JPH0644152B2 - Colored photosensitive resin composition - Google Patents
Colored photosensitive resin compositionInfo
- Publication number
- JPH0644152B2 JPH0644152B2 JP27984086A JP27984086A JPH0644152B2 JP H0644152 B2 JPH0644152 B2 JP H0644152B2 JP 27984086 A JP27984086 A JP 27984086A JP 27984086 A JP27984086 A JP 27984086A JP H0644152 B2 JPH0644152 B2 JP H0644152B2
- Authority
- JP
- Japan
- Prior art keywords
- photosensitive resin
- resin composition
- colored
- colored photosensitive
- dye
- 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 - Lifetime
Links
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/008—Azides
- G03F7/012—Macromolecular azides; Macromolecular additives, e.g. binders
- G03F7/0125—Macromolecular azides; Macromolecular additives, e.g. binders characterised by the polymeric binder or the macromolecular additives other than the macromolecular azides
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Optical Filters (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は透明な着色画像を形成するための着色感光性樹
脂組成物に関し更に詳しくは固体撮像素子又はカラー液
晶表示装置等に使用されるカラーフィルター用着色感光
性樹脂組成物に関する。Description: TECHNICAL FIELD The present invention relates to a colored photosensitive resin composition for forming a transparent colored image, more specifically for a color filter used in a solid-state image sensor, a color liquid crystal display device, or the like. The present invention relates to a colored photosensitive resin composition.
従来の技術 VTR用カメラとして需要の大きいカラー固体撮像素子
（例えばCCD,DID,BBD,MOSFET方式等の撮像ＩＣ）及び軽
量化、薄型化の趨勢でCRT方式からの転換が進みつつあ
るカラー液晶表示装置等に用いられるカラーフィルター
は、２種以上の色相に着色された微細な領域を固体撮像
素子あるいは透明基板上に設けることによつて形成され
ている。そして２種以上の色に着色されるべき微細な基
質膜を形成するには微細なパターンを形成しやすく、又
着色が比較的容易であるという理由から感光性樹脂が用
いられている。即ち例えば感光性樹脂をガラス板等の透
明基板上に塗布し乾燥後、その上に所定形状の開口パタ
ーンを有するマスクを介して紫外線を照射して露光部分
を光硬化せしめ、現像処理を経て所定のパターンを形成
せしめたあとこれを水溶性染料等で染色するという操作
を染料を変えて２回以上くりかえして２種以上の色相に
着色された微細なパターンを有する透明な基板等が製造
されている。2. Description of the Related Art A color solid-state image sensor (for example, CCD, DID, BBD, MOSFET type image pickup ICs), which is in great demand as a VTR camera, and a color liquid crystal display which is shifting from the CRT type due to the trend of weight reduction and thinning. A color filter used in an apparatus or the like is formed by providing fine areas colored in two or more kinds of hues on a solid-state image sensor or a transparent substrate. In order to form a fine matrix film to be colored in two or more colors, a photosensitive resin is used because it is easy to form a fine pattern and the coloring is relatively easy. That is, for example, a photosensitive resin is applied on a transparent substrate such as a glass plate and dried, and then ultraviolet rays are radiated through a mask having an opening pattern of a predetermined shape to photo-cure the exposed portion, and a predetermined process is performed after development processing. After the pattern is formed, the operation of dyeing it with a water-soluble dye etc. is repeated twice or more by changing the dye to produce a transparent substrate having a fine pattern colored in two or more hues. There is.
又、上記の染色工程を省くという観点から、ゼラチン水
溶液に酸性染料を溶解させた後、光硬化剤として重クロ
ム酸アンモニウムを加えて感光性着色物をつくり、それ
を用いてカラーフィルターを作製する方法も提案されて
いる（特開昭６１−１７２１０３） 発明が解決しようとする問題点 前記の染色法によるカラーフィルター作製法において
は、カラーフィルターとしての所定の光学特性を満たす
被染色パターン膜の染色濃度がその膜厚に依存するこ
と、又膜の染色性が使用する感光性樹脂の特性および染
色条件（染浴濃度、染浴温度、染浴pH、染色時間、使用
染料等）に影響されやすくカラーフィルター作製におけ
る品質および生産工程管理が煩雑になるという問題があ
る。一方、感光性着色物を使用してカラーフィルターを
作製する方法においては上記染色上の問題はないものの
前記の感光性着色物をつくりそれを用いる方法では所定
の光学特性を満たすに充分な着色濃度が得られないと
か、天然基材であるゼラチン、カゼイン等とその光硬化
剤としての重クロム酸アンモニウムを使用することによ
るその感光性着色物の保存安定性不良および重クロム酸
廃液による環境汚染等の問題を有する。Further, from the viewpoint of omitting the above dyeing step, after dissolving an acidic dye in a gelatin aqueous solution, ammonium dichromate is added as a photo-curing agent to prepare a photosensitive colored product, and a color filter is prepared using the photosensitive colored product. A method has also been proposed (Japanese Patent Laid-Open No. 61-172103). Problems to be Solved by the Invention In the method for producing a color filter by the dyeing method, dyeing of a pattern film to be dyed satisfying predetermined optical characteristics as a color filter. The concentration depends on the film thickness, and the dyeability of the film is easily affected by the characteristics of the photosensitive resin used and the dyeing conditions (dye bath concentration, dye bath temperature, dye bath pH, dyeing time, dyes used, etc.). There is a problem that the quality and production process control in the color filter production become complicated. On the other hand, in the method of producing a color filter using a photosensitive coloring matter, the above-mentioned dyeing problem does not occur, but in the method of using the above-mentioned photosensitive coloring matter and using it, a coloring density sufficient to satisfy predetermined optical characteristics is obtained. Is not obtained, the storage stability of the photosensitive colored product is poor due to the use of natural base materials such as gelatin and casein, and ammonium dichromate as a photo-curing agent, and environmental pollution due to dichromic acid waste liquid. Have the problem of.
