TW569043B - Radiation sensitive composition for color liquid crystal display devices - Google Patents

Radiation sensitive composition for color liquid crystal display devices Download PDF

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Publication number
TW569043B
TW569043B TW091112251A TW91112251A TW569043B TW 569043 B TW569043 B TW 569043B TW 091112251 A TW091112251 A TW 091112251A TW 91112251 A TW91112251 A TW 91112251A TW 569043 B TW569043 B TW 569043B
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TW
Taiwan
Prior art keywords
acid
radiation
pigment
pattern
sensitive composition
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Application number
TW091112251A
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Chinese (zh)
Inventor
Shigeru Abe
Takayoshi Koyama
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Jsr Corp
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Publication of TW569043B publication Critical patent/TW569043B/en

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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
    • G03F7/004—Photosensitive materials
    • 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
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images

Abstract

A radiation sensitive composition comprising (A) a colorant containing a pigment, (B) an alkali-soluble resin, (C) a polyfunctional monomer and (D) a photopolymerization initiator, having an erosion rate of a 20 mum dot pattern formed therefrom of 30% or less, and used to form a spacer and/or a black matrix on a drive substrate for a thin film transistor (TFT) color liquid crystal display device. This composition has a low erosion rate of a pattern formed therefrom, thereby making it difficult for the formed pattern to be tapered reversely at the time of development, can prevent effectively rubbing cloth from being caught by a pattern portion and the separation of the pattern, is free from a display failure such as image sticking and is used to form a spacer and/or a black matrix on a drive substrate for a thin film transistor (TFT) color liquid crystal display device.

Description

569043 經濟部智慧財產局員工消費合作社印製 A7 ___ B7_五、發明説明（1 ) 發明領域 本發明係關於一種用以在用於薄膜電晶體（T F T ) 彩色液晶顯示裝置的驅動基質上形成間隙壁及/或黑色基 質的輻射敏感性組合物。 先前技藝之描述 在先前技藝中，爲了由黑色輻射敏感性組合物生產用 於濾色器的間隙壁及黑色基質，將內含黑色著色劑分散於 其中的輻射敏感性組合物施用於基質上且乾燥，且經由光 罩將得到的塗覆膜曝光於輻射線（以下稱爲a曝光〃）且 顯影以形成所欲求之圖案。 雖然大量的黑色著色劑必須內含在黑色輻射敏感性組 合物之中以改良間隙壁或黑色基質的光過濾性質，輻射線 係經由著色劑吸收，從而必然地造成輻射線在塗層膜中的 有效之強度將由塗層膜之表面至底部（換言之，接近基質 之表面）逐步地減低之現象。因此，在塗層膜中的硬化反 應由表面至底部傾向變得更不完全的，從而使所形成圖案 較低的部分在顯影中將被顯影劑移除，且據此，圖案之邊 緣傾向在末端成爲反向逐漸變得尖細。然而，當邊緣呈反 向逐漸變得尖細，當用於結晶定向摩擦中，摩擦布將被邊 緣部分捕獲，而導致圖案可能剝離或摩擦布可能磨損。 此外，在濾色器放置在用於薄膜電晶體（T F T )彩 色液晶顯示裝置的驅動基質上的系統之中，其中，將導孔 形成在濾色器中以使I T〇（錫攙添氧化銦）膜與電極相 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -4- 569043 A7 B7 五、發明説明（2 ) 互導電。當於形成濾色器之後形成間隙壁或黑色基質，用 以形成間隙壁或黑色基質的輻射敏感性組合物之殘餘物傾 (請先閱讀背面之注意事項再填寫本頁) 向保持在導孔中。若將顯影條件製作得非常嚴格以去除該 殘餘物，圖案之侵蝕將將變得較大。在此案例中，摩擦布 可能被圖案捕獲且圖案可能剝離。用於彩色液晶顯示裝置 之間隙壁及黑色基質必須不含會導致顯示失效的影像黏著 〇 然而，在先前技藝中用以形成在薄膜電晶體（T F T )彩色液晶顯示裝置中間隙壁或黑色基質的輻射敏感性組 合物，不能完全地解決此類問題。 本發明槪要 本發明之目的在提供一種輻射敏感性組合物，用以在 用於薄膜電晶體（T F T )彩色液晶顯示裝置的驅動基質 上形成間隙壁及/或黑色基質。 經濟部智慧財產局員工消費合作社印製 本發明另一項目的在提供一種用於上述目的的輻射敏 感性組合物，其中其所形成圖案之侵蝕速率低，該圖案當 在顯影中難以反向逐漸變得尖細，可有效地預防摩擦布被 圖案捕獲與圖案分離，而不會發生顯示失效如影像黏著， 該圖案具有高的膜硬度與卓越的表面平滑性，膜殘餘物與 沾污難以發生在未受影響部分的基質上，且在顯影中圖案 對基質有卓越的黏著。 由以下描述，本發明之其它目標與優點將變得明顯的 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） -5· 569043 A7 --- B7 五、發明説明（3 ) (請先閲讀背面之注意事項再填寫本頁) 首先’依據本發明，上述本發明之目標及優點可經由 ~種_射敏感性組合物而獲得，該輻射敏感性組合物（1 )包含（A )內含顏料的著色劑、（b )鹼可溶解的樹脂 、（C )多官能基單體及（d )光聚合起始劑，（2 )對 其所形成之2 0 /zm點狀圖案的侵蝕速率在3 〇 %或更 低’及（3 )係用以在用於薄膜電晶體（τ F T )彩色液 晶顯示裝置的驅動基質上形成間隙壁及/或黑色基質。 如在此使用的〃輻射線〃包含可見光線、紫外線、遠 紫外線、電子束及X -輻射線。 圖示簡要敘沭 圖1爲或解釋點狀圖案侵鈾速率之測量方法的示圖。 主要元件對照表 a 頂端寬度 b 1/2高度位置之寬度 L 由圖案底部算起高度 經濟部智慧財產局員工消費合作社印製 L/2 1/2高度位置 本發明較佳亘體實施例之詳細描流^ 以下將詳細敘述本發明。 (A )著色劑 在本發明中的著色劑爲內含顏料的著色劑 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） _ 6 - 569〇43 A7 B7 五、發明説明（4) C請先閑讀背面之注意事項再填寫本頁，> 上述顏料可依據彩色液晶顯示裝置應用之目的及所欲 求之色彩而作適當地選擇。其可爲無機或有機的，且可爲 單一的顏料或二或更多顏料之混合物。在本發明中的顏料 宜爲具有筒色彩顯影性質及高耐熱性的顏料，特別有高的 熱降解抗性，特別較佳者爲含有碳黑及/或二或更多有機 顏料者。 碳黑之實施例包括爐黑如SAF、SAF-HS、569043 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 ___ B7_ V. Description of the Invention (1) Field of the Invention The present invention relates to a method for forming a gap on a driving substrate for a thin film transistor (TFT) color liquid crystal display device. Radiation-sensitive composition of walls and / or black matrix. Description of the Prior Art In the prior art, in order to produce a partition wall and a black substrate for a color filter from a black radiation-sensitive composition, a radiation-sensitive composition containing a black colorant dispersed therein is applied to the substrate and After drying, the obtained coating film is exposed to radiation (hereinafter referred to as “a exposure light”) through a photomask and developed to form a desired pattern. Although a large amount of black colorant must be contained in the black radiation-sensitive composition to improve the light filtering properties of the partition wall or the black matrix, the radiation is absorbed through the colorant, which inevitably causes the radiation in the coating film. The effective strength will gradually decrease from the surface of the coating film to the bottom (in other words, the surface close to the substrate). Therefore, the hardening reaction in the coating film tends to become more incomplete from the surface to the bottom, so that the lower portion of the formed pattern will be removed by the developer during development, and accordingly, the edge of the pattern tends to be The tip becomes tapered in the opposite direction. However, when the edges are tapered in the opposite direction, when used in crystalline orientation friction, the friction cloth will be captured by the edge portions, which may cause the pattern to peel or the friction cloth to wear. In addition, in a system in which a color filter is placed on a driving substrate for a thin-film transistor (TFT) color liquid crystal display device, a via hole is formed in the color filter so that IT0 (tin is added with indium oxide) ) Membrane and electrode phase (please read the precautions on the back before filling this page) This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) -4- 569043 A7 B7 V. Description of the invention (2) Mutual conductivity . When a spacer or black matrix is formed after forming the color filter, the residue of the radiation-sensitive composition used to form the spacer or black matrix is tilted (please read the precautions on the back before filling this page) and keep it in the guide hole in. If the development conditions are made very strict to remove this residue, the erosion of the pattern will become larger. In this case, the rubbing cloth may be captured by the pattern and the pattern may be peeled off. The spacers and black substrates used in color liquid crystal display devices must be