TW200540465A - Color filter - Google Patents
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- TW200540465A TW200540465A TW094114988A TW94114988A TW200540465A TW 200540465 A TW200540465 A TW 200540465A TW 094114988 A TW094114988 A TW 094114988A TW 94114988 A TW94114988 A TW 94114988A TW 200540465 A TW200540465 A TW 200540465A
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/201—Filters in the form of arrays
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D11/00—Producing optical elements, e.g. lenses or prisms
- B29D11/00634—Production of filters
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- 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
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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- 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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
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- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Ophthalmology & Optometry (AREA)
- Mechanical Engineering (AREA)
- Materials For Photolithography (AREA)
- Optical Filters (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
Abstract
Description
20Q540465 九、發明說明: 【發明所屬之技術領域】 本發明係關於一種用於LCD、影像感測器等之彩色濾光 片,特別關於一種適用於影像感測器之彩色濾光片。 【先前技術】 . 影像感測器用彩色濾光片係基於CCD等固體攝影元件 . 之解像度提高的要求,於1 9 9 0年代後半段,像素的大小約 爲5 μπι之大小,成爲第五代之現在,已逐漸縮小至2.5 μπι φ 以下之大小。 如此的話,隨著像素變小,關於藉由微影術所形成的像 素形狀之技術性問題已逐漸顯現。 亦即,藉由微影術而得的彩色濾光片製造之際,於基板 上進行塗布而形成了已被分散顏料或溶解染料所著色的光 阻劑塗膜上,透過光罩而進行像素圖案之曝光,並進行鹼顯 像而形成像素,隨著像素變小,像素形狀之倒塌將變多,於 與相鄰的其他顏色像素之間形成間隙,導致混合將變多。因 • 此,於固體攝影元件之再現影像的雜訊將變大、模糊將顯 現,容易損害畫質。 配合藉由微影術而得的像素圖案之形成,使已進行圖案 曝光之光阻劑塗膜中的光硬化性成分得以硬化,接著,藉由 顯現處理,進行非曝光部之光阻劑膜的溶解去除而形成像素 _ 圖案。因曝光而得的光阻劑膜之硬化若不足夠的話,因曝光 而得的光阻劑膜之光硬化,某種程度之曝光量爲必要的。換 言之,爲了使基板上之像素得以密著,某種程度之曝光爲必 200540465 要的。於其上,爲了得到忠於光罩圖案形狀之顯像圖案,更 多之曝光量爲必要的。 , 但是’像素圖案若變小的話,爲了保持對基板之密著性 的曝光量便已超過占有像素圖案之曝光量。而且,所顯像之 像素圖案較原本光罩之像素圖案爲大,形狀將改變而呈現圓 形。 針對於此,可列舉一種預估如此寬度而預先縮小光罩圖 案之光透過部分後進行曝光的方法,但是,此方法並無法防 Φ止形狀之變化。 另外,必須正確控制爲了形成一定尺寸之圖案的曝光 量,但是,實用上如此正確之控制爲困難的。 因此,尋求圖案尺寸之曝光量依存性爲小的著色感光性 組成物。 作爲圖案尺寸之曝光量依存性爲小的著色感光性組成 物,已有人提出數種含有磷系或硫系之抗氧化劑等的著色感 光性組成物(參照專利文獻1〜3 ),該任一篇專利文獻均是 φ有關於欲改良圖案尺寸曝光量依存性之發明。 然而,揭示於此等專利文獻之發明主要以液晶顯示裝置 用彩色濾光片之改良爲目的,像素之大小約爲1 〇〇/xm。近年 來,爲了忠實地重現影像感測器用之5 /xm以下的像素圖案形 ^ 狀,任一篇專利文獻之曝光量依存性仍不完備。 - 最近,已有人提出相關之專利文獻:一種改良使用鹼可 溶性樹脂之單體成分爲(甲基)丙烯酸烷基聚環氧乙烷酯之 共聚物的彩色濾光片用感光性著色樹脂組成物之塗布適宜 200540465 性與顯像特性(參照專利文獻4 ); 一種改良鹼可溶性樹脂 之單體成分爲(甲基)丙烯酸烷基聚環氧乙烷酯之共聚物的 彩色濾光片用感光性著色樹脂組成物之塗布適宜性(參照專 利文獻5 ); —種使用具有環氧乙烷側鏈作爲顏料分散用黏 結劑之丙烯酸系共聚物(參照專利文獻6 )等,但是,爲了 忠實地重現影像感測器用之5 μηι以下的像素圖案形狀,該任 一種專利文獻仍不完備。 【專利文獻1】日本公開專利第2003 -25 5 5 24號公報 ρ 【專利文獻2】日本公開專利第2003 -2 5 5 5 2 5號公報 【專利文獻3】日本公開專利第2003 -3 3 0 1 7 1號公報 【專利文獻4】日本公開專利第2003-222997號公報 【專利文獻5】曰本公開專利第2003-24 1 3 68號公報 【專利文獻6】刊登專利第2665 696號公報 【發明內容】 發明所欲解決之技術問穎 因而,本發明之目的在於提供一種彩色濾光片,其係藉 φ由微影術而將所得到的彩色濾光片之像素控制成所要之大 小、形狀。 解決問顆之枝術丰段 有鑑於如此之現狀,本發明人等進行鑽硏的結果,發現 ~ 若使用相對於曝光強度之顯像後的線寬變化率爲7.5x10 5/xm · m2/J以下之光硬化性組成物的話,解決了該課題而完 成本發明。 亦即,本發明提出了下列各項: 200540465 * , (1 ) 一種彩色濾光片,其係由基板上所形成的厚度爲 _ 2.0/xm以下、邊長爲由2.5/xm以下之數種顏色的像素而成 .的;及其特徵爲:該像素係藉由微影術而由含有著色劑與光 硬化性成分之光硬化性組成物所形成的,並且,對於利用下 列顯像條件(I )〜(III )而進行浸置式顯像時之該光硬化 性組成物塗膜曝光強度的顯像後之線寬變化率爲7.5><10-5μιιι · m2/J 以下。 (I )顯像劑係四甲基銨氫氧化物(TMAH )之0.3質量 φ %水溶液20Q540465 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a color filter for an LCD, an image sensor, and the like, and particularly to a color filter suitable for an image sensor. [Prior technology]. Color filters for image sensors are based on solid-state imaging elements such as CCDs. In the latter half of the 1990s, the pixel size was about 5 μπι, which became the fifth generation. At present, it has gradually reduced to a size below 2.5 μπι φ. In this case, as the pixels become smaller, technical problems regarding the shape of the pixels formed by lithography have gradually emerged. That is, when manufacturing a color filter obtained by lithography, coating is performed on a substrate to form a photoresist coating film colored with dispersed pigments or dissolved dyes, and pixels are transmitted through a photomask. The pattern is exposed and the alkali is developed to form a pixel. As the pixel becomes smaller, the shape of the pixel will collapse, and a gap will be formed between adjacent pixels of other colors, resulting in more mixing. Therefore, the noise of the reproduced image on the solid-state imaging element will become larger, and blurring will appear, which will easily damage the image quality. In combination with the formation of a pixel pattern obtained by lithography, the photocurable component in the photoresist coating film subjected to pattern exposure is cured, and then, the photoresist film in the non-exposed portion is subjected to a development process Dissolve and remove to form a pixel_ pattern. If the hardening of the photoresist film obtained by the exposure is not sufficient, the light hardening of the photoresist film obtained by the exposure requires a certain amount of exposure. In other words, in order to make the pixels on the substrate dense, a certain degree of exposure is necessary. On top of this, in order to obtain a developing pattern that is faithful to the shape of the mask pattern, a larger amount of exposure is necessary. However, if the pixel pattern becomes smaller, the exposure amount to maintain the adhesion to the substrate will exceed the exposure amount of the occupied pixel pattern. Moreover, the pixel pattern developed is larger than the pixel pattern of the original mask, and the shape will change to a round shape. In view of this, a method of estimating the width and reducing the light transmission portion of the mask pattern in advance and then exposing it can be cited, but this method cannot prevent the change in shape. In addition, it is necessary to accurately control the exposure amount in order to form a pattern of a certain size. However, such accurate control is difficult in practice. Therefore, a coloring photosensitive composition having a small pattern size-dependent exposure amount is sought. As a color-sensitive photosensitive composition having a small pattern size exposure dependence, there have been proposed several types of color-sensitive photosensitive compositions containing a phosphorus-based or sulfur-based antioxidant (see Patent Documents 1 to 3). Each of the patent documents is an invention concerning the dependency of the pattern size on the exposure amount. However, the inventions disclosed in these patent documents are mainly for the purpose of improving color filters for liquid crystal display devices, and the pixel size is about 1000 / xm. In recent years, in order to faithfully reproduce the pixel pattern shape of 5 / xm or less used for image sensors, the exposure dependency of any patent document is still incomplete. -Recently, a related patent document has been proposed: an improved photosensitive color resin composition for a color filter using a monomer component of an alkali-soluble resin as a copolymer of alkyl (meth) acrylate polyethylene oxide The coating is suitable for 200540465 properties and development characteristics (refer to Patent Document 4); an improved alkali-soluble resin whose monomer component is a (meth) acrylic acid alkylpolyethylene oxide copolymer for color filters Coating suitability of colored resin composition (refer to Patent Document 5);-an acrylic copolymer (refer to Patent Document 6) using an ethylene oxide side chain as a pigment dispersing adhesive, etc. The shape of the pixel pattern of 5 μm or less used in image sensors is still incomplete. [Patent Document 1] Japanese Laid-Open Patent Publication No. 2003 -25 5 5 24 ρ [Patent Document 2] Japanese Laid-Open Patent Publication No. 2003 -2 5 5 5 2 5 [Patent Literature 3] Japanese Laid-Open Patent Publication No. 2003 -3 3 0 1 7 1 [Patent Literature 4] Japanese Laid-Open Patent Publication No. 2003-222997 [Patent Literature 5] Japanese Patent Publication No. 2003-24 1 3 68 [Patent Literature 6] Published Patent Publication No. 2665 696 [Summary of the Invention] The technical problem to be solved by the invention is therefore the object of the present invention to provide a color filter which controls the pixels of the obtained color filter to a desired size by lithography by φ ,shape. In view of this situation, the present inventors performed drill collars and found out that if the line width change rate after using imaging with respect to exposure intensity is 7.5x10 5 / xm · m2 / When the photocurable composition is J or less, this problem is solved and the present invention has been completed. That is, the present invention proposes the following items: 200540465 *, (1) A color filter, which is formed by a substrate with a thickness of _2.0 / xm or less and a side length of 2.5 / xm or less The pixel is made of a color; and the characteristic is that the pixel is formed by a photolithography composition containing a colorant and a photohardenable component by lithography, and the following development conditions are used ( I) to (III) and when the immersion development is performed, the line width change rate after development of the exposure intensity of the coating film of the photocurable composition after development is 7.5 > < 10-5 μm · m2 / J or less. (I) 0.3 mass φ% aqueous solution of developer based on tetramethylammonium hydroxide (TMAH)