問題点を解決するための手段 本発明者らは前記したような問題点を解決するために鋭
意検討を重ねた結果、本発明に至ったものである。即ち
本発明は、 (i)親水性樹脂 (ii)ビスアジド化合物 (iii)上記親水性樹脂及びビスアジド化合物の合計に対
し20〜50％の割合の水溶性染料 からなる画像形成用着色感光性樹脂組成物を提供する。Means for Solving the Problems The present inventors have achieved the present invention as a result of intensive studies for solving the above-mentioned problems. That is, the present invention provides (i) a hydrophilic resin (ii) a bisazide compound (iii) a colored photosensitive resin composition for image formation comprising a water-soluble dye in a proportion of 20 to 50% with respect to the total amount of the hydrophilic resin and the bisazide compound. Provide things.
本発明を具体的に説明する。The present invention will be specifically described.
本発明に使用される親水性樹脂としては通常露光後の現
像処理において水あるいは親水性溶媒（例えばアルコー
ル、メチル（エチル）セロソルブ、ジオキサン、Ｎ−メ
チルピロリドン等が用いられることを考慮してこれらに
溶解性を有する樹脂が好ましい。そのような親水性樹脂
の具体例としてはポリビニルアルコール、ポリビニルピ
ロリドン、ポリアミド樹脂、カゼイン、ゼラチン等が挙
げられる。このうちポリアリミド樹脂（ナイロン樹脂）
としては重縮合成分として水溶性のピペラジン誘導体を
含んだもの、スルホン酸基、カルボキシル基を導入した
ポリアミド樹脂等が用いられる。As the hydrophilic resin used in the present invention, water or a hydrophilic solvent (for example, alcohol, methyl (ethyl) cellosolve, dioxane, N-methylpyrrolidone, etc.) is usually used in the development treatment after exposure in consideration of these. Soluble resins are preferable, and specific examples of such hydrophilic resin include polyvinyl alcohol, polyvinylpyrrolidone, polyamide resin, casein, gelatin, etc. Among them, polyarimid resin (nylon resin)
As the polycondensation component, a substance containing a water-soluble piperazine derivative, a sulfonic acid group- or carboxyl group-introduced polyamide resin, or the like is used.
ビスアジド化合物の例としては４，４′−ジアジドスチ
ルベン−２，２′−ジスルホン酸ナトリウム、２，６−
ビス（４−アジドベンザール）アセトン２−スルホン
酸、２，６−ビス（４−アジドベンザール）アセトン
２，２′−ジスルホン酸、２，６−ビス（４−アジドベ
ンザール）シクロヘキサノン−２，２′−ジスルホン
酸、２，６−ビス（４−アジドベンザール）メチルシク
ロヘキサノン−２，２′−ジスルホン酸等が挙げられ
る。Examples of bisazide compounds include sodium 4,4'-diazidostilbene-2,2'-disulfonate, 2,6-
Bis (4-azidobenzal) acetone 2-sulfonic acid, 2,6-bis (4-azidobenzal) acetone 2,2'-disulfonic acid, 2,6-bis (4-azidobenzal) cyclohexanone-2 , 2'-disulfonic acid, 2,6-bis (4-azidobenzal) methylcyclohexanone-2,2'-disulfonic acid and the like.
水溶性染料としては水あるいは親水性溶媒あるいは両者
の混合系に溶解する酸性染料、直接染料、カチオン染料
が好ましい。The water-soluble dye is preferably an acid dye, a direct dye or a cationic dye, which is soluble in water, a hydrophilic solvent or a mixture of both.