free of image sticking that would cause display failure. However, in the prior art, the spacers or black substrates used to form thin film transistor (TFT) color liquid crystal display devices Radiation-sensitive compositions cannot completely solve such problems. SUMMARY OF THE INVENTION The object of the present invention is to provide a radiation-sensitive composition for forming a partition wall and / or a black matrix on a driving substrate for a thin film transistor (T F T) color liquid crystal display device. The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed another item of the present invention to provide a radiation-sensitive composition for the above purpose, wherein the erosion rate of the pattern formed by it is low, and the pattern is difficult to reverse gradually during development. It becomes tapered, which can effectively prevent the friction cloth from being captured and separated by the pattern without display failure such as image sticking. The pattern has high film hardness and excellent surface smoothness, and film residues and stains are difficult to occur. On the unaffected part of the substrate, and the pattern has excellent adhesion to the substrate during development. From the following description, other objects and advantages of the present invention will become apparent. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -5 · 569043 A7 --- B7 V. Description of the invention (3 ) (Please read the notes on the back before filling this page) First of all, according to the present invention, the above-mentioned objects and advantages of the present invention can be obtained through a variety of radiation-sensitive compositions. The radiation-sensitive composition (1) contains (A) a pigment-containing coloring agent, (b) an alkali-soluble resin, (C) a polyfunctional monomer, and (d) a photopolymerization initiator, and (2) a 20 / zm point formed thereon The erosion rate of the pattern is 30% or lower, and (3) is used to form a partition wall and / or a black matrix on a driving substrate for a thin film transistor (τ FT) color liquid crystal display device. As used herein, "radiation rays" include visible light, ultraviolet rays, extreme ultraviolet rays, electron beams, and X-radiation rays. Brief description of the figure Figure 1 is a diagram illustrating or explaining a method for measuring the uranium invasion rate in a dot pattern. Comparison table of main components a Top width b 1/2 height position width L Counting from the bottom of the pattern Height printed by the Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperatives L / 2 1/2 height position Details of the preferred embodiment of the present invention Describing ^ The present invention will be described in detail below. (A) Coloring agent The coloring agent in the present invention is a coloring agent containing pigments. The paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) _ 6-569〇43 A7 B7 V. Description of the invention (4 ) C Please read the precautions on the back before filling in this page. ≫ The above pigments can be appropriately selected according to the purpose of the color liquid crystal display device application and the desired color. It may be inorganic or organic and may be a single pigment or a mixture of two or more pigments. The pigment in the present invention is preferably a pigment having a tube color developing property and high heat resistance, particularly a high resistance to thermal degradation, and particularly preferably one containing carbon black and / or two or more organic pigments. Examples of carbon black include furnace blacks such as SAF, SAF-HS,

ISAF、ISAF-LS、ISAF-HS、HAF、 HAF — LS、HAF — HS、NAF、FEF、FEF 一 HS、SRF、SRF-LM、SRF-LS、GPF 、ECF、N— 339 及 N— 351 ;熱黑如 FT 及MT ;及乙炔黑。 此類碳黑可單獨使用或合倂二或更多者而使用。 緩濟部智慧財產局員工消費合作社印製 除了碳黑之外的無機顏料之實施例包括金屬氧化物如 鈦黑、C u — F e - Μη爲主的氧化物及合成的鐵黑。 此類無機顏料可單獨使用或合倂二或更多者而使用。 此外，上述有機顏料之實施例包括依據色彩指數（ C.I.;由 The Society of Dyers and Colourists 頒佈）而分類 爲顏料類群的化合物，尤其是其具有以下色彩指數（C . 1 .)數字的化合物： C. I ·顏料黃色12，C· I ·顏料黃色13，C • I ·顏料黃色14，C· I ·顏料黃色17，C. I . 顏料黃色20，C. I .顏料黃色24、C. I ·顏料黃 色31、C.I·顏料黃色55、C.I.顏料黃色83 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） 、發明説明（ 經濟部智慧財產局員工消費合作社印製 C . Ϊ ·顏料黃色9 3、 •1.顏料黃色11〇 (：’1.顏料黃色10 L顏料黃色139、c .1.顏料黃色138 •類料黃色i03、c ·ι·顏料黃色150、 _料黃色155 c I·顏料黃色154、C 料黃色168及二2料黃色i“、c· 顏料黃色2 ；L工； ^•1.顏料橙色36、 • I .顏料橙色5 i、c L · 1 .顏料橙色4 顧料橙色γ i ; · 1 .顏料橙色6 1及C C . I .顏料紅色9、^ 1 ·顔料紅色]_ 2 2、C · I ·顏料紅色9 7 .顏料紅色1 4 9、c · · 1 _顏料紅色1 2 3、 顏料紅色1 7 6、。： 1 ·顏料紅色1 6 8、C 料紅色180、c· 1 _顏料紅色i”、c· 紅色2 1 5、C I :料紅色2 〇 9、C . 1 顏料紅色224、c、 4 2及° . I ·顏料紅色2 5 4 ; (：.1.顏料紫色19、^^ τ .I ·顏料紫色29 ; . 1 .顏料紫色2 顏料藍色15、C l .顏 I .顏料藍色；L 5 : 3、C 1 ^料-色5 r τ ••顏料藍色1 5c . I ·顏料藍色i 5 : 6 ; T I. 1 .顏料綠色7、C · 1 .顏料綠色36 .顏料綠色1 3 6及c」.顔料綠色2…ISAF, ISAF-LS, ISAF-HS, HAF, HAF — LS, HAF — HS, NAF, FEF, FEF — HS, SRF, SRF-LM, SRF-LS, GPF, ECF, N-339 and N-351; Hot black such as FT and MT; and acetylene black. Such carbon blacks can be used alone or in combination of two or more. Examples of inorganic pigments other than carbon black printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs include metal oxides such as titanium black, Cu-Fe-Mn-based oxides, and synthetic iron black. Such inorganic pigments may be used alone or in combination of two or more. In addition, the above examples of organic pigments include compounds classified as pigment groups according to the color index (CI; promulgated by The Society of Dyers and Colourists), especially compounds having the following color index (C. 1..) Numbers: C I · Pigment Yellow 12, C · I · Pigment Yellow 13, C • I · Pigment Yellow 14, C · I · Pigment Yellow 17, C. I. Pigment Yellow 20, C. I. Pigment Yellow 24, C. I · Pigment Yellow 31, CI · Pigment Yellow 55, CI Pigment Yellow 83 The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm), the invention description (printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs). Ϊ · Pigment yellow 9 3, • 1.Pigment yellow 11〇 (: '1.Pigment yellow 10 LPigment yellow 139, c.1.Pigment yellow 138 • Class yellow i03, c · ι · Pigment yellow 150, Yellow 155 c I · pigment yellow 154, C material yellow 168 and two materials yellow i ", c · pigment yellow 2; L engineering; ^ • 1. Pigment orange 36, • I. pigment orange 5 i, c L · 1 .Pigment Orange 4 Considering Orange γ i; · 1. Pigment Orange 6 1 and CC. I. Pigment Red 9, ^ 1 · Pigment Red] _ 2 2, C · I · Pigment Red 9 7 .Pigment Red 1 4 9, c · · 1 _Pigment Red 1 2 3, Pigment Red 1 7 6, ...: 1 · Pigment Red 1 6 8. C material red 180, c · 1 _ pigment red i ”, c · red 2 1 5, CI: material red 2 009, C. 1 pigment red 224, c, 4 2 and °. I · pigment red 2 5 4; (: .1.Pigment purple 19, ^^ τ.I · Pigment purple 29; .1.Pigment purple 2Pigment blue 15, C l .Pigment I.Pigment blue; L 5: 3, C 1 ^ Material-color 5 r τ •• Pigment blue 1 5c. I · Pigment blue i 5: 6; T I. 1. Pigment green 7, C · 1. Pigment green 36 .Pigment green 1 3 6 and c " .Pigment Green 2 ...