(Π )顯像溫度爲3 5 °C (ΠΙ )顯像時間爲60秒 (2 )揭示於(i )之彩色濾光片,其中光硬化性組成物 係包含於分子中具有聚環氧烷鏈與/或甲基丙烯酸羥乙酯 (HEMA)之丙嫌酸系樹脂。 (3 )揭示於(2 )之彩色濾光片,其中丙烯酸系樹脂中 之聚苯乙烯換算重量平均分子量爲5000〜50000。 • ( 4 )揭示於(2 )之彩色濾光片,其中丙烯酸系樹脂中 之聚環氧烷鏈含量的莫耳比爲5〜25莫耳%。 (5 )揭示於(3 )之彩色濾光片,其中丙烯酸系樹脂中 • 之聚環氧烷鏈含量的莫耳比爲5〜2 5莫耳%。 (6 )揭示於(2 )至(5 )項中任一項之彩色濾光片, 其中丙燒酸系樹脂中之聚環氧烷鏈爲聚環氧乙烷鏈,並且, 聚環氧乙烷(E〇)之加成莫耳數η爲2〜25。 (7 )揭示於(2 )之彩色濾光片,其中丙烯酸系樹脂中 200540465 之甲基丙烯酸羥乙酯含量的莫耳比爲1 〇〜3 〇莫耳%。 “ 【發明之實施態樣】 •本發明之彩色濾光片,其係由基板上所形成的厚度爲 2.0/xm以下、邊長爲由2.5 μπι以下之數種顏色的像素而成 的;及其特徵爲··該像素係藉由微影術而由含有著色劑與光 硬化性成分之光硬化性組成物所形成的,並且’對於利用該 顯像條件(I )〜(III )而進行浸置式顯像時之該光硬化性 組成物塗膜曝光強度的顯像後之線寬變化率爲 7.5><10-5μιη · xn2/J 以下。 本發明之彩色濾光片像素之大小,其邊長爲2 · 5 ΜΠΙ以 下,尤以2.0/xm以下較佳,1 ·5μηι以下更爲理想。 另外,像素之厚度爲2.0/xm以下,1 .5/xm以下較佳,尤 以1.2μιη以下更爲理想。 對於利用該顯像條件(I )〜(111 )而進行浸置式顯像 時之該光硬化性組成物塗膜曝光強度的顯像後之線寬變化 率爲 7.5 X 1 0·5μπι · m2/J 以下,較宜爲 6.〇χ 1 0_5μηι · m2/J 以 • 下,尤以3.〇xl(T5/xm · m2/J以下更爲理想。針對具有如此線 寬變化率之光硬化性組成物,進行如下之敘述。 <光硬化性組成物> 本發明所用之光硬化性組成物中含有著色劑、光硬化性 成分。 其中,「光硬化性成分」係指常用於微影術的光硬化性 組成物,其包含黏結劑樹脂(鹼可溶性樹脂等)、感光性聚 合成分(光聚合成單體等)、光聚合起始劑等。 200540465 [著色劑] '能夠用於本發明之著色劑並未予以特別限定,可以使用 •一種習知之各種染料或顏料或是混合二種以上後予以使用。 能夠用於本發明之顏料,可以使用習知之各種無機顏料 或有機顏料。另外,不論是無機顏料或有機顏料,若考量高 透過率的話,則較宜爲盡可能細的;若考量操作性的話,該 顏料之平均粒徑較宜爲 〇·(Π〜〇.1/χιη ;更佳爲 0.01〜 0·0 5/xm。另外,該無機顏料可列舉:金屬氧化物、金屬錯鹽 ® 等所示之金屬化合物,具體而言,可列舉:鐵、鈷、鋁、鎘、 鉛、銅、鈦、鎂、鉻、鋅、銻等金屬氧化物與該金屬之複合 氧化物。 例J如,該有機顏料可列舉: C.I.顏料黃色 n,24,31,53,83,93,99,108,109,110, 138,139,147,150,151,154,155,167,180,185,199 ; c · I ·顏料橙色 3 6,3 8,4 3,7 1 ; C·1·顏料紅色 81,105,122,149,150,155,171,175, 鲁 176,177,209,220,224,242,25 4,255,264,270 ; c · I ·顏料紫色 1 9,2 3,3 2,3 9 ; C.I.顏料藍色 1,2,15,15: 1,15: 3,15: 6,16,22, 60, 66 ; C ·1 ·顏料綠色7,3 6,3 7 ; C ·1 ·顔料褐色2 5,2 8 ; c · I ·賴料黑色1,7 ; 碳黑等。 -10- 200540465 f * 於本發明申請案能夠較宜使用之顏料,可列舉下列之顏 料。但是,本發明並非局限於此等顏料。 C.I.顏料黃色 11,24,108,109,110,138,1 3 9, 1 50, 151, 154, 167, 180, 185; C · I.顏料橙色3 6,7 1 ; C.I·顏料紅色 122,150,171,175,177,209,224,242, 25 4,25 5,264 ; C.I.顏料紫色 19,23,32 ; _ C.I·顏料藍色 15: 1,15: 3,15: 6,16,22,60,66; C.I·顏料黑色1。 此等有機顏料可以單獨使用,或是也可以爲了提高色純 度而使用各種組合。以下,顯示該組合之具體例。例如,紅 色顏料可以單獨使用蒽醌系顏料、茈系顏料、二氧代吡咯并 吡咯系顏料,或是也可以使用此等顏料之至少一種與二重氮 系黃色顏料、異吲哚滿系黃色顏料、奎酞酮系黃色顏料或與 茈系紅色顏料之混合等。例如,蒽醌系顏料可列舉:C.〗.顏 鲁料紅色177 ;茈系顏料可列舉:C·;[•顏料紅色155、C·;!.顏料 紅色2 2 4 ;二氧代吡咯并吡咯系顏料可列舉:c ·;[ •顏料紅色 2 5 4 ;基於顏色再現性之觀點,較宜爲與c . I.顏料黃色1 3 9 之混合。另外,紅色顏料與黃色顏料之質量比較宜爲i 00: 5〜 1 〇 0 : 7 5。若逾越此範圍的話,將有難以抑制光透過率且無 法提高顏色純度之情形。再者,較宜之質量比爲1 〇 〇 : ;[ 〇〜 100: 50 ° 另外’綠色顏料可以單獨使用鹵化酞菁系顏料,或是可 -11- 200540465 以使用鹵化駄靑系顏料與一重氣系黃色顏料、奎駄酮系萑色 - 顏料、甲亞胺系黃色顏料或異吲哚滿系黃色顏料之混合。例 -如,如此之例子,較宜爲C.I.顏料綠色7, 3 6, 3 7與d•顏料 黃色83、C.I.顏料黃色138、C.I·顏料黃色139、c.I·顏料黃 色150、C.I.顏料頁色180或C.I.顏料黃色185之混合。綠 色顏料與黃色顏料之質量比較宜爲1〇〇 : 5〜100 : 15〇。 藍色顏料可以單獨使用酞菁系顏料,或是可以使用駄菁 系顏料與二噁阱系紫色顏料之混合。例如,較宜爲C.I.顏料 鲁藍色15: 6與C.I·顏料紫色23之混合。藍色顏料與紫色顏 料之質量比較宜爲100: 0〜100: 30。 於本發明,著色劑爲染料之情形,均勻溶於組成物中而 得到光硬化性著色樹脂組成物。 能夠作爲構成本發明組成物之著色劑使用的染料並無 特別之限制,可以使用作爲習知彩色濾光片用之習知染料。 例如,可以使用下列專利所揭示之色素:日本公開專利第昭 64-90403 、昭 64-91102 、平 1-94301 、平 6-11614 、平 _ 5-333207 、平 6-35183 、平 6-51115 、平 6-194828 、平 8-211599、平 4-249549、平 10-123316、平 11-302283、平 7-286107、2001-4823、平 8-15522、平 8-2977卜平 8-146215、 平 11-343437 、平 8-62416 、 2002-14220 、 2002-14221 、 2002-14222 、 2002-14223 平 8-302224 、平 8-73758 、平 ' 8- 1 79 1 20、平8-151531號公報;專利刊登第2 5 92207號; 美國專利第4,808,501、5,667,920、5,059,500號說明書等。 化學構造可以使用下列之染料:吡唑偶氮系、苯胺偶氮 -12- 200540465 • 1 系、三苯基甲烷系、蒽醌系、蒽吡啶酮、苯亞甲基系、氧雜 '菁系、吡唑三氮雜茂偶氮系、吡啶酮偶氮系、菁系、吩噻阱 -系、吡啶吡唑偶氮甲烷系、咕噸系、酞菁系、苯并吡喃系、 靛藍系等。 另外,進行水或鹼性顯像液之光阻劑系的情形,基於藉 由顯像而完全去除光未照射部之黏結劑與/或染料的觀點, 有能夠採用酸性染料與/或其衍生物之情形。 除此之外,能夠有效使用直接染料、鹼性染料、媒染染 φ 料、酸性媒染染料、不溶偶氮染料、分散染料、油染染料、 食品染料與/或此等之衍生物等。 只要該酸性染料具有磺酸或羧酸等之酸性基即可,並未 予以特別限定,考量有機溶劑或顯像液之溶解性、與鹼性化 合物之鹽形成性、吸光度、與組成物中其他成分之相互作 用、耐光性、耐熱性等全般所必要之性能而加以選擇。 以下,列舉該酸性染料之具體例,但是,並非局限於此 等例子。例如,酸茜素紫N ;酸黑1, 2, 24, 48 ;酸藍1,7, 9, • 15,18,23,25,27,29,40,45,62,70,74,80,83,86,87, 90,92,103,112,113,120,129,138,147,158,171,182, 1 92, 24 3,3 24: 1 ;酸鉻紫 K;酸品紅;酸綠 1,3, 5, 9,16, 25, 27,50;酸橙 6,7,8,10,12,50,51,52,56,63,74,95;酸 紅 1, 4,8,14,17,18,26,27,29,31,34,35,37,42,44, 50, 51,52,57,66,73,80,87,88, 91,92,94, 97,103,111, 114,129,133,134,138,143,145,150,151,158,176,183, 198,211,215,216,217,249,252,257,260,266,274;酸紫 -13- 200540465 6B,7, 9,17,19 ;酸黃 1,3,7,9,11,17,23, 25,29,34,36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116, 184, 24 3 ;食用頁色3,與此等染料之衍生物。 其中,該酸性染料較宜爲酸黑24 ;酸藍23, 25, 29, 62, 80,86,87,92,138,158,182,243,324: 1,·酸橙 8,51,56, 63,74;酸紅 1,4,8,34,37,42,52,57,80,97,114,143, 145,151,183,217;酸紫 7;酸黃 17,25, 2 9, 3 4, 42,72,76, 99,1 1 1,1 12,1 14,1 16,1 84, 243 ;酸綠 25 等染料與此等染 φ 料之衍生物。 另外,除此之外,偶氮系、咕噸系、酞菁系之酸性染料 也較佳,較宜使用C . I.溶劑藍4 4,3 8 ; C . I.溶劑橙4 5 ;若丹 明B ;若丹明1 1 0等酸性染料與此等染料之衍生物。 本發明之光硬化性組成物全部固形成分中之著色劑含 有率並未予以特別限定,較宜爲3 0〜6 0質量%。著色劑若過 少的話,將有無法得到作爲彩色濾光片的適當色度之傾向。 於本發明,基於提高顏料分散性之目的,能夠添加習知 馨之顏料分散劑或界面活性劑。此等分散劑可以使用許多種之 化合物,例如,酞菁衍生物(市售品EFKA-745 ( EFKA公司 製))、Solspers 5 000 ( Zeneca (股)製);有機矽氧烷聚 合物KP341(日本信越化學工業(股)製)、(曱基)丙烯 酸系(共)聚合物 Polyflower Νο·75、Νο.90、Νο·95 (日本 • 共榮社油脂化學工業(股)製)、W001 (日本裕商製)等 之陽離子系界面活性劑;聚環氧乙烷月桂基醚、聚環氧乙烷 硬酯醯醚、聚環氧乙烷油醚、聚環氧乙烷辛基苯基醚、聚環 -14- 200540465 氧乙烷壬基苯基醚、聚乙二醇二月桂酯、聚乙二醇二硬脂酸 酯、山梨糖醇酐脂肪酸酯等非離子系界面活性劑;wo 04、 W0 05、W01 7 (日本裕商製)等之陰離子系界面活性劑; EFKA-46、EFKA-47、EFKA-47EA、EFKA 聚合物 100、EFKA 聚合物400、EFKA聚合物401、EFKA聚合物450(以下, 日本森下產業(股)製)、Disperse aid 6、Disperse aid 8、 Disperse aid 15、Disperse aid 9100( San Nopco 製)等高分 子分营夂齊!1 ; Solspers 3000、5000、9000、12000、13240、13940、 φ 17000、24000'26000、28000 等各種 Solspers 分散劑(Zeneca (股)製);Adeca Pluronic L31,F38,L42,L44,L61,L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121,P-123(日本旭電化(股)製)與isonet S-20(日本 三洋化成(股)製)。 [光硬化性成分] 其中,「光硬化性成分」係常用於微影術之光硬化性組 成物,係指由黏結劑樹脂(鹼可溶性樹脂等)、感光性聚合 鲁成分(光聚合性單體等)、光聚合起始劑等而成的組成物。 (鹼可溶性樹脂) 黏結劑樹脂較宜爲鹼可溶性樹脂。 鹼可溶性樹脂係分子中具有聚環氧烷鏈與/或甲基丙烯 酸羥乙酯(HEMA)之丙烯酸系樹脂,較宜用以使對於該塗 • 膜曝光強度的顯像後之線寬變化率爲7.5x10 5/xm · m2/J以 下。 該丙燃酸系樹脂之聚苯乙烯換算重量平均分子量較宜 -15- 200540465 • * 爲 5,000 〜5 0,000,更佳爲 6,000 〜3 0,000,最好爲 8,000 〜2 0,000。 另外,該聚環氧烷鏈之含量較宜爲莫耳比0.5〜18莫耳 %,更佳爲〇 . 8〜1 5莫耳%,最好爲1〜1 0莫耳%。 聚環氧烷鏈之中,較宜爲聚環氧乙烷鏈,其加成莫耳數 ((ΕΟ) η)較宜爲2〜25,更佳爲2〜15,最好爲5〜12。 該甲基丙烯酸羥乙酯之含量較宜爲莫耳比10〜30莫耳 %,更佳爲1 5〜2 5莫耳%。 分子中具有聚環氧烷鏈之丙烯酸系樹脂,例如,可列 φ舉:該鹼可溶性樹脂Α。 鹼可溶性樹脂 A係一種至少由下列單體而成的共聚 物:(i )由馬來酸酐(MAA )、丙烯酸(AA)、甲基丙烯 酸(MA)、甲基丙烯酸異丁酯(IBMA)與苯二甲酸(FA ) 所選出的至少一種酸成分單體;(Π )(甲基)丙烯酸烷基 聚環氧乙烷酯;及(iii )由(甲基)丙烯酸苯甲酯而成的共 聚物。 於該鹼可溶性樹脂A中,(i )酸成分單體、(ii )(甲 鲁基)丙烯酸烷基聚環氧乙烷酯(Acr( EO ) n: CH3( OC2H4 )nOCOC (CH3) = CHR)與(iii)(甲基)丙烯酸苯甲酯(BzMA) 之各單體成分的莫耳比較宜爲15〜30/1〜20/5 0〜84,更佳 爲17〜25/2〜1 5/60〜8 0。另外,根據鹼可溶性樹脂A之GPC 而得的聚苯乙烯換算重量平均分子量(Mw)較宜爲5,000〜 • 50,〇〇〇,更佳爲 6,000〜30,000。 (i )酸成分單體之莫耳比若低於該範圍的話,將有鹼 可溶性降低之傾向,另外,若超過該範圍的話,將有對溶劑 -16- 200540465 的溶解性降低之傾向。 (11 )(甲基)丙烯酸烷基聚環氧乙烷酯(Acr ( EO ) 1Ί : CH3 ( OC2H4 ) nOCOC ( CH3 ) = CHR)之組成質量比若低於 該範圍的話,因爲將有感光性著色樹脂組成物塗布液於基板 上之液體擴散方式變得不足而無法有效達成本發明之傾 向。另外,若超過該範圍的話,將有著色劑的分散性降低之 傾向而不佳。 (ίϋ )(甲基)丙烯酸苯甲酯(BzMA)之組成質量比 φ 若低於該範圍的話,因爲將有著色劑之分散劑或組成物中之 溶解性降低的傾向而不佳。另外,若超過該範圍的話,因爲 將有塗膜之鹼顯像適合性降低之傾向而不佳。 該(Π)(甲基)丙烯酸烷基聚環氧乙烷酯(Acr(EO) n: CH3( OC2H4) nOCOC( CH3) =CHR)之聚環氧乙烷(EO) n的重複數目n爲2〜25,較宜爲2〜15,尤以5〜12更爲理 想。問題在於此重複數目η若低於該範圍的話,於利用鹼性 顯像液顯像後,顯像殘渣變得容易發生,另外,相反地,若 鲁超過該範圍的話,因爲組成物塗布液之流動性將降低,變得 容易產生塗布不均,將有塗布膜厚之均勻性或省液性降低之 傾向。 分子中具有甲基丙烯酸羥乙酯(ΗΕΜΑ)之丙烯酸系樹 * 脂可列舉:甲基丙烯酸羥乙酯(ΗΕΜΑ )取代鹼可溶性樹脂 ’ Α之(ii )(甲基)丙烯酸烷基聚環氧乙烷酯。 分子中具有聚環氧烷鏈與甲基丙烯酸羥乙酯(ΗΕΜΑ) 之丙烯酸系樹脂可列舉··使甲基丙烯酸羥乙酯(ΗΕΜΑ )進 200540465 一步與鹼可溶性樹脂A進行共聚合。 另外,本發明之光硬化性組成物中的鹼可溶性樹脂之含 量較宜爲0 · 5〜1 5質量%,更佳爲1 · 〇〜1 2質量%。該鹼可溶 性樹脂之含量若低於0.5質量%的話,顯像之進行將變慢、 有可能導致製造成本之增大。另外,若超過1 5質量%的話, 將有無法得到良好的圖案輪廓之情形。 (感光性聚合成分(光聚合性單體等)) 用於本發明之感光性聚合成分,聚合性單體爲一般的。 φ該聚合性單體較宜爲具有至少一個可進行加成聚合的伸乙 基,常壓下具有沸點達1 〇〇°c以上之乙烯性不飽和基的化合 物,其例子可列舉:聚乙二醇一(甲基)丙烯酸酯、聚丙二 醇一(甲基)丙烯酸酯、(甲基)丙烯酸苯氧乙酯等官能基 之丙烯酸酯或甲基丙烯酸酯;聚乙二醇二(甲基)丙烯酸酯、 三羥甲基乙烷三(甲基)丙烯酸酯、新戊二醇二(甲基)丙 烯酸酯、異戊四醇三(甲基)丙烯酸酯、異戊四醇四(甲基) 丙烯酸酯、二異戊四醇五(甲基)丙烯酸酯、二異戊四醇六 Φ (甲基)丙烯酸酯、己二醇(甲基)丙烯酸酯、三羥甲基丙 烷三(丙烯醯基羥丙基)醚、三(丙烯醯基羥乙基)異氰酸 酯、將環氧乙烷基或伸丙氧基與甘油或三羥甲基乙烷等多官 能醇加成後之(甲基)丙烯酸酯化的感光性聚合成分,如揭 ' 示於日本公開專利第昭48-41708、昭50-6034、昭51-37193 • 號各公報的胺基甲酸酯丙烯酸酯類;揭示於日本公開專利第 昭48-64183、特公昭49-43191、特公昭52-30490號各公報 的聚酯丙烯酸酯類;環氧樹脂與(甲基)丙烯酸之反應生成 -18- 200540465 物的環氧丙烯酸酯類等之多官能性丙烯酸酯或甲基丙烯酸 酯以及此等之混合物。再者,也可以列舉:於日本接著協會 誌Vol. 20、No. 7、3 00〜3 08頁所介紹的光硬化性單體與寡 聚物。 於分子中具有聚環氧烷鏈之聚合性單體,較宜使得對於 該塗膜之曝光強度的顯像後之線寬變化率成爲7.5><10< · m2/:F以下。如此之聚合性單體可列舉如下所示之化合 物。