染料の親水性樹脂及びビスアジド化合物の合計に対する
割合（固型分）は２０％〜５０％である。The ratio (solid content) of the dye to the total of the hydrophilic resin and the bisazide compound is 20% to 50%.
又、ビスアジド化合物の親水性樹脂に対する割合（固型
分）は、２％〜４０％、好ましくは５％〜３０％、更に
好ましくは１０％〜２０％である。The ratio (solid content) of the bisazide compound to the hydrophilic resin is 2% to 40%, preferably 5% to 30%, more preferably 10% to 20%.
上記のようにして得た着色感光性樹脂組成物を用いて透
明着色画像を形成するには、この組成物を5.0〜５０％
含有する水溶液又は親水性溶媒（例えばメタノール、エ
タノール又はこれらと水との混合溶媒）溶液としたのち
基板上にスピンナー、ロールコーター、ディップコータ
ー、ホイルコーター、バーコーター等の塗布装置により
乾燥時の膜厚が0.1〜１０μｍ、好ましくは0.5〜３μｍ
程度になるように塗布し乾燥後マスクを介してキセノン
ランプ、メタルハライドランプ、(超)高圧水銀灯等の光
源を用いてパターン露光する。次いで水あるいは親水性
溶媒あるいは両者の混合溶媒の現像液でスプレー現像あ
るいはデイップ現像することにより非露光部を選択的に
除去すればよい。To form a transparent colored image using the colored photosensitive resin composition obtained as described above, 5.0% to 50% of this composition is used.
Aqueous solution or hydrophilic solvent (for example, methanol, ethanol or a mixed solvent of these and water) containing solution and then dried on the substrate by a coating device such as spinner, roll coater, dip coater, foil coater, bar coater Thickness is 0.1-10 μm, preferably 0.5-3 μm
It is applied to a desired extent and dried, and then pattern exposure is performed through a mask using a light source such as a xenon lamp, a metal halide lamp, or a (super) high pressure mercury lamp. Next, the non-exposed areas may be selectively removed by spray development or dip development with a developing solution of water or a hydrophilic solvent or a mixed solvent of both.
なお基板としては透明ガラス板、透明樹脂フィルム、固
体撮像素子等を用いることができる。A transparent glass plate, a transparent resin film, a solid-state image sensor, or the like can be used as the substrate.
本発明の着色感光性樹脂組成物はカラーフィルター作製
における品質及び生産工程の管理が容易で、カラーフィ
ルター作成時における重クロム酸廃液の放出等環境汚染
の懸念もない。又本発明の着色感光性樹脂組成物はカラ
ーフィルターとして十分な染色濃度を与えると共にその
透明性、解像性がすぐれている。The colored photosensitive resin composition of the present invention is easy to control the quality and production process in producing a color filter, and there is no concern about environmental pollution such as discharge of dichromic acid waste liquid in producing a color filter. Further, the colored photosensitive resin composition of the present invention provides a sufficient dyeing density as a color filter and has excellent transparency and resolution.
実施例 本発明を実施例によって更に詳細に説明する。なお実施
例中ことわりのない限り、部は重量部を、又％は重量パ
ーセントを表わすものとする。EXAMPLES The present invention will be described in more detail by way of examples. In the examples, "parts" means "parts by weight" and "%" means "percentages by weight" unless otherwise specified.
実施例１ 感光性樹脂着色組成物を以下のように調製した。Example 1 A photosensitive resin coloring composition was prepared as follows.
20％水溶性ナイロン （東レ（株）製、商品名Ａ−９０）水溶液 10部 ４，４′−ジアジドスチルベン−２，２′−ジスルホン
酸ナトリウム （シンコー技研（株）製） 0.3部 Blue５Ｐ（日本化薬（株）製、青色酸性染料） １
部 次いでこの青色感光性樹脂組成物をガラス基板上に0.7
μｍの膜厚で回転塗布し、１００℃で１５分乾燥後マス
クを介して露光した。続いて水中で１分浸漬して現像後
９０℃で１０分乾燥させて青色画像を得た。このものは
従来の染色法で得られる画像と比べて遜色のないもので
あった。20% water-soluble nylon (manufactured by Toray Industries, Inc., trade name A-90) aqueous solution 10 parts 4,4′-diazidostilbene-2,2′-sodium disulfonate (manufactured by Shinko Giken Co., Ltd.) 0.3 parts Blue5P ( Nippon Kayaku Co., Ltd., blue acid dye) 1
Then, the blue photosensitive resin composition was applied to a glass substrate with 0.7
It was spin-coated at a film thickness of μm, dried at 100 ° C. for 15 minutes, and then exposed through a mask. Subsequently, it was immersed in water for 1 minute, developed, and dried at 90 ° C. for 10 minutes to obtain a blue image. This was comparable to the image obtained by the conventional dyeing method.
