis), IR (infrared absorption spectrum analysis) and elemental analysis. NMR (ppm) 4.07 (d, 2H) 4.16 (d, 2H) 4.52 (m, 1H) 5.69 (s, 1H) 6.02 (s, 1H) 6.28 (m, 1H) 7.11 (d, 2H) 7.17 (d, 2H) 7.70 (d, 1H) 7.90 (d, 1H) 7.94 (d, 2H) 8.18 (d, 2H) IR (cm -1 ) 3422.0 3059.0 3003.0 2930.0 2122.0 1640.0 1605.0 1566.0 1505.0 1423.0 1342.0 1299.0 1256.0 1220.0 1171.0 1126.0 1006.0 985.0 912.0 In addition, the UV (ultraviolet absorption spectrum) of this compound (A)
Is shown in FIG.
【００１３】[0013]
【図１】[Figure 1]
【００１４】本発明の化合物の合成例 ２ ４−アジド−４’−グリシドキシカルコン10.0g(31.3mm
ol)とメタアクリル酸2.9g(33.7mmol)とベンジルトリメ
チルアンモニウムクロライド0.86g(4.6mmol)とをメチル
セロソルブ160mlに溶解する。これを７０℃まで昇温し
て５時間攪拌する。これをアルカリ水洗したのち、得ら
れた褐色のペースト状物質を乾燥して本発明の化合物
（Ｂ）を得た。化合物（Ｂ）の構造は、ＮＭＲ（核磁気
共鳴スペクトル分析）、ＩＲ（赤外吸収スペクトル分
析）および元素分析により確認した。 NMR(ppm) 1.88(s,3H) 4.07(d,2H) 4.14(d,2H) 4.53(m,1H) 5.70(s,1H) 6.02(s,1H) 6.25(m,1H) 7.11(d,2H) 7.19(d,2H) 7.72(d,1H) 7.90(d,1H) 7.92(d,2H) 8.20(d,2H) IR(cm-1) 3420.0 3063.0 3000.0 2950.0 2120.0 1652.0 1601.0 1560.0 1505.0 1424.0 1337.0 1297.0 1260.0 1220.0 1170.0 1126.0 1000.0 990.0 910.0 また、本化合物（Ｂ）のＵＶ（紫外線吸収スペクトル）
のチャートを図１に示す。Synthesis Example 2 of Compound of the Present Invention 2 4-azido-4'-glycidoxychalcone 10.0 g (31.3 mm
ol), 2.9 g (33.7 mmol) of methacrylic acid and 0.86 g (4.6 mmol) of benzyltrimethylammonium chloride are dissolved in 160 ml of methyl cellosolve. This is heated to 70 ° C. and stirred for 5 hours. This was washed with alkaline water, and the obtained brown paste-like substance was dried to obtain the compound (B) of the present invention. The structure of the compound (B) was confirmed by NMR (nuclear magnetic resonance spectrum analysis), IR (infrared absorption spectrum analysis) and elemental analysis. NMR (ppm) 1.88 (s, 3H) 4.07 (d, 2H) 4.14 (d, 2H) 4.53 (m, 1H) 5.70 (s, 1H) 6.02 (s, 1H) 6.25 (m, 1H) 7.11 (d, 2H) 7.19 (d, 2H) 7.72 (d, 1H) 7.90 (d, 1H) 7.92 (d, 2H) 8.20 (d, 2H) IR (cm -1 ) 3420.0 3063.0 3000.0 2950.0 2120.0 1652.0 1601.0 1560.0 1505.0 1424.0 1337.0 1297.0 1260.0 1220.0 1170.0 1126.0 1000.0 990.0 910.0 In addition, the UV (ultraviolet absorption spectrum) of this compound (B)
Is shown in FIG.
【００１５】[0015]
【図２】FIG. 2
【００１６】[0016]
【発明の効果】本発明の化合物は、単独重合あるいは通
常の付加重合型モノマーと共重合することによって、３
００ｎｍ以上に紫外線感光域を持つ感光性樹脂が得られ
る。この感光性樹脂は、該波長域の光を透過する工業的
に安価な乳剤被覆製フォトマスクあるいはソーダガラス
製のフォトマスクの使用が可能となる。従ってこの感光
性樹脂は、例えばＬＳＩ用フォトレジスト、プリント基
板用フォトレジスト、印刷版製造用フォトレジスト、ブ
ラウン管蛍光面製造用フォトレジスト、液晶ディスプレ
ー用カラーフィルター製造用フォトレジスト、金属の精
密加工用フォトレジスト等に使用できる。従って本発明
の化合物は感光性樹脂用原料として有用である。INDUSTRIAL APPLICABILITY The compound of the present invention can be homopolymerized or copolymerized with a usual addition-polymerization type monomer to give 3
It is possible to obtain a photosensitive resin having an ultraviolet light sensitive region of 00 nm or more. With this photosensitive resin, it is possible to use an industrially inexpensive emulsion-coated photomask or soda glass-made photomask that transmits light in the wavelength range. Therefore, this photosensitive resin is, for example, photoresist for LSI, photoresist for printed circuit board, photoresist for printing plate production, photoresist for cathode ray tube fluorescent screen production, photoresist for color filter production for liquid crystal displays, photoresist for precision metal processing. It can be used as a resist. Therefore, the compound of the present invention is useful as a raw material for a photosensitive resin.
【図１】図１は実施例１で合成した化合物（Ａ）のＵＶ
チャートである。FIG. 1 is UV of the compound (A) synthesized in Example 1.
It is a chart.
【図２】図２は実施例２で合成した化合物（Ｂ）のＵＶ
チャートである。FIG. 2 is UV of the compound (B) synthesized in Example 2.