(Π) Development temperature is 3 5 ° C (ΠΙ) Development time is 60 seconds (2) The color filter disclosed in (i), wherein the photohardenable composition is contained in the molecule and has a polyalkylene oxide Chain and / or hydroxyethyl methacrylate (HEMA) acrylic acid resin. (3) The color filter disclosed in (2), wherein the polystyrene equivalent weight average molecular weight in the acrylic resin is 5,000 to 50,000. (4) The color filter disclosed in (2), wherein the molar ratio of the content of the polyalkylene oxide chain in the acrylic resin is 5 to 25% by mole. (5) The color filter disclosed in (3), wherein the mole ratio of the polyalkylene oxide chain content in the acrylic resin is 5 to 25 mole%. (6) The color filter disclosed in any one of (2) to (5), wherein the polyalkylene oxide chain in the acrylic acid-based resin is a polyethylene oxide chain, and the polyethylene oxide is The addition mole number η of the alkane (E0) is 2 to 25. (7) The color filter disclosed in (2), in which the molar ratio of the hydroxyethyl methacrylate content of 200540465 in the acrylic resin is 100 to 300% by mole. "[Embodiments of the invention] • The color filter of the present invention is made up of pixels with a thickness of 2.0 / xm or less and a side length of 2.5 μm or less formed on a substrate; and It is characterized in that the pixel is formed by photolithography using a photolithography composition containing a colorant and a photohardenable component by lithography, and is performed using the development conditions (I) to (III) The line width change rate after the development of the exposure intensity of the coating film of the photocurable composition at the time of immersion development was 7.5 > < 10-5 μm · xn2 / J. The size of the color filter pixel of the present invention , Its side length is below 2.5 μM, more preferably below 2.0 / xm, more preferably below 1.5 μm. In addition, the thickness of the pixel is below 2.0 / xm, preferably below 1.5 / xm, especially 1.2 μm or less is more preferable. The line width change rate after the development of the exposure intensity of the coating film of the photocurable composition when the immersion development is performed under the development conditions (I) to (111) is 7.5 X 1 0 · 5μπι · m2 / J or less, preferably 6.〇χ 1 0_5μηι · m2 / J or less, especially It is more preferable to be 3.0 × l (T5 / xm · m2 / J or less. A photocurable composition having such a line width change rate is described below. ≪ Photocurable composition > Used in the present invention The photocurable composition contains a coloring agent and a photocurable component. The "photocurable component" refers to a photocurable composition commonly used in lithography, and includes a binder resin (such as an alkali-soluble resin) and a photosensitive material. Polymerization components (photopolymerization into monomers, etc.), photopolymerization initiators, etc. 200540465 [Colorant] 'The coloring agent that can be used in the present invention is not particularly limited, and one of various conventional dyes or pigments or It is used after mixing two or more kinds. The pigments that can be used in the present invention can use various conventional inorganic or organic pigments. In addition, whether the inorganic or organic pigments are considered to have a high transmittance, it is better to use It may be fine; if the operability is taken into consideration, the average particle diameter of the pigment is preferably 0 · (Π ~ 〇.1 / χιη; more preferably 0.01 ~ 0 · 0 5 / xm. In addition, the inorganic pigment may be enumerated: Metal oxygen Compounds such as compounds, metal salts, etc., specifically, include iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony and other metals For example, the organic pigment may be: CI pigment yellow n, 24, 31, 53, 83, 93, 99, 108, 109, 110, 138, 139, 147, 150, 151, 154, 155, 167, 180, 185, 199; c · I · Pigment Orange 3 6,3,8,4 3,7 1; C · 1 · Pigment Red 81,105,122,149,150,155,171,175, Lu 176 , 177, 209, 220, 224, 242, 25 4, 255, 264, 270; c · I · pigment purple 1 9, 2 3, 3 2, 3 9; CI pigment blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66; C · 1 · Pigment Green 7, 3 6, 3 7; C · 1 · Pigment Brown 2 5, 2 8; c · I · Material Black 1,7; carbon black and so on. -10- 200540465 f * The pigments which can be suitably used in the application of the present invention include the following pigments. However, the present invention is not limited to these pigments. CI Pigment Yellow 11, 24, 108, 109, 110, 138, 1 3 9, 1 50, 151, 154, 167, 180, 185; C · I. Pigment Orange 3 6,7 1; CI · Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 25 4, 25 5, 264; CI Pigment Purple 19, 23, 32; _ CI · Pigment Blue 15: 1, 15: 3, 15: 6, 16 , 22, 60, 66; CI · Pigment Black 1. These organic pigments may be used alone, or various combinations may be used in order to improve color purity. Specific examples of this combination are shown below. For example, the red pigment may be an anthraquinone-based pigment, a fluorene-based pigment, a dioxopyrrolopyrrole-based pigment alone, or at least one of these pigments may be used with a diazo-based yellow pigment and an isoindolin-based yellow Pigments, quinolone-based yellow pigments, or mixtures with fluorene-based red pigments. For example, anthraquinone-based pigments can be listed: C. 〖. Yan Lu material red 177; fluorene-based pigments can be listed: C ·; [• Pigment Red 155, C ·;!. Pigment Red 2 2 4; Dioxopyrrole Examples of the pyrrole-based pigment include: c ·; [• pigment red 2 5 4; from the viewpoint of color reproducibility, it is more preferable to mix with c. I. pigment yellow 1 3 9. In addition, the quality comparison of the red pigment and the yellow pigment is preferably i 00: 5 to 100: 75. If it exceeds this range, it may become difficult to suppress the light transmittance and improve the color purity. In addition, the preferred mass ratio is 100: 100; 50 ° In addition, 'green pigments can be halogenated phthalocyanine pigments alone, or -11-200540465 can be used with halogenated fluorene pigments and one heavy A mixture of gas-based yellow pigments, quinone-based ochre-pigments, methylimine-based yellow pigments, or isoindolin-based yellow pigments. Examples-For example, this example is more suitable for CI Pigment Green 7, 3 6, 3 7 and d • Pigment Yellow 83, CI Pigment Yellow 138, CI · Pigment Yellow 139, cI · Pigment Yellow 150, and CI Pigment Page Color 180. Or a mixture of CI Pigment Yellow 185. The quality comparison of the green pigment and the yellow pigment is preferably 100: 5 to 100: 150. As the blue pigment, a phthalocyanine-based pigment may be used alone, or a mixture of a cyanine-based pigment and a dioxin-based purple pigment may be used. For example, a mixture of C.I. pigment Lu blue 15: 6 and C.I. pigment purple 23 is preferred. The quality comparison of blue pigment and purple pigment should be 100: 0 to 100: 30. In the present invention, when the colorant is a dye, it is uniformly dissolved in the composition to obtain a photocurable coloring resin composition. The dye that can be used as the coloring agent constituting the composition of the present invention is not particularly limited, and a conventional dye for a conventional color filter can be used. For example, the pigments disclosed in the following patents can be used: Japanese Laid-Open Patent No. Sho 64-90403, Sho 64-91102, Hei 1-94301, Hei 6-11614, Hei 5-333207, Hei 6-35183, Hei 6-51115 , Ping 6-194828, Ping 8-211599, Ping 4-249549, Ping 10-123316, Ping 11-302283, Ping 7-286107, 2001-4823, Ping 8-15522, Ping 8-2977 Ping 8-146215, Hei 11-343437, Hei 8-62416, 2002-14220, 2002-14221, 2002-14222, 2002-14223 Hei 8-302224, Hei 8-73758, Hei 8- 1 79 1 20, Hei 8-151531 ; Patent Publication No. 2 5 92207; US Patent Nos. 4,808,501, 5,667,920, 5,059,500, and the like. The chemical structure can use the following dyes: pyrazole azo series, aniline azo-12- 200540465 • 1 series, triphenylmethane series, anthraquinone series, anthrapyridone, benzylidene series, oxa'cyanine series , Pyrazol triazine azo-based, pyridone azo-based, cyanine-based, phenothi trap-based, pyridylazolyl azomethane-based, Gouton-based, phthalocyanine-based, benzopyran-based, indigo-based Wait. In addition, when a photoresist system using water or an alkaline developer is used, it is possible to use an acid dye and / or a derivative thereof from the viewpoint of completely removing the binder and / or dye from the unirradiated portion by development. Things. In addition, direct dyes, basic dyes, mordant dyes, acid mordant dyes, insoluble azo dyes, disperse dyes, oil dyes, food dyes, and / or derivatives thereof can be effectively used. The acid dye is not particularly limited as long as it has an acidic group such as a sulfonic acid or a carboxylic acid, and the solubility of an organic solvent or a developing solution, the salt-forming property with a basic compound, the absorbance, and others in the composition are considered. Interaction of ingredients, light resistance, heat resistance, etc. are all necessary and selected. Specific examples of the acid dye are listed below, but the examples are not limited to these examples. For example, Acid Alizarin Violet N; Acid Black 1, 2, 24, 48; Acid Blue 1,7, 9, • 15, 18, 23, 25, 27, 29, 40, 45, 62, 70, 74, 80 , 83, 86, 87, 90, 92, 103, 112, 113, 120, 129, 138, 147, 158, 171, 182, 1 92, 24 3, 3 24: 1; Acid Chrome Violet K; Acid Magenta ; Acid green 1, 3, 5, 9, 16, 25, 27, 50; lime 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95; acid red 1, 4 , 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94 , 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266 , 274; Acid Violet-13- 200540465 6B, 7, 9, 17, 19; Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73 , 76, 79, 98, 99, 111, 112, 114, 116, 184, 24 3; edible page color 3, and derivatives of these dyes. Among them, the acid dye is preferably acid black 24; acid blue 23, 25, 29, 62, 80, 86, 87, 92, 138, 158, 182, 243, 324: 1, · lime 8, 51, 56 , 63, 74; Acid Red 1, 4, 8, 34, 37, 42, 52, 57, 80, 97, 114, 143, 145, 151, 183, 