実施例２〜３ 表に示される着色感光性樹脂組成物を調製した。Examples 2 to 3 Colored photosensitive resin compositions shown in Tables were prepared.
これらの着色感光性樹脂組成物を用い実施例１同様にし
て得られた着色画像は従来の染色法で得られる画像に比
べて遜色のないものであった。 The colored image obtained by using these colored photosensitive resin compositions in the same manner as in Example 1 was comparable to the image obtained by the conventional dyeing method.
発明の効果 従来のカラーフィルター作製の際にみられる染色するこ
とに伴なう品質および生産工程管理上の煩雑さを少なく
し、更に従来のゼラチン／重クロム酸アンモニウム系着
色剤にみられる保存安定性、環境汚染の問題を解決した
着色感光性樹脂組成物がえられた。Advantages of the Invention The quality and production process control complexity associated with dyeing, which is seen in conventional color filter production, is reduced, and the storage stability found in conventional gelatin / ammonium dichromate colorants is improved. A colored photosensitive resin composition that solves the problems of properties and environmental pollution was obtained.
Claims (1)
対し20〜50％の割合の水溶性染料 からなる画像形成用着色感光性樹脂組成物1. A colored photosensitive resin composition for image formation comprising (i) a hydrophilic resin, (ii) a bisazide compound, (iii) a water-soluble dye in a proportion of 20 to 50% with respect to the total of the hydrophilic resin and the bisazide compound. object
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27984086A JPH0644152B2 (en) | 1986-11-26 | 1986-11-26 | Colored photosensitive resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27984086A JPH0644152B2 (en) | 1986-11-26 | 1986-11-26 | Colored photosensitive resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63133148A JPS63133148A (en) | 1988-06-04 |
| JPH0644152B2 true JPH0644152B2 (en) | 1994-06-08 |
Family
ID=17616659
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27984086A Expired - Lifetime JPH0644152B2 (en) | 1986-11-26 | 1986-11-26 | Colored photosensitive resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0644152B2 (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5952549B2 (en) * | 1981-08-12 | 1984-12-20 | 株式会社日立製作所 | Color solid-state image sensor |
| JPS58164677A (en) * | 1982-03-25 | 1983-09-29 | Toshiba Corp | Composition and method for forming fluorescent screen on picture tube |
| JPS592009A (en) * | 1982-06-29 | 1984-01-07 | Toshiba Corp | Manufacture of color filter |
| JPS5972410A (en) * | 1982-10-18 | 1984-04-24 | Mitsubishi Electric Corp | Manufacture of color light separating filter |
| JPS60129738A (en) * | 1983-12-16 | 1985-07-11 | Agency Of Ind Science & Technol | transparent colored images |
-
1986
- 1986-11-26 JP JP27984086A patent/JPH0644152B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63133148A (en) | 1988-06-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4203765A (en) | Etch bleaching liquid with iron(III)ions | |
| JPS62127735A (en) | Photosensitive resin composition and preparation of color filter by using it | |
| JPH0834923A (en) | Method for producing black photosensitive resin composition and black matrix | |
| US4469772A (en) | Water developable dye coating on substrate with two diazo polycondensation products and water soluble polymeric binder | |
| US3598586A (en) | Aromatic azide material and process for producing color images | |
| US4391894A (en) | Colored photosensitive composition | |
| JP2643307B2 (en) | Photosensitive resin composition | |
| JPH0644152B2 (en) | Colored photosensitive resin composition | |
| JP2926364B2 (en) | Negative photosensitive composition and method for producing color filter using the same | |
| JP2668782B2 (en) | Color pattern manufacturing method | |
| JPH01128064A (en) | Photocurable resin composition | |
| DE2949022A1 (en) | METHOD FOR PRODUCING CROSS-LINKED POLYMER IMAGES ON A LAYER | |
| DE3008824C2 (en) | ||
| JPH01130102A (en) | Method for dyeing coating film | |
| US3407065A (en) | Photosensitive lithographic plate coating comprising dichromated colloid and unmordanted mordant dye | |
| US1953175A (en) | Subtractive two-color picture | |
| JP2696921B2 (en) | Manufacturing method of color filter | |
| JP2006010910A (en) | Colored photosensitive composition | |
| JP2652064B2 (en) | Color filter | |
| JPS63125934A (en) | Photosensitive resin composition | |
| DE3831290A1 (en) | LIGHT-SENSITIVE MATERIAL AND PICTURE-MAKING METHOD | |
| JP2800940B2 (en) | Manufacturing method of color filter | |
| JPH01241541A (en) | Colored pattern forming method | |
| JPS5972410A (en) | Manufacture of color light separating filter | |
| JPH04218001A (en) | Color filter |