It is a chart.
【手続補正書】[Procedure amendment]
【提出日】平成６年１月１８日[Submission date] January 18, 1994
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１４[Correction target item name] 0014
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１４】本発明の化合物の合成例 ２ ４−アジド−４’−グリシドキシカルコン１０．０ｇ
（３１．３ｍｍｏｌ）とメタアクリル酸２．９ｇ（３
３．７ｍｍｏｌ）とベンジルトリメチルアンモニウムク
ロライド０．８６ｇ（４．６ｍｍｏｌ）とをチルセロソ
ルブ１６０ｍｌに溶解する。これを７０℃まで昇温して
５時間攪拌する。これをアルカリ水洗したのち、得られ
た褐色のペースト状物質を乾燥して本発明の化合物
（Ｂ）を得た。化合物（Ｂ）の構造は、ＮＭＲ（核磁気
共鳴スペクトル分析）、ＩＲ（赤外吸収スペクトル分
析）および元素分析により確認した。 Synthesis Example 2 of the compound of the present invention: 10.0 g of 4-azido-4'-glycidoxychalcone
(31.3 mmol) and 2.9 g of methacrylic acid (3
3.7 mmol) and 0.86 g (4.6 mmol) of benzyltrimethylammonium chloride are dissolved in 160 ml of chill cellosolve. This is heated to 70 ° C. and stirred for 5 hours. This was washed with alkaline water, and the obtained brown paste-like substance was dried to obtain the compound (B) of the present invention. The structure of the compound (B) was confirmed by NMR (nuclear magnetic resonance spectrum analysis), IR (infrared absorption spectrum analysis) and elemental analysis.
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１５[Name of item to be corrected] 0015
【補正方法】削除[Correction method] Delete
【手続補正３】[Procedure 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】図面の簡単な説明[Name of item to be corrected] Brief description of the drawing
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【図面の簡単な説明】[Brief description of drawings]
【図１】図１は実施例１で合成した化合物（Ａ）のＵＶ
チャートである。FIG. 1 is UV of the compound (A) synthesized in Example 1.
It is a chart.
Claims (1)
ド基含有付加重合型モノマー。1. A compound of the general formula (In the formula, X is a methyl group or a hydrogen atom), and is an azide group-containing addition polymerization type monomer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7109093A JPH0820568A (en) | 1993-03-05 | 1993-03-05 | Addition polyermizable type monomer containing azide group |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7109093A JPH0820568A (en) | 1993-03-05 | 1993-03-05 | Addition polyermizable type monomer containing azide group |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0820568A true JPH0820568A (en) | 1996-01-23 |
Family
ID=13450495
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7109093A Pending JPH0820568A (en) | 1993-03-05 | 1993-03-05 | Addition polyermizable type monomer containing azide group |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0820568A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016047902A (en) * | 2014-08-28 | 2016-04-07 | 住友ベークライト株式会社 | Polymer compound, coating material, molded product coated with coating material and method for producing the same |
-
1993
- 1993-03-05 JP JP7109093A patent/JPH0820568A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016047902A (en) * | 2014-08-28 | 2016-04-07 | 住友ベークライト株式会社 | Polymer compound, coating material, molded product coated with coating material and method for producing the same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5370894B2 (en) | Alkali-soluble resin and negative photosensitive resin composition containing the same | |
| JP7034175B2 (en) | Polymerizable group-containing fluorene oxime ester-based photoinitiator, production method and its application | |
| KR101473511B1 (en) | Photosensitive graft polymer, and photosensitive resin composition comprising the same | |
| JP4781083B2 (en) | Copolymer containing structural unit having 3,4-epoxytricyclo [5.2.1.02,6] decane ring and process for producing the same | |
| KR20130140096A (en) | Oxime ester compound and photoinitiator containing said compound | |
| KR20160066482A (en) | Black photosensitive resin composition, black matrix and image display device comprising thereof | |
| JP3442173B2 (en) | Color filter dye, color resist containing the same, and color filter | |
| JP4806611B2 (en) | Photosensitive resin composition | |
| JP3643491B2 (en) | COMPOUND, COPOLYMER AND METHOD FOR PRODUCING SAME, PHOTORESIST COMPOSITION, METHOD FOR FORMING PHOTORESIST PATTERN USING THE SAME, AND SEMICONDUCTOR DEVICE | |
| KR940001555B1 (en) | Visible radiation sensitive composition | |
| CN111032720B (en) | Resin, photosensitive resin composition, resin cured film, and image display device | |
| KR20010018075A (en) | Photosensitive resin composition | |
| JP4571188B2 (en) | Display panel with patterned spacer | |
| WO2016184429A1 (en) | Pyrazoline sensitizer and preparation method and use thereof | |
| JPH0820568A (en) | Addition polyermizable type monomer containing azide group | |
| CN110066352B (en) | Oxime ester photoinitiator, preparation method, photosensitive resin composition and application | |
| CN111615650B (en) | Photosensitive resin composition for color filter, image display element, and method for producing color filter | |
| JPH06107617A (en) | Azido group-containing addition polymerizable type monomer | |
| KR20090046108A (en) | Oxim ester compounds, photosensitive composition comprising the same and usage | |
| CN116529670A (en) | Photosensitive resin composition and method for producing photosensitive resin composition | |
| JPH06116222A (en) | Addition polymerization-type monomer bearing azide group | |
| KR101767079B1 (en) | Black photosensitive resin composition and black matrix using the same | |
| JP3163036B2 (en) | Photosensitive compound and photosensitive resin | |
| KR102594321B1 (en) | Photosensitive resin composition and image display device | |
| KR20160071994A (en) | Black photosensitive resin composition, black matrix and image display device comprising thereof |