217; Acid Violet 7; Acid Yellow 17, 25, 2 9, 3 4, 42, 72, 76, 99, 1 1 1, 1 12, 1, 14, 14, 16, 84, 243; acid green 25 and other derivatives of these materials. In addition, in addition, azo-based, glutton-based, and phthalocyanine-based acid dyes are also preferred, and C. I. Solvent Blue 4 4, 3 8; C. I. Solvent Orange 4 5; Damn B; acid dyes such as rhodamine 1 10 and derivatives of these dyes. The content of the coloring agent in the total solid content of the photocurable composition of the present invention is not particularly limited, but is preferably 30 to 60% by mass. If there is too little colorant, there is a tendency that an appropriate chromaticity as a color filter cannot be obtained. In the present invention, for the purpose of improving the dispersibility of the pigment, a pigment dispersant or a surfactant of the conventional xinxin can be added. Many kinds of compounds can be used for these dispersants, for example, a phthalocyanine derivative (commercial product EFKA-745 (manufactured by EFKA)), Solspers 5 000 (manufactured by Zeneca (stock)); an organosiloxane polymer KP341 ( Shin-Etsu Chemical Industry (Co., Ltd.), (fluorenyl) acrylic (co) polymer Polyflower No. 75, No. 90, No. 95 (Japan • Kyoeisha Oil Chemical Industry Co., Ltd.), W001 ( (Made by Yusho, Japan) and other cationic surfactants; polyethylene oxide lauryl ether, polyethylene oxide stearyl ether, polyethylene oxide oleyl ether, polyethylene oxide octylphenyl ether Non-ionic surfactants such as polycyclo-14-200540465 oxyethane nonylphenyl ether, polyethylene glycol dilauryl ester, polyethylene glycol distearate, sorbitan fatty acid ester, etc. wo 04, W0 05, W01 7 (manufactured by Yusho, Japan) and other anionic surfactants; EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymerization 450 (Hereafter, Japan's Morishita Industries Co., Ltd.), Disperse aid 6, Disperse aid 8, Disperse aid 15, Disperse aid 9100 (made by San Nopco) and other high-ranking camps! 1; Solspers 3000, 5000, 9000, 12000, 13240, 13940, φ 17000, 24000'26000, 28000 and other Solspers dispersants (Zeneca (stock)); Adeca Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (Japan Asahi Kasei Corporation) and isonet S-20 (Japan Sanyo Kasei Corporation). [Photocurable component] Among them, "Photocurable component" is a photocurable composition commonly used in lithography, and refers to a binder resin (alkali soluble resin, etc.), a photosensitive polymer component (photopolymerizable monomer) Composition) and a photopolymerization initiator. (Alkali-soluble resin) The binder resin is preferably an alkali-soluble resin. An acrylic resin having a polyalkylene oxide chain and / or hydroxyethyl methacrylate (HEMA) in an alkali-soluble resin molecule is more preferably used to make the line width change rate after the exposure of the coating film is developed. 7.5x10 5 / xm · m2 / J or less. The polystyrene-equivalent weight average molecular weight of the propionic acid-based resin is preferably -15-200540465 • * is 5,000 to 50,000, more preferably 6,000 to 30,000, and most preferably 8,000 to 20,000. In addition, the content of the polyalkylene oxide chain is more preferably 0.5 to 18 mol%, more preferably 0.8 to 15 mol%, and most preferably 1 to 10 mol%. Among the polyalkylene oxide chains, polyethylene oxide chains are more preferable, and the addition mole number ((ΕΟ) η) is more preferably 2 to 25, more preferably 2 to 15, and most preferably 5 to 12. . The content of the hydroxyethyl methacrylate is more preferably 10 to 30 mol%, more preferably 15 to 25 mol%. The acrylic resin having a polyalkylene oxide chain in the molecule can be listed, for example, φ: the alkali-soluble resin A. Alkali soluble resin A is a copolymer made of at least the following monomers: (i) made of maleic anhydride (MAA), acrylic acid (AA), methacrylic acid (MA), isobutyl methacrylate (IBMA) and Phthalic acid (FA) selected at least one acid component monomer; (Π) alkyl (meth) acrylate polyethylene oxide; and (iii) copolymerization of benzyl (meth) acrylate Thing. In this alkali-soluble resin A, (i) an acid component monomer, (ii) (methyl meth) alkyl polyalkylene oxide (Acr (EO)) n: CH3 (OC2H4) nOCOC (CH3) = CHR The molar content of each monomer component of () and (iii) benzyl (meth) acrylate (BzMA) is preferably 15 to 30/1 to 20/5 0 to 84, and more preferably 17 to 25/2 to 1. 5/60 ~ 80. The polystyrene-equivalent weight average molecular weight (Mw) obtained based on the GPC of the alkali-soluble resin A is preferably 5,000 to • 50,000, and more preferably 6,000 to 30,000. (i) If the molar ratio of the acid component monomer is lower than this range, the alkali solubility tends to decrease, and if it exceeds the range, the solubility to the solvent -16-200540465 tends to decrease. (11) The composition-to-mass ratio of alkyl poly (ethylene oxide) (meth) acrylate (Acr (EO) 1Ί: CH3 (OC2H4) nOCOC (CH3) = CHR) is lower than this range because it will have photosensitivity The liquid diffusion method of the colored resin composition coating liquid on the substrate becomes insufficient, and the tendency of the invention cannot be effectively achieved. In addition, if it exceeds this range, the dispersibility of the colorant tends to decrease, which is not preferable. (ί 之) If the composition mass ratio φ of benzyl (meth) acrylate (BzMA) is lower than this range, the dispersant of the colorant or the solubility in the composition tends to decrease, which is not preferable. In addition, if it exceeds this range, the alkali developing suitability of the coating film tends to decrease, which is not preferable. The (Π) (meth) acrylic acid alkyl polyethylene oxide (Acr (EO) n: CH3 (OC2H4) nOCOC (CH3) = CHR) has a repeating number n of n 2 ~ 25, more preferably 2 ~ 15, especially 5 ~ 12. The problem is that if the number of repetitions η is lower than this range, development residues tend to occur after development with an alkaline developer, and, on the other hand, if Lu exceeds the range, the composition coating The fluidity is reduced, and uneven coating tends to occur, and there is a tendency that the uniformity of the thickness of the coating film or the liquid saving property tends to decrease. Examples of acrylic resins having hydroxyethyl methacrylate (ΗΕΜΑ) in the molecule include: hydroxyethyl methacrylate (ΗΕΜΑ) instead of alkali-soluble resins' Α (ii) (meth) acrylic alkyl polyepoxides Ethane ester. Examples of acrylic resins having a polyalkylene oxide chain and hydroxyethyl methacrylate (ΗΕΜΑ) in the molecule include: · Making hydroxyethyl methacrylate (ΗΕΜΑ) further copolymerize with alkali-soluble resin A in 200540465. In addition, the content of the alkali-soluble resin in the photocurable composition of the present invention is preferably from 0.5 to 15% by mass, and more preferably from 1.0 to 12% by mass. If the content of the alkali-soluble resin is less than 0.5% by mass, the progress of development will be slowed, which may increase the manufacturing cost. If it exceeds 15% by mass, a good pattern profile may not be obtained. (Photosensitive polymerizable component (photopolymerizable monomer, etc.)) The photosensitive polymerizable component used in the present invention is generally a polymerizable monomer. φ The polymerizable monomer is preferably a compound having at least one ethylenic group capable of addition polymerization and having an ethylenically unsaturated group having a boiling point of 100 ° C or higher under normal pressure. Examples thereof include polyethylene. Glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) acrylate and other functional acrylates or methacrylates; polyethylene glycol di (meth) Acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, isopentaerythritol tri (meth) acrylate, isopentaerythritol tetra (methyl) Acrylate, Diisopentaerythritol penta (meth) acrylate, Diisopentaerythritol hexa (meth) acrylate, Hexanediol (meth) acrylate, Trimethylolpropane tris (acryl fluorenyl) (Hydroxypropyl) ether, tris (propenyl hydroxyethyl) isocyanate, (meth) acrylic acid after adding ethylene oxide or propylene oxide to polyfunctional alcohols such as glycerol or trimethylolethane The esterified photosensitive polymerization component, as disclosed, is disclosed in Japanese Laid-Open Patent No. Sho 48-41708, 50-6034, Sho 51-37193 • Urethane acrylates in each gazette; Polyesters disclosed in Japanese Laid-open Patent Sho 48-64183, Sho 49-43191, Sho 52-30490 Acrylates; polyfunctional acrylates or methacrylates of epoxy resins (meth) acrylic acid and (meth) acrylic acid to produce -18-200540465, etc., and mixtures thereof. In addition, photo-curable monomers and oligomers described in the Japan Adv. Association Vol. 20, No. 7, 3 00 to 3 08 pages can also be cited. The polymerizable monomer having a polyalkylene oxide chain in the molecule is preferably such that the line width change rate after development of the exposure intensity of the coating film becomes 7.5 > < 10 < m2 /: F or less. Examples of such a polymerizable monomer include compounds shown below.