9、C 、C . C . I .I . I .顏 3 、C 、c . C . I .I . I •顏 .顏料 顏料紅 3及C 0、C :4及 、C . ----^--J---衣-- (請先閲讀背面之注意事項再填寫本頁) 訂9, C, C. C. I. I. I. Yan 3, C, c. C. I. I. I • Yan. Pigment Pigment Red 3 and C 0, C: 4 and C. ---- ^-J --- yi-- (Please read the precautions on the back before filling this page) Order

C·1 _顏料棕色23及C 本紙張尺度適用中ίί家標準（( 21〇X297i¥TC · 1 _Pigment Brown 23 and C This paper is applicable to Chinese standards ((21〇X297i ¥ T

5 ;及 -8 - 569043 經濟部智慧財產局員工消費合作杜印製 A7 __ B7_五、發明説明（6 ) c.I·顏料黑色1及C.I·顏料黑色7。 此類有機顏料可單獨使用或合倂二或更多者而使用。 在此類有機顏料之中，特別較佳者爲C .；[.顏料紅 色177與C . I ·顏料藍色15 : 4之混合物及/或（： .· I ·顏料紅色1 7 7與C . I .顏料藍色1 5 : 6之混 合物。 本發明的著色劑可視需要包含增量劑顏料。 上述增量劑顏料之實施例包括硫酸鋇、碳酸鋇、碳酸 鈣、二氧化矽、鹼性的碳酸鎂、氧化鋁白色、光澤白色、 锻白色及氫滑石粉。 此類增量劑顏料可單獨使用或合倂二或更多者而使用 〇 增量劑顏料之含量宜在0至1 0 0重量份，更佳者在 5至5 0重量份，大幅更佳者在1 0至4 0重量份，此係 基於1 0 0重量份的所有顏料之總量。 本發明中，上述顏料之表面可在使用之前經由聚合物 作改良。 除了顏料之外的著色劑爲染料、天然的著色劑或其類 似者。 -氨基甲酸酯爲主的分散劑- 本發明中，內含在此著色劑中的顏料合意地經由分散 劑作分散，特別較佳者爲具有氨基甲酸酯鍵結的分散劑（ 以下稱爲 > 氨基甲酸酯爲主的分散劑〃）。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁)5; and -8-569043 employee cooperation of Intellectual Property Bureau of the Ministry of Economic Affairs, printed by Du A7 __ B7_ V. Description of Invention (6) c.I. Pigment Black 1 and C.I. Pigment Black 7. Such organic pigments can be used alone or in combination of two or more. Among such organic pigments, C .; [.Pigment Red 177 and C. I. Pigment Blue 15: 4 mixture and / or (: .. I. Pigment Red 1 7 7 and C I. Pigment blue 15: 6 mixture. The coloring agent of the present invention may contain extender pigments as required. Examples of the above extender pigments include barium sulfate, barium carbonate, calcium carbonate, silicon dioxide, alkaline Magnesium carbonate, alumina white, glossy white, wrought white, and hydrotalcite powder. Such extender pigments can be used alone or in combination of two or more. The content of the extender pigment should be 0 to 1 0. 0 parts by weight, more preferably 5 to 50 parts by weight, and much more preferably 10 to 40 parts by weight, which is based on the total amount of 100 parts by weight of all pigments. In the present invention, The surface may be modified by a polymer before use. The coloring agents other than pigments are dyes, natural coloring agents, or the like.-Carbamate-based dispersants-In the present invention, coloring is included herein The pigment in the agent is desirably dispersed via a dispersant, and particularly preferably a carbamate Ester-bonded dispersant (hereinafter referred to as > urethane-based dispersant 〃). This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back first) (Fill in this page)

-9- 569043 A7 ___B7_____ 五、發明説明（7 ) 接著描述氨基甲酸酯爲主的分散劑。 (請先閲讀背面之注意事項再填寫本頁) 氨基甲酸酯爲主的分散劑的氨基甲酸酯鍵結一般由式 R — NH — C〇◦一 R >代表的（R及R >係各自爲脂肪 族、脂環族或芳香族單價或多價有機基團，其係鍵結至帶 有氨基甲酸酯鍵結的基團或另一基團）。該氨基甲酸酯鍵 結可存在內含在此氨基甲酸酯爲主的分散劑中的親油性基 團又及/或親水性基團之中，或在氨基甲酸酯爲主的分散 劑主鏈及/或側鏈中，且進一步的一或更多氨基甲酸酯鍵 結可存在於氨基甲酸酯爲主的分散劑中。當二或更多氨基 甲酸酯鍵結存在於氨基甲酸酯爲主的分散劑中，其可相同 或不同。 此氨基甲酸酯爲主的分散劑可爲陽離子性、陰離子性 、非離子性或兩性且可帶有矽酮爲主的或氟爲主的結構。 此氨基甲酸酯爲主的分散劑爲下列者之反應產物：二 異氰酸酯及/或三異氰酸酯，與在一端具有羥基基團的聚 酯及/或在兩端具有羥基基團的聚酯。 經濟部智慧財產局員工消費合作社印製 二異氰酸酯之實施例包括芳香族二異氰酸酯如苯二異 氰酸酯包含苯一 1 ，3 -二異氰酸酯及苯一 1 ，4 一二異 氰酸酯；甲苯二異氰酸酯包含甲苯- 2，4 一二異氰酸酯 、甲苯一 2 ，5 —二異氰酸酯、甲苯—2，6 —二異氰酸 酯及甲苯一 3，5 -二異氰酸酯；及二甲苯二異氰酸酯包 括1 ，2 —二甲苯—3 ，5 —二異氰酸酯、1 ，2 —二甲 苯一 3，6 —二異氰酸酯、1 ，2 —二甲苯一 4，6 —二 異氰酸酯、1 ，3 —二甲苯一 2，4 一二異氰酸酯、1 ， 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ~ -10- 569043 A7 B7 五、發明説明（8 ) (請先閲讀背面之注意事項再填寫本頁) 3 —二甲苯一2 ，5 —二異氰酸酯、1 ，3 —二甲苯一2 ，6—二異氰酸酯、1 ，3—二甲苯一4，6 —二異氰酸 酯、1 ，4 —二甲苯一 2，5 —二異氰酸酯及1，4 —二 甲苯- 2，6 -二異氰酸酯。三異氰酸酯之實施例包括芳 香族三異氰酸酯如苯三異氰酸酯包含苯-1，2，4 -三 異氰酸酯、苯一 1，2，5 -三異氰酸酯及苯一 1，3， 5 —三異氰酸酯；甲苯三異氰酸酯包含甲苯—2，3，5 一三異氰酸酯、甲苯一 2，3 ，6 —三異氰酸酯、甲苯— 2，4，5 —三異氰酸酯、甲苯—2，4，6 —三異氰酸 酯、甲苯—3 ，4，6 —三異氰酸酯及甲苯一 3 ，5 ，6 -三異氰酸酯；及二甲苯三異氰酸酯包含1 ，2 -二甲苯 —3 ，4，6 —三異氰酸酯、1 ，2 —二甲苯一3，5， 6 —三異氰酸酯、1，3 —二甲苯—2，4，5 —三異氰 酸酯、1 ，3 —二甲苯—2，4，6 —三異氰酸酯、1 ， 3 一二甲苯一3 ，4，5 —三異氰酸酯、1 ，4 —二甲苯 一 2，3 ，5 —三異氰酸酯及1 ，4 一二甲苯—2，3 ， 6 -三異氰酸酯。 經濟部智慧財產局員工消費合作社印製 此類二異氰酸酯及三異氰酸酯可單獨使用或合倂二或 更多者而使用。 在一端具有羥基基團的的聚酯或其在兩端具有羥基基 團的聚酯之實施例，包括其在一端或兩端具有羥基基團的 聚內酯如在一端或兩端具有羥基基團的聚己內酯、在一端 或兩端具有羥基基團的聚戊內酯、及在一端或兩端具有羥 基基團的聚丙內酯；及在一端或兩端具有羥基基團的聚縮 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X297公釐） -11 - 569043 A7 ___ B7_ 五、發明説明（9 ) 合聚酯，如一端或兩端具有羥基基團的聚對酞酸乙二醇酯 ’與在一端或兩端具有羥基基團的聚對酞酸丁二醇酯。 (請先閲讀背面之注意事項再填寫本頁) 此類在一端具有羥基基團的聚酯與在兩端具有羥基基 團的聚酯，可單獨使用或合倂二或更多者而使用。 在本發明中氨基甲酸酯爲主的分散劑較佳者爲芳香族 二異氰酸酯與在一端具有羥基基團的聚內酯兩者之反應產 物，及/或芳香族二異氰酸酯與在兩端具有羥基基團的聚 內酯兩者之反應產物，特別較佳者爲甲苯二異氰酸酯與在 一端具有羥基基團的聚己內酯兩者之反應產物，及/或甲 苯二異氰酸酯與在兩端具有羥基基團的聚己內酯兩者之反 應產物。 氨基甲酸酯爲主的分散劑之特色可在於經由任何一或 更多的熱處理、酸値、胺値及電壓保持所造成的不溶解。 經濟部智慧財產局員工消費合作社印製 針對經由熱處理所造成的不溶解之存在，氨基甲酸酯 爲主的分散劑宜在1 5 0°C或更高，更佳者在1 5 0至 2 5 0 °C加熱，且加熱時間宜在3 0分鐘或更長，更佳者 在3 0至9 0分鐘，彼合意地在極性溶劑如N，N -二甲 基曱醯胺、N，N -二甲基乙醯胺、N —甲基吡咯烷酮或 r -丁內酯之中變得不溶的。 針對酸値及胺値，該氨基甲酸酯爲主的分散劑合意地 具有（i)酸値宜在5至25 mgK〇H/g，更佳者 在8至20 mgK〇H/g且胺値爲〇 mgKOH/ g，或（i i)胺値宜在5至25 mgK〇H/g，更 佳者在8至20 mgK〇H/g且酸値在〇 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -12- 569043 A7 B7 五、發明説明（10) mgK〇H/g。（i)與（ii)不能同時滿足。 (請先閲讀背面之注意事項再填寫本頁) 針對電壓保持，該氨基甲酸酯爲主的分散劑合意地爲 具有由以下方法測量的電壓保持在8 0 %或更多，較佳 者在8 5 %或更多。測量電壓保持之方法： 將1 w t %氨基甲酸酯爲主的分散劑加入可經由溶 解成分（B ) 、（ C )及（D )在本發明中溶劑之中所製 備之溶液中，且將生成的溶液施用於在表面上有氧化銦（ I T〇）膜的基質上，以形成3 // m —厚的乾燥塗覆膜， 且然後曝光且於2 0 0至2 5 0 °C作後烘烤。於6 0 °C測 量使用得到的基質所組裝的液晶小室之電壓保持，而滯留 時間選在1 6 . 7 ms。 當經由熱處理所造成的不溶解之存在，在本發明中的 氨基甲酸酯爲主的分散劑之酸値、胺値或電壓保持將滿足 上述條件，可大幅地降低發生在液晶小室中的影像黏著。 