【化學式1】[Chemical Formula 1]
NK酯 A-TMP-6E0 (日本新中村化學)NK Ester A-TMP-6E0 (Shin Nakamura Chemical, Japan)
KAYARAD RP-1040 (曰本化藥) -19- 200540465 【化學式2】KAYARAD RP-1040 (Japanese medicine) -19- 200540465 [Chemical formula 2]
ί R1 一一R1 :_r2 R2= m:1, R1 :3, R2:3 KAYARAD DPCAP-30 (日本化藥)ί R1 one to one R1: _r2 R2 = m: 1, R1: 3, R2: 3 KAYARAD DPCAP-30 (Japanese chemical)
KAYARAD DPCA-50 (曰本化藥) 相對於固形成分,該聚合性單體於光硬化性組成物中$ 含量較宜爲0.1〜90質量%,更佳爲1.0〜80質量%,尤以 2 · 0〜7 0質量%更爲理想。 (光聚合起始劑) 只要該光聚合起始劑使該聚合性單體與該鹼可溶性樹 脂予以聚合的話,並未予以特別限定,基於聚合特性、起始 劑效率、吸收波長、取得容易性、成本等觀點,較宜含有由 三鹵化甲基三阱系化合物、肟系化合物、心胺基酮系化合物 -20- 200540465 而成的群中所選出的至少一種化合物。 •鹵化甲基三哄系化合物之光聚合起始劑可列舉:揭示 . 於日本公開專利第昭 59- 1 2 8 1號公報之乙烯鹵化甲基三 阱系化合物、揭示於日本公開專利第昭5 3 - 1 3 342 8號公報之 2-(萘并-1-醯)-4,6-雙鹵化甲基-s-三哄系化合物與4-(厂 胺苯基)-2,6 - __•齒化甲基-s-二哄系化合物。 除此之外,可列舉:Midori化學公司製之TAZ系列、 TAZ-107、TAZ-110、TAZ-104、TAZ-109、TAZ-140、TAZ-204、 • TAZ-113、TAZ-123、TAZ-104 等。 α-胺基酮系化合物之光聚合起始劑可列舉:Ciba Geigy 公司製之 Irgacure 系列、Irgacure 907、Irgacure 367、2 -甲 基-1-苯基-2-嗎琳代丙院-1-酮[、2 -甲基- l- [4-(己基)苯基]-2-嗎啉代丙烷-1-酮、2_乙基-2-二甲胺基-1- ( 4-嗎啉代苯基) -1 -丁酮等。 肟系化合物之光聚合起始劑,並未予以特別限定,可列 舉:2-(0 -苯甲醯肟)-1-[4-(苯硫基)苯基]-1,2 -辛二酮、 φ 卜(4-甲磺基苯基)丁烷-1,2-丁烷、2-肟-0-醋酸酯、1- ( 4-甲磺基苯基)丁烷-1-酮肟-0-醋酸酯、羥基亞胺基- (4-甲磺 基苯基)-醋酸乙酯-〇-醋酸酯、羥基亞胺基-(4-甲磺基苯基) -醋酸乙酯-〇 -苯甲酸酯等。 於此等光聚合起始劑中,可以倂用增感劑或光安定劑。 其具體例可列舉:苯偶因、苯偶因甲基醚、9-芴酮、2-氯-9-荀酮I、2 -甲基-9-荀酮、9 -蒽酮、2 -溴-9-蒽酮I、2 -乙基- 9-蒽酮、9,1〇-蒽醌、2-乙基-9,10-蒽醌、2-卜丁基-9,10-蒽醌、 -21 - 200540465 ι · 2,6 - 一·氯-9,1 0 -恩It;、咕卩頓、2 -甲基咕囉、2 -甲氧基咕II頓、口塞 噸酮、2,4-二乙基噻噸酮、吖啶酮、ίο-丁基-2-氯吖啶酮、 苯甲基、二苯基丁烯酮、(二甲胺基)苯基苯乙烯基酮、 户-(一甲胺基)苯基-p-甲基苯乙嫌基酮、二苯甲酮、p-(二 甲胺基)二苯甲酮(或米希勒酮)(二乙胺基)二苯甲 酮、苯嵌蒽酮等;或揭示於日本公開專利第昭5 1 -48 5 1 6號 公報之苯并噻唑系化合物等;或Tinuvin 1130、Tinuvin 400 等。 • 於本發明,除了該光聚合起始劑之外,可以使用其他習 知之光聚合起始劑。 具體而言,可列舉:揭示於美國專利第2,3 67,660號專 利說明書之連位聚乙酮醇糖醛化合物、揭示於美國專利第 2,3 67,66 1與2,3 67,6 70號專利說明書之α-羰基化合物、揭示 於美國專利第2,4 4 8,8 2 8號專利說明書之偶姻醚、揭示於美 國專利第2,7 2 2,5 1 2號專利說明書之α-烴所取代之芳香族偶 姻醚化合物、揭示於美國專利第3,046,127與2,951,7 5 8號 鲁專利說明書之多核醌化合物、揭示於美國專利第3,S49,3 67 號專利說明書之三烯丙基咪唑二聚物以-胺基苯酮之組合、揭 示於日本公開專利第昭5 1 -4 8 5 1 6號公報之苯并噻唑系化合 物/三鹵化甲基三阱系化合物等。 該光聚合起始劑可列舉:由鹵化甲基噁二哗化合物、鹵 化甲基三阱系化合物所選出的至少一種活性鹵化物、3_ 芳基取代香豆素化合物、洛芬鹼二聚物、二苯甲酮化合物、 乙醯酮化合物及其衍生物、環戊二烯-苯-鐵配位化合物及其 -22- 200540465 鹽類、肟系化合物等。 另外,能夠有效使用鹵化甲基噁二唑等活性鹵化物’此 等活性鹵化物之實例可列舉:揭示於日本公開專利第昭 57-6096號公報之2 -鹵化甲基-5 -乙烯基-1,3,4-噁二唑化合物 等、或是2-三氯甲基-5-苯乙烯基-1,3,4-噁二唑、2-三氯甲基 -5- (/?-氰基苯乙烯基)-1,3,4-噁二唑、2-三氯甲基- 5-(/7-甲氧基苯乙烯基)-1,3,4-噁二唑等。 另外,該光聚合起始劑可以有效使用PANCHIM公司製 | 之 T系歹[J,此等實例可列舉:T-OMS、T-BMP、T-R、T-B 等。 再者,該光聚合起始劑可以有效使用Ciba Geigy公司製 之Irgacure系列,此等實例可列舉:Irgacure 651、Irgacure 184、Irgacure 500、Irgacure 1 000、Irgacure 149、Irgacure 819、Irgacure 261、Darocure 系歹ij、Darocure 1173 等。 其他,該光聚合起始劑也可以有效使用4,4’-雙(二乙 胺基)二苯甲酮、2-( 0-苯醯肟)-1-[4-(苯硫基)苯基]-1,2-• 辛二酮、2-苯甲基-2-二甲胺基-4-嗎啉代丁醯苯、2,2-二甲氧 基_2_苯基乙薩苯、2-(〇 -氯苯基)-4,5 -二苯基咪嗤二聚物、 2-(心氟苯基)-4,5-二苯基咪唑二聚物、2-(;7-甲氧苯基) -4,5-二苯基咪唑二聚物、2- ( 二甲氧苯基)-4,5_二苯基咪 唑二聚物、2- (2,4 -二甲氧苯基)-4,5 -二苯基咪唑二聚物、 2- 甲氫硫基苯基)-4,5-二苯基咪唑二聚物、苯偶因異丙 基醚等。 相對於該聚合性單體之固形成分,本發明之該光聚合起 -23 - 200540465KAYARAD DPCA-50 (Japanese chemical) Relative to the solid content, the content of the polymerizable monomer in the photohardenable composition is preferably 0.1 to 90% by mass, more preferably 1.0 to 80% by mass, especially 2 0 to 70% by mass is more preferable. (Photopolymerization initiator) The photopolymerization initiator is not particularly limited as long as it polymerizes the polymerizable monomer and the alkali-soluble resin, and is based on polymerization characteristics, initiator efficiency, absorption wavelength, and ease of acquisition. From the viewpoints of cost and cost, it is preferable to include at least one compound selected from the group consisting of a trihalogenated methyl triple well-based compound, an oxime-based compound, and a cardiac ketone-based compound-20-200540465. • Examples of photopolymerization initiators of halogenated methyltriazine compounds are disclosed: disclosed in Japanese Laid-Open Patent Publication No. Sho 59- 1 2 8 1 and disclosed in Japanese Published Patent No. Sho 5 3-1 3 342 Publication No. 8 2- (naphtho-1-pyrene) -4,6-dihalogenated methyl-s-triazine compound and 4- (Plantaminephenyl) -2,6- __ • dentified methyl-s-dioxine compounds. Other examples include: TAZ series, TAZ-107, TAZ-110, TAZ-104, TAZ-109, TAZ-140, TAZ-204, TAZ-113, TAZ-123, TAZ manufactured by Midori Chemical Co., Ltd. -104 and so on. Examples of the photopolymerization initiators of α-amino ketone compounds include: Irgacure series manufactured by Ciba Geigy, Irgacure 907, Irgacure 367, and 2-methyl-1-phenyl-2-morphinyl-propionate-1- Ketone [, 2-methyl-l- [4- (hexyl) phenyl] -2-morpholinopropane-1-one, 2-ethyl-2-dimethylamino-1- (4-morpholine Phenyl) -1 -butanone and the like. The photopolymerization initiator of the oxime-based compound is not particularly limited, and examples thereof include 2- (0 -benzyloxime) -1- [4- (phenylthio) phenyl] -1,2-octane Ketone, φ (4-methylsulfophenyl) butane-1,2-butane, 2-oxime-0-acetate, 1- (4-methylsulfophenyl) butane-1-one oxime -0-acetate, hydroxyimino- (4-methylsulfophenyl) -ethyl acetate-〇-acetate, hydroxyimino- (4-methylsulfophenyl) -ethyl acetate-〇 -Benzoates and the like. Among these photopolymerization initiators, a sensitizer or a light stabilizer may be used. Specific examples include benzoin, benzoin methyl ether, 9-fluorenone, 2-chloro-9-fluorenone I, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo -9-anthrone I, 2-ethyl-9-anthrone, 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, 2-butyl-9,10-anthraquinone, -21 -200540465 ι · 2,6-monochloro-9,1 0 -En It ;, Glutton, 2-Methyl Glutton, 2-methoxy Glutton, Gestolone, 2,4- Diethylthioxanthone, acridone, ο-butyl-2-chloroacridone, benzyl, diphenylbutenone, (dimethylamino) phenylstyryl ketone, household- ( Monomethylamino) phenyl-p-methylacetophenone, benzophenone, p- (dimethylamino) benzophenone (or Michler's ketone) (diethylamino) diphenyl Methyl ketone, benzoxanthone, etc .; or benzothiazole-based compounds disclosed in Japanese Laid-Open Patent Publication No. 5 1-48 5 16; etc .; or Tinuvin 1130, Tinuvin 400, and the like. • In the present invention, in addition to the photopolymerization initiator, other conventional photopolymerization initiators can be used. Specific examples include the vicinal polyketal aldose compounds disclosed in the specification of U.S. Patent No. 2,3,67,660, and the U.S. Patent Nos. 2,3,67,66 1 and 2,3,67,6 70 Alpha-carbonyl compound of Patent Specification No. 2, disclosed in US Patent No. 2,4,4,8,8,2, Ether ether, disclosed in US Patent No. 2,7 2 2,5 1 2 -Aromatic substituted ether compounds substituted by hydrocarbons, polynuclear quinone compounds disclosed in U.S. Patent Nos. 3,046,127 and 2,951,7 58, and disclosed in U.S. Patent No. 3, S49,3,67 The triallyl imidazole dimer is a combination of amine benzophenone, benzothiazole compounds / trihalogenated methyl triple well compounds disclosed in Japanese Laid-Open Patent Publication No. 5 1 -4 8 5 16 . Examples of the photopolymerization initiator include at least one active halide selected from a halogenated methyloxadioxo compound, a halogenated methyl triple trap compound, a 3-aryl substituted coumarin compound, a loffine base dimer, Benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene-benzene-iron complexes and their -22-200540465 salts, oxime-based compounds, etc. In addition, active halides such as halogenated methyloxadiazole can be effectively used. Examples of such active halides include: 2-Halogenated methyl-5 -vinyl- disclosed in Japanese Laid-Open Patent Publication No. Sho 57-6096 1,3,4-oxadiazole compounds, etc., or 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (/?- Cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5-(/ 7-methoxystyryl) -1,3,4-oxadiazole and the like. In addition, the photopolymerization initiator can effectively use T series 歹 [J of PANDIM Corporation]. Examples include T-OMS, T-BMP, T-R, T-B, and the like. Furthermore, the photopolymerization initiator can effectively use the Irgacure series manufactured by Ciba Geigy. Examples of these examples include: Irgacure 651, Irgacure 184, Irgacure 500, Irgacure 1 000, Irgacure 149, Irgacure 819, Irgacure 261, Darocure series歹 ij, Darocure 1173, etc. In addition, this photopolymerization initiator can also effectively use 4,4'-bis (diethylamino) benzophenone, 2- (0-phenylhydrazine) -1- [4- (phenylthio) benzene Phenyl] -1,2- • octanedione, 2-benzyl-2-dimethylamino-4-morpholinobutyrylene, 2,2-dimethoxy-2-phenylethazaphene , 2- (〇-chlorophenyl) -4,5-diphenylimidium dimer, 2- (cardiofluorophenyl) -4,5-diphenylimidazole dimer, 2-(; 7 -Methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (dimethoxyphenyl) -4,5-diphenylimidazole dimer, 2- (2,4-dimethylformaldehyde) (Oxyphenyl) -4,5-diphenylimidazole dimer, 2-methylhydrothiophenyl) -4,5-diphenylimidazole dimer, benzoin isopropyl ether, etc. Relative to the solid content of the polymerizable monomer, the photopolymerization of the present invention starts at -23-200540465