至少具有一種的上述特性質的氨基甲酸酯爲主的分散 劑之說明性實施例包括商購之產物如E F K A - 4 6及 4 7 ( EFKA Chemicals B.V. ) 、Disperbyk(BYK Chem.公 經濟部智慧財產局員工消費合作社印製 司）及 Disparon(Kusumoto Kasei 公司）。 經由凝膠滲透層析法（G P C )測量，在本發明中的 氨基甲酸酯爲主的分散劑其就聚苯乙烯而言的重量平均分 子量（以下縮寫爲Mw)宜在5, 000至50, 000， 更佳者在7, 000至20, 000。 本發明中，該氨基甲酸酯爲主的分散劑可單獨使用或 合倂二或更多者而使用。 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） -13 - 569043 A7 ______ B7 五、發明説明（n) 該氨基甲酸酯爲主的分散劑之含量宜在0 . 5至 1 0 〇重量份’更佳者在1至7 〇重量份，大幅更佳者在 1 0S5 0重量份，此係基於1 〇 〇重量份的內含在此著 色齊ί中的顏料。當該氨基甲酸酯爲主的分散劑之含量低於 〇 · 5重量份’顏料分散之穩定性可能降低，且當其含量 高於1 0 0重量份，所得到輻射敏感性組合物之性質如可 顯影性可能會有損。 本發明中’可將分散助劑與分散劑共同使用。 上述分散助劑例如爲鄰苯二甲醯青藍磺銅化合物。 上述鄰苯二甲醯青藍磺銅化合物之特定的實施例包括 鄰苯二甲醯青藍磺銅，鄰苯二甲醯青藍銨磺酸銅、鄰苯二 甲醯青藍四甲基銨磺酸銅、鄰苯二甲醯青藍四乙基銨磺酸 銅、鄰苯二甲醯青藍四正丙基銨磺酸銅、鄰苯二曱醯青藍 四異丙基銨磺酸銅及鄰苯二甲醯青藍四正丁基銨磺酸銅。 此類鄰苯二甲醯青藍磺銅化合物可單獨使用或合倂二 或更多者而使用。 分散助劑之含量宜在2 0重量份或更低，更佳者在 1 0重量份或更低，大幅更佳者在5重量份或更低，此係 基於1 0 0重量份的內含在此著色劑中的顏料。 (Β )鹼可溶解的樹脂 在本發明中任何鹼可溶解的樹脂可接受的，g #彳系作 爲著色劑（A )之黏合劑且可溶解在顯影劑之中，特別較 佳者爲鹼性顯影劑，而用以形成間隙壁或黑色基質。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) .·裝·-9- 569043 A7 ___B7_____ 5. Description of the Invention (7) Next, the urethane-based dispersant will be described. (Please read the notes on the back before filling in this page) The urethane bond of urethane-based dispersant is generally represented by the formula R — NH — C〇◦-R > (R and R > Are each an aliphatic, cycloaliphatic, or aromatic monovalent or polyvalent organic group that is bonded to a group with a urethane bond or another group); The urethane bond may exist in a lipophilic group and / or a hydrophilic group contained in the urethane-based dispersant, or in a urethane-based dispersant In the main chain and / or side chain, and further one or more urethane bonds may be present in the urethane-based dispersant. When two or more urethane bonds are present in the urethane-based dispersant, they may be the same or different. The urethane-based dispersant may be cationic, anionic, non-ionic or amphoteric and may have a silicone-based or fluorine-based structure. The urethane-based dispersant is the reaction product of the following: diisocyanate and / or triisocyanate, polyester with a hydroxyl group at one end, and / or polyester with a hydroxyl group at both ends. Examples of diisocyanates printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs include aromatic diisocyanates such as benzenediisocyanate containing benzene-1,3-diisocyanate and benzene-1,4-diisocyanate; toluene diisocyanate containing toluene-2 4,4-diisocyanate, toluene-2,5-diisocyanate, toluene-2,6-diisocyanate, and toluene-1,3,5-diisocyanate; and xylene diisocyanate includes 1,2-xylene-3, 5— Diisocyanate, 1,2-xylene-1, 3, 6-diisocyanate, 1,2-xylene-1, 4, 6-diisocyanate, 1, 3-xylene-1, 2, 4-diisocyanate, 1, paper size Applicable to China National Standard (CNS) A4 specification (210X297mm) ~ -10- 569043 A7 B7 V. Description of the invention (8) (Please read the precautions on the back before filling this page) 3 —Xylene 1 2, 5 — Diisocyanate, 1,3-xylene-2,6-diisocyanate, 1,3-xylene-1,4,6-diisocyanate, 1,4-xylene-2,5-diisocyanate, and 1,4-diisocyanateBenzene - 2,6 - diisocyanate. Examples of triisocyanates include aromatic triisocyanates such as benzenetriisocyanate containing benzene-1,2,4-triisocyanate, benzene-1,2,5-triisocyanate and benzene-1,3,5-triisocyanate; toluene triisocyanate; Isocyanates include toluene-2,3,5-triisocyanate, toluene-2,3,6-triisocyanate, toluene-2,4,5-triisocyanate, toluene-2,4,6-triisocyanate, toluene-3, 4,6-triisocyanate and toluene-1,3,5,6-triisocyanate; and xylene triisocyanate contains 1,2-xylene-3,4,6-triisocyanate, 1,2-xylene-3,5 , 6-triisocyanate, 1,3-xylene-2,4,5-triisocyanate, 1,3-xylene-2,4,6-triisocyanate, 1,3-xylene-3,4,5 —Triisocyanate, 1,4-xylene-2,3,5-triisocyanate and 1,4-xylene-2,3,6-triisocyanate. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs These diisocyanates and triisocyanates can be used alone or in combination of two or more. Examples of polyesters having hydroxyl groups at one end or polyesters having hydroxyl groups at both ends include polylactones having hydroxyl groups at one or both ends such as having hydroxyl groups at one or both ends Polycaprolactone, polyvalerolactone having a hydroxyl group at one or both ends, and polypropiolactone having a hydroxyl group at one or both ends; and polycondensation having a hydroxyl group at one or both ends This paper size applies to Chinese National Standard (CNS) A4 (210 X297 mm) -11-569043 A7 ___ B7_ V. Description of the invention (9) Polyester, such as poly-terephthalic acid with hydroxyl groups at one or both ends Ethylene glycol ester 'and polybutylene terephthalate having a hydroxyl group at one or both ends. (Please read the precautions on the back before filling out this page) This type of polyester with hydroxyl groups at one end and polyesters with hydroxyl groups at both ends can be used alone or in combination of two or more. In the present invention, the urethane-based dispersant is preferably a reaction product of an aromatic diisocyanate and a polylactone having a hydroxyl group at one end, and / or an aromatic diisocyanate having The reaction product of both hydroxy group-containing polylactones, particularly preferred are the reaction products of toluene diisocyanate and polycaprolactone having a hydroxyl group at one end, and / or toluene diisocyanate and The reaction product of both hydroxy-group polycaprolactone. The urethane-based dispersant may be characterized by insolubility caused by any one or more heat treatments, acid hydrazones, amine hydrazones, and voltage maintenance. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs for the presence of insolubilization caused by heat treatment, the urethane-based dispersant should be at 150 ° C or higher, more preferably at 150 to 2 Heating at 50 ° C, and the heating time should be 30 minutes or longer, more preferably 30 to 90 minutes, which is desirably in a polar solvent such as N, N-dimethylamidamine, N, N -Insoluble in dimethylacetamide, N-methylpyrrolidone or r-butyrolactone. For urethanes and amines, this urethane-based dispersant desirably has (i) urethanes preferably at 5 to 25 mgKOH / g, more preferably 8 to 20 mgKOH / g and amines.値 is 0mgKOH / g, or (ii) the amine is preferably 5 to 25 mgKOH / g, more preferably 8 to 20 mgKOH / g and the acid is 〇 This paper standard applies Chinese national standards (CNS ) A4 specification (210X297mm) -12- 569043 A7 B7 V. Description of the invention (10) mgKOH / g. (I) and (ii) cannot be satisfied at the same time. (Please read the precautions on the back before filling this page) For voltage retention, this urethane-based dispersant desirably has a voltage measured by the following method to maintain the voltage at 80% or more, preferably at 8 5% or more. Method for measuring voltage holding: 1 wt% of a urethane-based dispersant is added to a solution prepared by dissolving the components (B), (C), and (D) in the solvent in the present invention, and The resulting solution was applied to a substrate with an indium oxide (ITO) film on the surface to form a 3 // m-thick dry coating film, and then exposed to light at 2000 to 250 ° C. bake. The voltage holding of the liquid crystal cell assembled using the obtained matrix was measured at 60 ° C, and the retention time was selected to be 16.7 ms. When there is insolubility caused by heat treatment, the acid, amine, or voltage of the urethane-based dispersant in the present invention will meet the above conditions, which can greatly reduce the image occurring in the liquid crystal cell. Sticky. Illustrative examples of urethane-based dispersants with at least one of the above characteristics include commercially available products such as EFKA-4 6 and 47 (EFKA Chemicals BV), Disperbyk (BYK Chem. Ministry of Public Economics Wisdom (Printing Division, Consumer Cooperatives, Property Bureau Employees) and Disparon (Kusumoto Kasei). As measured by gel permeation chromatography (GPC), the weight average molecular weight (hereinafter abbreviated as Mw) of the urethane-based dispersant in the present invention in terms of polystyrene is preferably 5,000 to 50 7,000, more preferably between 7,000 and 20,000. In the present invention, the urethane-based dispersant may be used alone or in combination of two or more. This paper size is applicable to Chinese National Standard (CNS) A4 specification (210 X 297 mm) -13-569043 A7 ______ B7 V. Description of the invention (n) The content of the urethane-based dispersant should be 0.5 To 100 parts by weight, 'better' is 1 to 70 parts by weight, and much more preferable is 10 to 50 parts by weight, which is based on 100 parts by weight of the pigment contained in the coloring material. When the content of the urethane-based dispersant is less than 0.5 parts by weight, the stability of pigment dispersion may be reduced, and when the content is more than 100 parts by weight, the properties of the radiation-sensitive composition obtained Such as developability may be impaired. In the present invention, a dispersing aid and a dispersing agent may be used together. The dispersing aid is, for example, a phthalocyanine blue sulfonate copper compound. Specific examples of the above-mentioned phthalocyanine cyanocyanine copper sulfonate compound include phthalocyanine cyanocyanine copper sulfonate, phthalate cyanocyanine blue ammonium sulfonate, phthalate cyanocyanine tetramethylammonium Copper sulfonate, copper phthalate cyanine blue tetraethylammonium sulfonate, copper phthalate cyanine blue tetra-n-propylammonium sulfonate, copper phthalate cyanine blue tetraisopropylammonium sulfonate And copper phthalate cyanine tetra-n-butylammonium sulfonate. Such phthalocyanine blue sulfonate copper compound may be used alone or in combination with two or more. The content of the dispersing aid should be 20 parts by weight or less, more preferably 10 parts by weight or less, and much more preferably 5 parts by weight or less. This is based on the content of 100 parts by weight. Pigments in this colorant. (B) Alkali-soluble resin In the present invention, any alkali-soluble resin is acceptable, and g # 彳 is used as a binder for the colorant (A) and is soluble in a developer, particularly preferably an alkali. It is used as a developing agent to form a partition wall or a black matrix. This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page).