* A 始劑的用量較宜爲〇 . 〇 1〜5 0質量%,更佳爲1〜3 0 '尤以1〜20質量%更爲理想。光聚合起始劑之用量 .質量%爲少的話,聚合將難以進行,另外,若超過 的話,雖然聚合率變大,但是,有分子量變低、膜 之情形。 於本發明之光硬化性組成物中,除此之外,較 預先添加熱聚合防止劑。例如,氫醌、;^甲氧基! 丁基甲酚、焦掊酚、丁基兒茶酚、對苯醌、4,4 • (3-甲基-6-卜丁基酚)、2,2’-亞甲基雙(4-甲基· 酚)、2-氫硫基苯并咪唑等爲有用的。 (溶劑) 用於本發明之光硬化性組成物中,必要時所用 要滿足組成物之溶解性、塗布性的話,基本上並未 限定,尤以考量染料、黏結劑(鹼可溶性樹脂)之 塗布性、安全性而加以選擇更爲理想。 可以使用於調製光硬化性組成物之際的溶劑可 #類,例如,醋酸乙酯、醋酸丁酯、醋酸異丁酯 酯、醋酸異戊酯、醋酸異丁酯、丙酸丁酯、丁酸異 酸乙酯、丁酸丁酯、烷酯類;乳酸甲酯、乳酸乙酯 酸甲酯、羥基醋酸乙酯、羥基醋酸丁酯、甲氧基醋 甲氧基醋酸乙酯、甲氧基醋酸丁酯、乙氧基醋酸甲 基醋酸乙酯、3-羥基丙酸甲酯、3-羥基丙酸乙酯等; 丙酸烷酯類;3 -甲氧基丙酸甲酯、3 -甲氧基丙酸乙 氧基丙酸甲酯、3 -乙氧基丙酸乙酯、2 -羥基丙酸甲 質量%, 若較〇 . 〇 1 5 0質量% 強度變弱 宜進一步 ©、二 硫基雙 -6-卜丁基 之溶劑只 予以特別 溶解性、 列舉:酯 、甲酸戊 丙酯、丁 、羥基醋 酸甲酯、 酯、乙氧 之3-羥基 酯、3-乙 酯、2-羥 -24- 200540465 基丙酸乙酯、2 -羥基丙酸丙酯、2 -甲氧基丙酸甲酯、2 -甲氧 •基丙酸乙酯、2-甲氧基丙酸丙酯、2_乙氧基丙酸甲酯' 2-乙 ,氧基丙酸乙酯、2 -羥基丙酸乙酯、2 -羥基-2-甲基丙酸甲酯、 2-羥基-2-甲基丙酸乙酯、2-甲氧基-2-甲基丙酸甲酯、2-乙氧 基-2 -甲基丙酸乙酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸丙 酯、乙醯乙酸甲酯、乙醯乙酸乙酯、2-羥基丁酸甲酯、2-羥 基丁酸乙酯等;醚類,例如’二乙二醇二甲基醚、四氫呋喃、 乙二醇一甲基醚、乙二醇一乙基醚、甲基纖維素醋酸酯、乙 φ 基纖維素醋酸酯、二乙二醇一甲基醚、二乙二醇一乙基醚、 二乙二醇一丁基醚、丙二醇甲基醚、丙二醇甲基醚醋酸酯、 丙二醇乙基醚醋酸酯、丙二醇丙基醚醋酸酯等;酮類,例如, 甲基乙基酮、環己酮、2 -庚酮、3 -庚酮等;芳香族烴類,例 如,甲苯、二甲苯等。 此等之中,3 -乙氧基丙酸甲酯、3 -乙氧基丙酸乙酯、乙 基纖維素醋酸酯、乳酸乙酯、二乙二醇二甲基醚、醋酸丁酯、 3 -甲氧基丙酸甲酯、2 -庚酮、環己酮、乙基卡必醇醋酸酯、 φ 丁基卡必醇醋酸酯、丙二醇甲基醚、丙二醇甲基醚醋酸酯等 更爲適合。 (其他之添加物) 本發明之光硬化性組成物中,必要的話,也可以摻合各 ' 種添加劑,例如,塡充劑、該以外之高分子化合物、界面活 性劑、密著促進劑、抗氧化劑、紫外線吸收劑、抗凝聚劑等。 此等之添加物之具體例,可列舉:玻璃、氧化鋁等之塡 充劑;聚乙烯醇、聚丙烯酸、聚乙二醇一烷基醚、聚氟化烷 -25- 200540465 基丙烯酸酯等黏結樹脂以外之高分子化合物;非離子系、陽 '離子系、陰離子系等之界面活性劑;乙烯三甲氧基矽烷、乙 ,烯三乙氧基矽烷、乙烯三(2-甲氧基乙氧基)矽烷、N- ( 2-胺乙基)-3-胺丙基甲基二甲氧基矽烷、N- ( 2-胺乙基)-3-胺丙基甲基三甲氧基矽烷、3-胺丙基三乙氧基矽烷、3-環氧 丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基甲基二甲氧基 矽烷、2- ( 3,4-環氧環己基)乙基三甲氧基矽烷、3-氯丙基 甲基二甲氧基矽烷、3-氯丙基三甲氧基矽烷、3-甲基丙烯醯 φ 氧基三甲氧基矽烷、3-氫硫基丙基三甲氧基矽烷等密著促進 劑;2,2-硫基雙(4-甲基-6 +丁基酚)、2,6-二丁基酚等 抗氧化劑;2 - ( 3-卜丁基-5-甲基-2-羥苯基)-5-氯苯并***、 烷氧基二苯甲酮等紫外線吸收劑;與聚丙烯酸鈉等抗凝聚 劑。 另外,於期望加速放射線未照射部之鹼溶解性,並針對 光硬化性組成物的顯像性進一步提高之情形下,於光硬化性 組成物中,能夠進行有機羧酸,較宜爲分子量1 0 0 0以下之 Φ 低分子量有機羧酸的添加。具體而言,例如,可列舉:甲酸、 乙酸、丙酸、戊酸、己酸、三甲基己酸、二乙基乙酸、庚酸、 辛酸等脂肪族一羧酸;草酸、丙二酸、琥珀酸、戊二酸、己 二酸、庚二酸、辛二酸、壬二酸、癸二酸、巴西二酸、甲基 ' 丙二酸、乙基丙二酸、二甲基丙二酸、甲基琥珀酸、四甲基 琥珀酸、檸康酸等脂肪族二羧酸;均苯三甲酸、丙烯三甲酸、 樟腦三酸等脂肪族三羧酸;安息香酸、苯乙酸、對異丙基苯 甲酸、2,3-二甲基苯基酸、3,5-二甲基苯基酸等芳香族一羧 -26- 200540465 酸;苯二甲酸、間苯二甲酸、對苯二甲酸、偏苯三甲酸、均 -苯三甲酸、偏苯四甲酸、均苯四甲酸等芳香族聚羧酸;苯乙 -酸、心甲基苯乙酸、氫化肉桂酸、苦杏仁酸、苯基琥珀酸、 阿托酸、肉桂酸、肉桂酸甲酯、肉桂酸苯甲酯、肉桂叉乙酸、 香豆酸、傘形酸等其他之羧酸。 <彩色濾光片> 本發明之彩色濾光片係使用該光硬化性組成物所製造 的。本發明之彩色濾光片的製法,其特徵上包括:將該光硬 φ 化性組成物,直接或隔著其他薄層而塗布於基板上,之後, 進行乾燥而形成塗膜的步驟(塗膜形成步驟);於該塗膜上 進行特定圖案之曝光的步驟(曝光步驟);利用鹼性顯像液, 進行已曝光之該塗膜的顯像處理的步驟(曝光步驟);與對 已進行顯像處理之該塗膜進行加熱處理的步驟(後烤步 驟)。能夠藉由此等步驟而形成已著色之圖案。另外,必要 的話,本發明之彩色濾光片的製法也可以包含藉由進行該光 阻劑圖案之加熱與曝光而予以硬化的步驟。 φ 該塗膜形成步驟係藉由旋轉塗布、流塑塗布、滾筒塗 布、狹縫塗布等塗布方法而於基板上進行光硬化性組成物之 塗布與乾燥後,形成感光性組成物層(塗膜層)。 該基板可列舉:例如,用於液晶顯示元件之鈉鈣玻璃、 ' 硬質(R )玻璃、石英玻璃與將透明導電性膜附著於此等玻 璃之基板,或是用於攝影元件等之光電變換元件基板,例 如,矽基板等或互補式金屬氧化膜半導體(CMOS )等。此 等基板也有形成隔離各像素之黑色矩陣的情形。 -27- 200540465 ► · 另外,必要的話,爲了改良與上部薄層之密著、防止物 •質之擴散或基板表面之平坦化,也可以於此等基板上設置底 塗層。 該曝光步驟係對於該塗膜形成步驟所形成的塗膜,例 如,隔著光罩等而進行特定圖案之曝光。於曝光之際所用之 放射線,尤以使用g線、h線、i線等紫外線特別適合。 該顯像步驟係一種利用鹼性顯像液而將已曝光之塗膜 予以顯像處理的步驟。該鹼性顯像液可以使用只要能溶解本 φ 發明之組成物,並且,不溶解曝光部(放射線照射部)的任 一種鹼性顯像液。具體而言,可以使用各種有機溶劑之組合 或鹼性水溶液。 該有機溶劑可列舉:於調配用於本發明之該光硬化性組 成物之際所用的該溶劑。 另外,該鹼性水溶液,例如,可列舉:氫氧化鈉、氫氧 化鉀、碳酸鈉、矽酸鈉、偏矽酸鈉、氨水、乙胺、二乙胺、 二甲基乙醇胺、四甲基銨氫氧化物、四乙基銨氫氧化物、膽 • 鹼、吡咯、哌啶、1,8-吖雙環-[5·4·0]-7-十一烯等。 用於本發明之鹼性顯像液較宜使用將鹼濃度調整成pH 1 1〜1 3,更佳爲調整成pH 1 1 · 5〜1 2 · 5的鹼性水溶液。該鹼 濃度若超過pH 1 3的話,有產生圖案粗糙或是剝離、殘膜率 ' 之降低的情形,若低於pH 1 1的話,將有顯像速度變慢、觀 • 察到殘渣發生之情形。 該顯像步驟係利用由如此鹼性水溶液而成的顯像液而 進行顯像處理。例如,顯像方法可列舉:浸漬法、噴霧法、 -28 - 20Q540465 水坑法等’溫度較宜爲1 5〜4 0 °C下進行。另外,通常,顯像 '後利用一般水流進行洗淨。 再者,本發明之彩色濾光片的製法,爲了使顯像後之塗 膜予以充分硬化,於後烤步驟進行加熱處理。該加熱步驟之 加熱溫度較宜爲100〜300 °c、更佳爲150〜250 °C。另外, 加熱時間較宜約爲1 0分鐘〜1小時,更佳約爲5〜3 0分鐘。 本發明之彩色濾光片可以用於LCD用之彩色濾光片, 也適用於C C D等影像感測器,尤以超過如i 〇 〇萬像素之高 φ 解像度的CCD元件或CMOS元件等。例如,本發明之彩色 濾光片最適用於作爲配置於構成C C D之各像素受光部與爲 了進行聚光之微攝鏡頭之間的彩色濾光片。 【實施方式】 【實施例1】 藉由實施例,更具體說明本發明,但是,本發明並非局 限於此等實施例。還有,只要無特別之說明,「份」係質量 基準。 φ <比較例1 > 甲基丙烯酸苯甲酯/甲基丙烯酸共聚物 16.4質量份 (莫耳比7 0/30、重量平均分子量30000) 二異戊四醇五丙烯酸酯 6.5質量份 ‘ 丙二醇一甲基乙基醋酸酯 13.8質量份 •乙基-3-乙氧基丙酸酯 12.3質量份 三哄系起始劑(VI) 0.3質量份 利用攪拌機進行該等成分之混合,製作平坦化膜用光阻 -29- 200540465 劑溶液。 利用旋轉塗布而將此平坦化膜用光阻劑溶液塗布於6吋 矽晶圓上,調整旋轉塗布之塗布旋轉數,使得塗布後之於表 面溫度120°C熱板上進行120秒鐘之加熱處理後的膜厚成爲 約2 ,再以此旋轉數,於晶圓上進行平坦化膜用光阻劑之 均勻塗布。之後,置於烘箱中,於220 °C進行1小時之烘烤 而使塗膜予以硬化。 3.3質量份 3.6質量份 25質量份 1 1質量份 4.4質量份 0.5質量份* The amount of the A starter is more preferably 〇 1 to 50% by mass, more preferably 1 to 30%, and more preferably 1 to 20% by mass. The amount of the photopolymerization initiator. If the mass% is small, the polymerization will be difficult to proceed. If it exceeds, the polymerization rate will increase, but the molecular weight may become low and the film may be used. In addition to the photocurable composition of the present invention, a thermal polymerization inhibitor is added in advance. For example, hydroquinone, ^ methoxy! Butylcresol, pyrogallol, butylcatechol, p-benzoquinone, 4,4 • (3-methyl-6-bubutylphenol), 2,2'-methylenebis (4-methyl · phenol) , 2-hydrothiobenzimidazole, and the like are useful. (Solvent) The photocurable composition used in the present invention is basically not limited if it is used to satisfy the solubility and coating properties of the composition when necessary. In particular, the application of dyes and adhesives (alkali soluble resin) is considered. It is more ideal to choose it with safety and security. Solvents that can be used when preparing photocurable compositions include, for example, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, isobutyl acetate, butyl propionate, and butyric acid. Ethyl isocyanate, butyl butyrate, alkyl esters; methyl lactate, methyl lactate, ethyl hydroxyacetate, butyl hydroxyacetate, methoxyacetoxyethyl acetate, methoxyacetic acid Butyl ester, ethoxyacetic acid methyl ethyl acetate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, etc .; alkyl propionates; methyl 3-methoxypropionate, 3-methoxy Methyl propionate ethoxy propionate methyl ester, 3-ethoxy propionate ethyl ester, 2-hydroxy propionate methyl mass%, if it is weaker than 0.0050 mass%, the strength should be further reduced. Solvents for bis-6-butylene are only specifically soluble. Examples are: esters, pentyl formate, butyl, methyl glycolate, esters, 3-hydroxyesters of ethoxy, 3-ethyl esters, 2-hydroxy-24- 200540465 ethyl propionate, propyl 2-hydroxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2-ethoxy base Methyl propionate '2-ethyl, ethyl oxypropionate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, Methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate , Ethyl acetate, methyl 2-hydroxybutyrate, ethyl 2-hydroxybutyrate, etc .; ethers, such as' diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol Alcohol monoethyl ether, methyl cellulose acetate, ethyl φ cellulose acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether Ethers, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc .; ketones, for example, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc. ; Aromatic hydrocarbons, for example, toluene, xylene and the like. Among these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellulose acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3 -Methyl methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, φ butyl carbitol acetate, propylene glycol methyl ether, propylene glycol methyl ether acetate, etc. are more suitable . (Other Additives) In the photocurable composition of the present invention, various kinds of additives may be blended, if necessary, for example, fillers, polymer compounds other than this, surfactants, adhesion promoters, Antioxidants, UV absorbers, anticoagulants, etc. Specific examples of such additives include glass, alumina, and other fillers; polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluorinated alkane 25-200540465 based acrylate, etc. Polymer compounds other than adhesive resins; non-ionic, cationic, anionic surfactants, etc .; ethylenetrimethoxysilane, ethylene, ethylenetriethoxysilane, ethylenetri (2-methoxyethoxy) Group) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyltrimethoxysilane, 3 -Aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxy Cyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryl 醯 φoxytrimethoxysilane, 3-hydrogen Adhesion promoters such as thiopropyltrimethoxysilane; antioxidants such as 2,2-thiobis (4-methyl-6 + butylphenol) and 2,6-dibutylphenol; 2-(3 -Butyl-5-methyl-2-hydroxyphenyl) -5-chloro And triazole, alkoxy benzophenone ultraviolet absorbers and the like; and anti-aggregating agents such as sodium polyacrylate. In addition, when it is desired to accelerate the alkali solubility of the unirradiated portion and further improve the developability of the photocurable composition, an organic carboxylic acid can be used in the photocurable composition, and a molecular weight of 1 is preferred. 0 0 0 or less Φ addition of low molecular weight organic carboxylic acid. Specific examples include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, valeric acid, hexanoic acid, trimethylhexanoic acid, diethylacetic acid, heptanoic acid, and octanoic acid; oxalic acid, malonic acid, Succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, azelaic acid, methyl'malonic acid, ethylmalonic acid, dimethylmalonic acid , Disuccinic acid, tetramethylsuccinic acid, citraconic acid and other aliphatic dicarboxylic acids; trimellitic acid, propylene tricarboxylic acid, camphor tricarboxylic acid and other aliphatic dicarboxylic acids; benzoic acid, phenylacetic acid, p-isopropyl Aromatic monocarboxylic acids such as benzoic acid, 2,3-dimethylphenyl acid, 3,5-dimethylphenyl acid, etc .; 200540465; phthalic acid, isophthalic acid, terephthalic acid, Aromatic polycarboxylic acids such as trimellitic acid, pyromellitic acid, trimellitic acid, pyromellitic acid; phenethyl-acid, cardiomethylphenylacetic acid, hydrogenated cinnamic acid, picric acid, phenylsuccinic acid , Atomic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamic acid, coumaric acid, umbellic acid and other carboxylic acids. < Color filter > The color filter of the present invention is manufactured using the photocurable composition. The method for producing a color filter of the present invention is characterized in that it comprises the step of applying the photohardening φ composition to a substrate directly or through another thin layer, and then drying to form a coating film (coating). A film forming step); a step of exposing a specific pattern on the coating film (exposure step); a step (exposure step) of performing an image processing treatment of the exposed coating film using an alkaline developing solution; and A step (post-baking step) of applying heat treatment to the coating film subjected to the development processing. Through these steps, a colored pattern can be formed. In addition, if necessary, the method for producing a color filter of the present invention may include a step of curing by heating and exposing the photoresist pattern. φ This coating film forming step is to apply and dry a photocurable composition on a substrate by coating methods such as spin coating, flow coating, roll coating, and slit coating to form a photosensitive composition layer (coating film Floor). Examples of the substrate include, for example, soda-lime glass for a liquid crystal display element, 'hard (R) glass, quartz glass, and a substrate having a transparent conductive film attached to such glass, or photoelectric conversion for a photographic element, etc. Element substrates, such as silicon substrates or complementary metal oxide film semiconductors (CMOS). These substrates may also form a black matrix that isolates each pixel. -27- 200540465 ► In addition, if necessary, an undercoat layer may be provided on these substrates in order to improve the adhesion to the upper thin layer, prevent the diffusion of substances, or flatten the substrate surface. The exposure step is to expose the coating film formed in the coating film forming step, for example, to expose a specific pattern through a mask or the like. The radiation used for exposure is particularly suitable for ultraviolet rays such as g-line, h-line, and i-line. This developing step is a step of developing an exposed coating film using an alkaline developing solution. As the alkaline imaging solution, any type of alkaline imaging solution that does not dissolve the exposed portion (radiation irradiated portion) as long as it can dissolve the composition of the φ invention can be used. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used. Examples of the organic solvent include the solvent used when the photocurable composition used in the present invention is prepared. Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, diethylamine, dimethylethanolamine, and tetramethylammonium. Hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-azinecyclo- [5 · 4 · 0] -7-undecene, etc. The alkaline developing solution used in the present invention is preferably an alkaline aqueous solution whose alkali concentration is adjusted to pH 1 1 to 1 3, and more preferably adjusted to pH 1 1 · 5 to 1 2 · 5. If the alkali concentration exceeds pH 1 3, the pattern may be rough or peeling, and the residual film rate may decrease. If it is lower than pH 1 1, the development speed will be slower, and the occurrence of residues will be observed. situation. This developing step is performed by using a developing solution made of such an alkaline aqueous solution. Examples of the development method include dipping method, spray method, -28-20Q540465 puddle method, and the like, and the temperature is preferably 15 to 40 ° C. In addition, usually, the image is washed with a general water stream after development. Furthermore, in the method for producing a color filter of the present invention, in order to sufficiently harden the coating film after development, a heat treatment is performed in a post-baking step. The heating temperature in this heating step is preferably 100 to 300 ° C, and more preferably 150 to 250 ° C. The heating time is preferably about 10 minutes to 1 hour, and more preferably about 5 to 30 minutes. The color filter of the present invention can be used as a color filter for LCD, and is also suitable for image sensors such as CC, especially CCD elements or CMOS elements with a high φ resolution of more than 1 million pixels. For example, the color filter of the present invention is most suitable as a color filter disposed between a light receiving portion of each pixel constituting CC and a micro-lens for focusing. [Embodiment] [Embodiment 1] The present invention will be described more specifically by way of examples. However, the present invention is not limited to these embodiments. In addition, unless otherwise specified, "parts" are the basis of quality. φ < Comparative Example 1 > 16.4 parts by mass of benzyl methacrylate / methacrylic copolymer (Molar ratio 7 0/30, weight average molecular weight 30,000) 6.5 parts by mass of diisopentaerythritol pentaacrylate ' 13.8 parts by mass of monomethyl ethyl acetate • 12.3 parts by mass of ethyl-3-ethoxypropionate 0.3 parts by mass of trioxane-based starter (VI) 0.3 parts by mass are blended with a blender to produce a flat film Use Photoresist-29-200540465 agent solution. The photoresist solution for this flattening film was coated on a 6-inch silicon wafer by spin coating, and the number of spins of the spin coating was adjusted so that the coating was heated on a hot plate with a surface temperature of 120 ° C for 120 seconds. The thickness of the film after the treatment becomes about 2 and then the number of rotations is used to uniformly coat the photoresist for the planarization film on the wafer. After that, it was placed in an oven and baked at 220 ° C for 1 hour to harden the coating film. 3.3 parts by mass 3.6 parts by mass 25 parts by mass 1 1 parts by mass 4.4 parts by mass 0.5 parts by mass
甲基丙烯酸苯甲酯/甲基丙烯酸共聚物 (丙烯酸系樹脂)Benzyl methacrylate / methacrylic acid copolymer (acrylic resin)
山陽色素製顏料分散液SP Blue C921 丙二醇一甲基乙基醋酸酯 乙基-3-乙氧基丙酸酯 作爲光聚合起始劑之三哄系起始劑(VI ) 利用攪拌機進行該等成分之混合,製作光硬化性組成 φ物。 三阱系起始劑(VI)係下列之化合物。 【化學式3】Sanyo Pigment Pigment Dispersion Solution SP Blue C921 Propylene Glycol Monomethyl Ethyl Acetate Ethyl-3-Ethoxypropionate as a Photopolymerization Initiator (VI) Trio-based Initiator (VI) These ingredients are prepared with a blender These are mixed to produce a photocurable composition φ. The triple well initiator (VI) is the following compound. [Chemical Formula 3]