、1T 經濟部智慧財產局員工消費合作社印製 -14- 569043 A7 五、發明説明（12) 經濟部智慧財產局員工消費合作社印製 在本發 樹脂，特別 和單體（以 一可共聚合 單體"）的 聚物〃）。 內含羧 酸如丙烯酸 酸；不飽和 反丁烯二酸 蒸餾檸檬酸 的不飽和聚 烯醯基氧基 酯類如琥珀 (2 —甲基 氧基乙基） 及（ω -竣 甲基丙烯酸 此類內 明中鹼可溶解的樹脂較佳者爲內含羧基基團的 較佳者爲至少具有一種羧基基團的乙烯系不飽 下稱爲、、內含羧基基團的不飽和單體〃）與另 的乙燒系不飽和單體（以下稱爲、、另一不飽和 共聚物（以下簡單地稱爲、、內含羧基基團的共 (請先閲讀背面之注意事項再填寫本頁) 基基團的 、甲基丙 二羧酸（ 、分解烏 酐及甲基 羧酸（酐 乙基）酯 酸單（2 丙烯醯氧 酯及酞酸 基聚己內 酯。 含羧基基 多者而使 體之實 豆酸、 丁烯二 解烏頭 酸；帶 施例包括不飽和單竣 不飽和單 烯酸、巴 酐）如順 頭酸、分 反丁烯二 );非可聚合的二羧酸之單（2 -丙 α -氯丙烯酸及肉桂 酸、順丁烯二酸酐、 酸酐、蒸餾檸檬酸、 有三或更多羧基基團 類或單（2 -甲基丙烯醯氧基乙基） -丙烯醯基氧基乙基）酯、琥珀酸單 基乙基）酯、酞酸單（2 -丙烯醯基 單（2 —甲基丙烯醯氧基乙基）酯； 酯單丙烯酸酯及〇 一羧基聚己內酯單 團的乙烯系不飽和單體可單獨使用或 另一不飽和單體之實施例包括芳香族乙烯基化合物如 合倂二或更 苯乙烯、α —甲基苯乙烯、鄰一乙烯基甲苯、間一乙烯基 甲苯、對一乙燒基曱 烯、間甲氧基苯乙烯 苯、對-氯苯乙烯、鄰-甲氧基苯乙 、對甲氧基苯乙烯、對一乙烯基苄基 張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） 15 569043 A7 B7 五、發明説明（13) (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 甲基醚及對-乙烯基苄基甘油基醚；因烯（indene)(衍生 物）如因燏（indene)及卜甲基因烯（incjene);不飽和竣酸酯 類如丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙 烯酸乙酯、丙烯酸正丙酯、甲基丙烯酸正丙酯、丙烯酸異 丙酯、甲基丙烯酸異丙酯、丙烯酸正丁酯、甲基丙烯酸正 丁酯、丙烯酸異丁酯、甲基丙烯酸異丁酯、丙烯酸第二丁 酯、甲基丙烯酸第二丁酯、丙烯酸第三丁酯、甲基丙烯酸 第三丁酯、丙烯酸2 -羥乙酯、甲基丙烯酸2 -羥乙酯、 丙烯酸2-羥丙酯、甲基丙烯酸2-羥丙酯、丙烯酸3-羥丙酯、甲基丙烯酸3 -羥丙酯、丙烯酸2 -羥丁酯、甲 基丙烯酸2 -羥丁酯、丙烯酸3 -羥丁酯、甲基丙烯酸3 -羥丁酯、丙烯酸4 -羥丁酯、甲基丙烯酸4 -羥丁酯、 丙烯酸烯丙酯、甲基丙烯酸烯丙酯、丙烯酸苄酯、甲基丙 烯酸苄酯、丙烯酸苯酯、甲基丙烯酸苯酯、甲氧基二甘醇 丙烯酸酯、甲氧基二甘醇甲基丙烯酸酯、甲氧基三甘醇丙 烯酸酯、甲基丙烯酸甲氧基三甘醇酯、丙烯酸甲氧基二丙 二醇酯、甲氧基二丙二醇甲基丙烯酸酯、甘油單丙烯酸酯 及甘油單甲基丙烯酸酯；不飽和羧酸氨基烷酯類如丙烯酸 2-氨基乙酯、甲基丙烯酸2-氨基乙酯、丙烯酸2-二 甲氨基乙酯、甲基丙烯酸2 -二甲氨基乙酯、丙烯酸2 -氨基丙酯、甲基丙烯酸2 一氨基丙酯、丙烯酸2 一二甲氨 基丙酯、甲基丙烯酸2 -二甲氨基丙酯、丙烯酸3 -氨基 丙酯、甲基丙烯酸3 -氨基丙酯、丙烯酸3 -二甲氨基丙 酯及甲基丙烯酸3 -二甲氨基丙酯；不飽和羧酸甘油酯類 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -16- 569043 A7 _ B7_ 五、發明説明（14) (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 如甘油基丙烯酸酯及甘油基甲基丙烯酸酯；羧酸乙烯酯類 如乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯及苯甲酸乙烯酯 ;不飽和醚類如乙烯基甲基醚、乙烯基乙醚、烯丙基甘油 基醚及甲基丙烯基甘油基醚；乙烯基氰化物化合物如丙烯 腈、甲基丙烯基腈，α -氯丙烯腈及亞乙烯基氰化物；不 飽和醯胺如丙烯醯胺、甲基丙烯醯胺、α -氯丙烯醯胺、 Ν - 2 -羥乙基丙烯醯胺、Ν - 2 —羥乙基甲基丙烯醯胺 、Ν-羥甲基丙烯醯胺及Ν -羥甲基甲基丙烯醯胺；Ν -取代的順丁烯二醯亞胺如Ν -環己基順丁烯二醯亞胺、Ν -苯基順丁烯二醯亞胺、Ν -鄰羥基苯基順丁烯二醯亞胺 、Ν -間羥基苯基順丁烯二醯亞胺、Ν -對羥基苯基順丁 烯二醯亞胺、Ν -鄰一甲基苯基順丁烯二醯亞胺、Ν -間 甲基苯基順丁烯二醯亞胺、Ν -對甲基苯基順丁烯二醯亞 胺、Ν -鄰一甲氧基苯基順丁烯二醯亞胺、Ν -間甲氧基 苯基順丁烯二醯亞胺及Ν -對甲氧基苯基順丁烯二醯亞胺 ;脂肪族的共軛二烯如1，3 - 丁二烯、異戊間二烯及氯 丁二烯；以及在聚合物（如聚苯乙烯、聚丙烯酸曱酯、聚 甲基丙烯酸甲酯、聚-丙烯酸正丁酯、聚-甲基丙烯酸正 丁酯及聚矽氧烷）的分子鏈末端帶有單丙烯醯基基團或單 曱基丙烯醯基基團的巨單體。 此類不飽和單體可單獨使用或合倂二或更多者而使用 〇 該內含羧基基團的共聚物特別較佳者爲以下二者之共 聚物（以下稱爲ν、內含羧基基團的共聚物（1)〃 ）:( 本紙張尺度適用中國國家標準（CNS ) Α4規格（210 X297公釐） -17- 569043 A7 __ B7____ 五、發明説明（15) 1 )內含羧基基團的不飽和單體，以丙烯酸及/或甲基丙 烯酸作爲基本成分，且視需要而包括琥珀酸單（2 -丙烯 醯基氧基乙基）酯及/或琥珀酸單（2 -甲基丙烯醯氧基 乙基）酯，與（2 )至少一種選启下列類群者：苯乙烯、 丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸2—羥乙酯、甲基 丙烯酸2 -羥乙酯、丙烯酸苄酯、甲基丙烯酸苄酯、丙烯 酸苯酯、甲基丙烯酸苯酯、甘油單丙烯酸酯、甘油單甲基 丙烯酸酯、N -苯基順丁烯二醯亞胺、聚苯乙烯巨單體及 聚甲基丙烯酸甲酯巨單體。 內含羧基基團的共聚物（I )之說明性實施例包括共 聚物及三聚物（以下稱爲、、內含羧基基團的共聚物（I a )〃）如（甲基）丙烯酸/(甲基）丙烯酸苄酯之共聚物 、（甲基）丙烯酸/苯乙烯/(甲基）丙烯酸苄酯之三聚 物、（甲基）丙烯酸/(甲基）丙烯酸苄酯/聚苯乙烯巨 單體之三聚物，及（曱基）丙烯酸/(甲基）丙烯酸苄酯 /聚甲基丙烯酸曱酯巨單體之三聚物；四聚合物（以下稱 爲 ''內含羧基基團的共聚物（Ib)〃 ）如（甲基）丙烯 酸/(甲基）丙烯酸2 -羥乙酯/(甲基）丙烯酸苄酯/ 聚苯乙烯巨單體之四聚合物、（甲基）丙烯酸/(甲基） 丙酸2 -羥乙酯/(甲基）丙烯酸苄酯/聚甲基丙烯酸 甲酯巨單體之四聚合物、（甲基）丙烯酸/苯乙烯/(甲 基）丙烯酸苄酯/N-苯基順丁烯二醯亞胺之四聚合物、 (甲基）丙烯酸/苯乙烯/(甲基）丙烯酸苯酯/N -苯 基順丁烯二醯亞胺之四聚合物、及（甲基）丙烯酸/甘油 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公羡) (請先閲讀背面之注意事項再填寫本頁) 訂 經濟部智慧財產局員工消費合作社印製 -18- 569043 A7 B7 五、發明説明（16) (請先閲讀背面之注意事項再填寫本頁) 單（甲基）丙烯酸酯/苯乙烯/N -苯基順丁烯二醯亞胺 之四聚合物；五聚合物（以下稱爲、、內含羧基基團的共聚 物（Ic)〃 ）如（甲基）丙烯酸/苯乙烯/(甲基）丙 經濟部智慧財產局員工消費合作社印製 烯酸苄酯/N -苯基順丁烯二醯亞胺/聚苯乙烯巨單體之 五聚合物、（甲基）丙烯酸/苯乙烯/(甲基）丙烯酸苄 酯/N -苯基順丁烯二醯亞胺/聚甲基丙烯酸甲酯巨單體 之五聚合物、（甲基）丙烯酸/苯乙烯/(甲基）丙烯酸 苯酯/N -苯基順丁烯二醯亞胺/聚苯乙烯巨單體之五聚 合物、（甲基）丙烯酸/苯乙烯/(甲基）丙烯酸苯酯/ N -苯基順丁烯二醯亞胺/聚甲基丙烯酸甲酯巨單體之五 聚合物、（甲基）丙烯酸/甘油單（甲基）丙烯酸酯/苯 乙烯/(曱基）丙烯酸甲酯/N -苯基順丁烯二醯亞胺之 五聚合物、（甲基）丙烯酸/甘油單（甲基）丙烯酸酯/ 苯乙烯/(甲基）丙烯酸2 -羥乙酯/N —苯基順丁烯二 醯亞胺之五聚合物、（甲基）丙烯酸/甘油單（甲基）丙 烯酸酯/苯乙烯/(甲基）丙烯酸苄酯/N -苯基順丁烯 —^釀亞fee之五聚合物、（曱基）丙儲酸/甘油單（甲基） 丙烯酸酯/苯乙烯/(甲基）丙烯酸苯酯/ N -苯基順丁 烯二醯亞胺之五聚合物、（甲基）丙烯酸/單〔2 -（甲 基）丙烯醯基氧基乙基〕琥珀酸酯/甘油單（甲基）丙烯 酸酯/苯乙烯/N-苯基順丁烯二醯亞胺之五聚合物、（ 甲基）丙烯酸/甘油單（甲基）丙烯酸酯/苯乙烯/N -苯基順丁烯二醯亞胺/聚苯乙烯巨單體之五聚合物，及（ 甲基）丙烯酸/甘油單（甲基）丙烯酸酯/苯乙烯/N- 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇X297公釐） -19- 569043 A7 ____ B7_ 五、發明説明（17) (請先閱讀背面之注意事項再填寫本頁) 苯S順丁烯二醯亞胺/聚曱基丙烯酸甲酯巨單體之五聚合 物；及六聚合物（以下稱爲、、內含羧基基團的共聚物（ Id)")如（甲基）丙烯酸/苯乙烯/(甲基）丙烯酸 2 -經乙酯/(甲基）丙烯酸苄酯/N -苯基順丁烯二醯 亞胺/聚苯乙烯巨單體之六聚合物、（甲基）丙烯酸/苯 乙燒/(甲基）丙烯酸2 -羥乙酯/(甲基）丙烯酸苄酯 /N -苯基順丁烯二醯亞胺/聚甲基丙烯酸甲酯巨單體之 六聚合物、（甲基）丙烯酸/苯乙烯/(曱基）丙烯酸2 -羥乙酯/(甲基）丙烯酸苯酯/N -苯基順丁烯二醯亞 胺/聚苯乙烯巨單體之六聚合物、（甲基）丙烯酸/苯乙 烯/(甲基）丙烯酸2 -羥乙酯/(曱基）丙烯酸苯酯/ N -苯基順丁烯二醯亞胺/聚甲基丙烯酸甲酯巨單體之六 聚合物。 經濟部智慧財產局員工消費合作社印製 內含羧基基團的不飽和單體對內含羧基基團的共聚物 之共聚合比例宜在5至5 0 wt%，更佳者在1 0至 4 0 w t%。當內含羧基基團的不飽和單體之共聚合比 例小於5 w t %，所得到輻射敏感性組合物在鹼性顯影 劑之中的溶解度可能降低，且當該共聚合比例大於5 ◦ w t %，當在使用鹼性顯影劑的顯影中，所形成圖案可能 自基質上脫落或其表面可能會粗糙化。 在本發明中鹼可溶解樹脂的Mw宜在1，0 0 0至 1，000,0 0 0，更佳者在 5, 000 至 1〇〇, 〇〇〇 〇 本發明中，鹼可溶解的樹脂可單獨使用或合倂二或更 本紙張尺度適用中國國家標準（CNS ) A4規格（2丨〇><297公釐） -20 - 569043 A7 B7 五、發明説明（18) 多者而使用。 (請先閲讀背面之注意事項再填寫本頁) 在本發明中鹼可溶解的樹脂之含量宜在1 〇至 1，0 0 0重量份，更佳者在2 0至5 0 0重量份，此係 基於1 0 0重量份的著色劑（A )。當鹼可溶解的樹脂之 含量小於1 0重量份，鹼可顯影性可能降低，或可能在除 了圖案形成部分的區域之外造成沾污或膜的殘餘，且當該 含量高於1，0 0 0重量份，著色劑之濃度將相對地降低 ，從而可能將難於達成的在薄膜中的目標色彩密度。 (C )多官能某單體 經濟部智慧財產局員工消費合作社印製 在本發明中多官能基單體之實施例包括伸烷基二醇如 乙二醇及丙二醇的二丙烯酸酯及二丙烯酸甲酯；聚伸烷基 二醇如聚乙二醇及聚丙二醇的二丙烯酸酯及二丙烯酸甲酯 ;其具有3或更多羥基基團的多元醇及二羧酸改良的產物 (如甘油、三羥甲基丙烷、異戊四醇及二異戊四醇）之聚 丙烯酸酯及聚丙烯酸甲酯；寡丙烯酸酯及寡丙烯酸甲酯如 聚酯、環氧樹脂、氨基曱酸酯樹脂、醇酸樹脂、矽酮樹脂 及螺烷樹脂；下列各者之二丙烯酸酯及二丙烯酸甲酯：兩 端羥基化聚合物如其在兩端具有羥基基團的聚- 1 ，3 -丁二烯、其在兩端具有羥基基團的聚異戊間二烯、其在兩 端具有羥基基團的聚己內酯；及三（2 -丙烯醯基氧基乙 基）磷酸酯’及三（2 -甲基丙烯醯氧基乙基）磷酸酯。 在此類多官能基單體之中，其帶有3或更多羥基基團 的多元醇之聚丙烯酸酯及聚丙烯酸甲酯及其二羧酸改良的 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -21 - 569043 A7 _____ B7 五、發明説明（19) (請先閲讀背面之注意事項再填寫本頁) 產物爲較佳的，可舉例如三羥甲基丙烷三丙烯酸酯、三羥 甲基丙烷三丙烯酸酯、異戊四醇三丙烯酸酯、異戊四醇三 甲基丙烯酸酯，琥珀酸改良的異戊四醇三甲基丙烯酸酯之 產物、琥珀酸改良的異戊四醇三甲基丙烯酸酯之產物、異 戊四醇四丙烯酸酯、異戊四醇四甲基丙烯酸酯、二異戊四 醇四丙烯酸酯、二異戊四醇四甲基丙烯酸酯、二異戊四醇 六丙烯酸酯及二異戊四醇六甲基丙烯酸酯。