調整旋轉塗布之塗布旋轉數而塗布此光硬化性組成物 之後’於100°C熱板上進行120秒鐘加熱處理後之膜厚成爲 -30- 200540465 i · 約1 . 0/xm,於矽晶圓上進行該平坦化膜之均勻塗布。 接著,進行已塗布之彩色光阻劑層的加熱處理,使乾燥 塗膜得以形成。此情形之加熱處理係於1 1 〇°C熱板上進行1 20 秒鐘熱烤。 接著,利用Canon製FPA-3 000ist之i線步進式曝光機, 將2,000〜10,000J/m2之曝光量,以l,〇〇〇mJ/m2之間隔,分 別透過基板上之已配置於4x3mm中的2.0/xm之正方形像素 的光罩,對該乾燥塗膜進行步進式曝光。 II 歷經圖案曝光之薄膜係利用四甲基銨氫氧化物(TMAH ) 之0.3質量%水溶液,進行35°C、60秒鐘之浸置式顯像之後, 利用2 0秒旋轉沖淋方式進行純水沖洗,進一步再進行純水 之水洗。之後,利用高度之空氣吹散水滴,使基板自然乾燥 後得到像素圖案。將其輪廓顯示於第1圖。 <實施例1〜3 > 除了變更比較例1之丙烯酸系樹脂的甲基丙烯酸苯甲酯 /甲基丙烯酸共聚物3.3質量份,而使用下表1之丙烯酸系樹 #脂之外,利用相同於比較例1之條件製作光硬化性組成物, 並利用相同之條件得到像素圖案。將其輪廓顯示於第1圖。 【表1】 丙烯酸系樹脂 實施例1 BzMA/MAA/PME400 重量平均分子量 = 76/20/4 (莫耳比) Mw : 15,000 實施例2 BzMA/IBMA/HEMA/MAA/PME400 重量平均分子量 = 30/38/8/20/4 (莫耳比) Mw ; 10,000 實施例3 BzMA/MAA/HEMA 重量平均分子量 = 60/21/19 (莫耳比) Mw : 13,000 200540465After adjusting the number of spins of the spin coating to apply this photocurable composition, the film thickness after heat treatment on a 100 ° C hot plate for 120 seconds becomes -30- 200540465 i · about 1.0 / xm in silicon The wafer is uniformly coated with the planarizing film. Next, a heat treatment is performed on the coated color resist layer to form a dried coating film. The heat treatment in this case was performed on a hot plate at 110 ° C for 120 seconds. Next, using an i-line stepping exposure machine manufactured by Canon FPA-3 000ist, an exposure amount of 2,000 to 10,000 J / m2 was passed through the substrate at an interval of 1, 000 mJ / m2, which had been arranged at 4x3 mm. A 2.0 / xm square pixel photomask is used for stepwise exposure of the dried coating film. II The pattern-exposed thin film was developed by using a 0.3 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) for 35 seconds at 60 ° C for immersion development, followed by 20 seconds of spin-on shower for pure water. Rinse and then rinse with pure water. After that, the water droplets are blown away by using a high degree of air, and the substrate is naturally dried to obtain a pixel pattern. The outline is shown in Figure 1. < Examples 1 to 3 > Except that 3.3 parts by mass of benzyl methacrylate / methacrylic acid copolymer of the acrylic resin of Comparative Example 1 was changed, and the acrylic resin #ester of Table 1 below was used, A photocurable composition was produced under the same conditions as in Comparative Example 1, and a pixel pattern was obtained under the same conditions. The outline is shown in Figure 1. [Table 1] Acrylic resin Example 1 BzMA / MAA / PME400 Weight average molecular weight = 76/20/4 (Molar ratio) Mw: 15,000 Example 2 BzMA / IBMA / HEMA / MAA / PME400 Weight average molecular weight = 30 / 38/8/20/4 (Molar ratio) Mw; 10,000 Example 3 BzMA / MAA / HEMA Weight average molecular weight = 60/21/19 (Molar ratio) Mw: 13,000 200540465
BzM A :甲基丙烯酸苯甲酯 MAA :甲基丙烯酸酯 PME400 : CH2 = C ( CH3 ) -C〇〇- ( C2H4〇 ) 9-〇CH3 IBMA :甲基丙烯酸異丁酯 HEMA :甲基丙烯酸羥甲酯 <實施例4 > 除了將實施例1之光聚合性單體由二異戊四醇五丙儲酸 酯變更成KAY ARAD RP-1040(日本化藥(股)製)之外’ φ利用相同於實施例1之條件製作光硬化性組成物’並利用相 同之條件而得到像素圖案。將其輪廓顯示於第1圖° KAY ARAD RP- 1 040 (日本化藥(股)製)係如下列構 造式,於分子內具有環氧乙焼基。 【化學式4】 KAYARAD RP- 1 040BzM A: benzyl methacrylate MAA: methacrylate PME400: CH2 = C (CH3) -C〇〇- (C2H4〇) 9-〇CH3 IBMA: isobutyl methacrylate HEMA: hydroxyl methacrylate Methyl ester < Example 4 > Except changing the photopolymerizable monomer of Example 1 from diisopentaerythritol pentapropionate to KAY ARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd.) φ A photocurable composition was produced under the same conditions as in Example 1 and a pixel pattern was obtained under the same conditions. The outline is shown in Figure 1. KAY ARAD RP-1 040 (manufactured by Nippon Kayaku Co., Ltd.) has the following structural formula, and has an ethylene oxide fluorenyl group in the molecule. [Chemical Formula 4] KAYARAD RP- 1 040
<實施例5、6 ;比較例2、3 > 除了將實施例1之PME400聚環氧乙院鏈之重複數次由 9變更成下表2所示者之外’利用相同於實施例1之條件而 得到像素圖案。將其輪廓顯示於第1圖。 -32- 200540465 【表2】 η (EO鏈之重複數目) 線寬變化率 實施例5 4 ( ΡΜΕ200) 6.21xl(T5 實施例6 23 (ΡΜΕ1000) 6.5><10巧 比較例2 1 8·5χ10·5 比較例3 30 8.7Χ10'5 由第1圖可以明確得知,該實施例、比較例所得到的像 素圖案,相較於比較例,實施例之像素圖案的形狀、大小之 φ 變化較少。 另外,測定該實施例、比較例所得到的2.0/xm之正方形 像素圖案上部之寬度,將其相對於曝光量之寬度變化予以作 圖’進一步利用電腦進行直線回歸處理,得到回歸直線(參 照第2圖)。其回歸直線之斜率爲相對於塗膜曝光強度的顯 像後線寬變化率。 由第2圖得知,比較例之該線寬變化率爲大的,顯像後 之像素圖案的寬度也變大。 • 針對於此,實施例之該線寬變化率爲小的,顯像後之像 素圖案的寬度也變小。尤以使用分子中具有環氧乙烷基鏈之 光聚合性單體之實施例4的話,該線寬變化率更爲小’顯像 後之像素圖案的寬度也變得更小。 <線寬變化率> 比較例1 … 1 .07χ 1 0'4 實施例1 … 5.96X10·5 實施例 2 ... 4.9〇χ 1 (Γ5 -33- 200540465 實施例 3 ... 6.77x 1 0_5 實施例 4 ... 3.29x1 0'6 【產業上利用之可能性】 根據本發明的話,能夠提供一種彩色濾光片,其係藉由 微影術而將所得到的像素控制成所要之大小、形狀。因而, 本發明之彩色濾光片係以LCD用彩色濾光片爲主,能夠用 於CCD等之影像感測器,尤以超過如1 〇〇萬像素之高解像 度的CCD元件或CMOS元件等。例如,本發明之彩色濾光 0 片最適合於作爲配置於構成CCD之各像素受光部與爲了進 行聚光之微攝鏡頭之間的彩色濾光片使用。 【發明之效果】 本發明之彩色濾光片係藉由微影術而將所得到的彩色 濾光片之像素控制成所要之大小、形狀。 【圖式簡單說明】 第1圖係顯示像素圖案之輪廓的圖形。 第2圖係顯示相對於塗布膜曝光強度之顯像後線寬變化 φ的圖形。 【元件符號說明】 iffi 〇 -34-< Examples 5, 6; Comparative Examples 2, 3 > The same use as in the example was performed except that the repeat of the PME400 polyethylene oxide chain of Example 1 was changed from 9 to the number shown in Table 2 below. The pixel pattern is obtained under the condition of 1. The outline is shown in Figure 1. -32- 200540465 [Table 2] η (repeated number of EO chain) Line width change rate Example 5 4 (PME200) 6.21xl (T5 Example 6 23 (PME1000) 6.5 > < 10) Comparative Example 2 1 8 · 5χ10 · 5 Comparative Example 3 30 8.7 × 10'5 As can be clearly seen from FIG. 1, the pixel patterns obtained in this embodiment and the comparative example are compared with the comparative example in terms of the shape and size of the pixel pattern φ In addition, the width of the upper part of the square pixel pattern of 2.0 / xm obtained in this example and the comparative example was measured, and the change in width with respect to the exposure amount was plotted. Further, a linear regression process was performed using a computer to obtain regression. Straight line (refer to Figure 2). The slope of the regression straight line is the line width change rate after development relative to the exposure intensity of the coating film. From Figure 2, it is known that the line width change rate of the comparative example is large and the image is developed. The width of the subsequent pixel pattern also becomes larger. • In view of this, the line width change rate of the embodiment is small, and the width of the pixel pattern after development is also reduced. Especially the ethylene oxide group is used in the molecule Photopolymerizable monomer of chain of Example 4 If the line width change rate is smaller, the width of the pixel pattern after development becomes smaller. ≪ Line width change rate > Comparative Example 1… 1.07 × 1 0'4 Embodiment 1… 5.96X10 · 5 Example 2 ... 4.9〇χ 1 (Γ5 -33- 200540465 Example 3 ... 6.77x 1 0_5 Example 4 ... 3.29x1 0'6 [Possibility of industrial use] According to the present invention If so, a color filter can be provided which controls the obtained pixels to a desired size and shape by lithography. Therefore, the color filter of the present invention is mainly a color filter for LCD It can be used for image sensors such as CCDs, especially high-resolution CCD elements or CMOS elements, such as 10 million pixels. For example, the color filter 0 of the present invention is most suitable for being configured as a CCD. Use a color filter between the light-receiving part of each pixel and a micro-lens for focusing. [Effects of the Invention] The color filter of the present invention is a color filter obtained by lithography. The pixels are controlled to the desired size and shape. [Simplified description of the figure] Figure 1 shows the pixels Pattern. FIG. 2 pattern of contour lines showed iffi square pattern after developing the exposed coating film strength with respect to the line width variation φ. [Description of Symbols] -34- element
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JP5164409B2 (en) * | 2006-09-28 | 2013-03-21 | 富士フイルム株式会社 | PHOTOCURABLE COMPOSITION, COLOR FILTER, ITS MANUFACTURING METHOD, AND SOLID-STATE IMAGING DEVICE |
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US8158307B2 (en) | 2007-02-14 | 2012-04-17 | Fujifilm Corporation | Color filter and method of manufacturing the same, and solid-state image pickup element |
JP2008241744A (en) | 2007-03-23 | 2008-10-09 | Fujifilm Corp | Method of manufacturing color filter |
JP2009198664A (en) | 2008-02-20 | 2009-09-03 | Fujifilm Corp | Color filter, method for producing the same, and solid imaging element |
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