特別較佳者爲 三羥甲基丙烷三丙烯酸酯、異戊四醇三丙烯酸酯及二異戊 四醇六丙烯酸酯。此類聚丙烯酸酯、聚曱基丙烯酸酯及其 二羧酸改良的產物爲較佳的，因爲所得到圖案之強度高， 該圖案的表面平滑性特佳，且在除了圖案形成部分之外的 區域中難以造成沾污及膜殘餘物。 上述多官能基單體可單獨使用或合倂二或更多者而使 用。 經濟部智慧財產局員工消費合作社印製 多官能基單體之含量在本發明中宜在5至5 0 0重量 份，更佳者在2 0至3 0 0重量份，此係基於1 〇 〇重量 份的鹼可溶解的樹脂（B )。當多官能基單體之含量小於 5重量份，圖案的強度及表面平滑性可能降低，且當含量 大於5 0 0重量份，鹼可顯影性可能降低，或在除了圖案 形成部分之外的區域中可能造成沾污與膜殘餘。 本發明中，部分的上述多官能基單體可經取代以單官 能單體。 單官能單體之實施例包括內含羧基基團的不飽和單體 ，及或鹼可溶解的樹脂（B )所列舉的其它不飽和單體、 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -22- 569043 A7 B7 五、發明説明（20) 丙烯酸2 -羥基- 3 -苯氧基丙酯、甲基丙烯酸2 -羥基 一 3 -苯氧基丙酯及如商購之產物Μ - 5 3 0 0 (商品名 (請先閱讀背面之注意事項再填寫本頁) ，由Toagosei化學的工業公司製作）。 在此類單官能單體之中，較佳者爲琥珀酸單（2 -丙 烯醯基氧基乙基）酯，琥珀酸單（2 -甲基丙烯醯氧基乙 基）酯、ω -羧基聚己內酯單丙烯酸酯（M - 5 3 0 0) 、ω -羧基聚己內酯單甲基丙烯酸酯、甲氧基三甘醇丙烯 酸酯、甲基丙烯酸甲氧基三甘醇酯、丙烯酸甲氧基二丙二 醇酯、甲氧基二丙二醇甲基丙烯酸酯、丙烯酸2 -羥基- 3 -苯氧基丙酯及甲基丙烯酸2 -羥基- 3 -苯氧基丙酯 〇 上述單官能單體可單獨使用或合倂二或更多者而使用 〇 該單官能單體之含量宜在9 0 wt%或更低，更佳 者在5 0 w t%或更低，此係基於多官能基單體與單官 能單體之總量。 經濟部智慧財產局員工消費合作社印製 (D )光聚合紀始劑 在本發明中光聚合起始劑爲一種化合物，經由於曝光 下的降解或切除其鍵結其可形成活化的物種，而能引發上 述多官能基單體（C )聚合且視需要使用作爲單官能單體 ’如自由基聚合，陰離聚合子或陽離子聚合。 該光聚合起始劑之實施例包括二咪唑爲主的化合物， 其具有二苯乙二酮鍵結的化合物，其它光自由基產生劑及 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -23· 569043 Α7 Β7 五、發明説明（21) 經濟部智慧財產局員工消費合作社印製 其 具 有 二 鹵 甲 基 基 團 的 化合 物 〇 該 二 咪 唑 爲 主 的 化合 物 包括 2 2 — 雙 ( 2 — 氯 苯 基 ) — 4 4 5 5 5 〆 — 四 ( 4 — 乙 氧 羰 基 苯 基 ) — 1 2 一 — 二 咪 唑 2 2 — 雙 ( 2 — 溴 苯 基 ) — 4 4 5 5 〆 — 四 ( 4 — 乙 氧 Wi m 基 苯 基 ) — 1 ， 2 — 二 咪 唑 > 2 2 〆 — 雙 ( 2 — 氯 苯 基 ) — 4 5 4 5 5 9 5 — 四 苯 基 — 1 2 〆 — 二 咪 唑 % 2 2 〆 — 雙 ( 2 ， 4 — 二 氯 苯 基 ) — 4 ， 4 5 ， 5 — 四 苯 基 — 1 5 2 — 二 咪 唑 2 ， 2 〆 — 雙 ( 2 4 5 6 — 三 氯 苯 基 ) — 4 4 5 5 〆 — 四 苯 基 — 1 5 2 - — 二 咪 唑 2 2 — 雙 ( 2 — 溴 苯 基 ) — 4 4 〆 5 5 — 四 苯 基 — 1 2 〆 — 二 咪 唑 .、 2 9 2 > — 雙 ( 2 9 4 — 二 溴 苯 基 ) — 4 > 4 5 5 〆 — 四 苯 基 — 1 2 〆 — 二 咪 唑 及 2 2 — 雙 ( 2 j 4 6 — 三 溴 苯 基 ) — 4 > 4 ， 5 5 — 四 苯 基 — 1 ， 2 > — 二 咪 唑 〇 此 類 二 咪 唑 爲 主 的 化合 物 在 溶 劑 之 中 具 有 卓 越 的 溶 解 度 ， 不 會 形 成 外來 的 物 質 如 未 溶 解 的 產 物 及 沈 澱 物 ， 具 有 尚 敏 感 性及 高 對 比 經 由 曝 光 以 少 量 之 能 量 即 可 充 分促 進 硬 化 反 應 5 且 在未 曝 光 的 部 分 之 中 不 會 引 起 硬 化 反 應 〇 因 此 該 塗 層 膜 於 曝 光 之 後 可 淸 楚 地 分 爲 不 溶 在 顯 影 劑 之 中 的 硬 化 部 分 與 其在 顯 影 劑 中 具 有 筒 溶 解 度 的 未 硬 化 部 分 y 從 而 使 彼 有 可 能 形 成 極 佳 的 圖 案 不 含 缺掉 的 部 分 失 去 的 部 分及 側 侵 蝕 〇 上 述 具 有 二 苯 乙 二 酮 鍵 結 的 化 合 物 及其 它 光 白 由 基 產 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210Χ297公釐） -24- 569043 A7 B7 五、發明説明（22) (請先閲讀背面之注意事項再填寫本頁) 生劑包括2-羥基一2-甲基一1一苯基丙一1一酮、1 一（4 一異丙基苯基）一 2 -羥基一 2 —甲基丙一 1—酮 、4一（2 -羥基乙氧基）苯基—（2 —羥基一 2 -丙基 )酮，1 一羥基環己基苯基酮、2，2 -二甲氧基一 2 -苯基乙醯苯酮、2 -甲基一（4 —甲基噻吩基）一 2 -嗎 福啉基—1 一丙—1_酮、2 -苄基一 2 —二甲氨基一 1 一（4 一嗎福啉基苯基）丁 — 1—酮、苯甲酮、3，3 一 —二甲基一 4 一甲氧基苯甲酮、2，4-二乙基硫兩苯駢 辰哧，4 -疊氮基苯甲醛，4 一疊氮基乙醯苯酮、4 一疊 氮基亞苄基乙醯苯酮、疊氮基芘、4 -重氮基聯苯胺、4 一重氮基一 4 / 一甲氧基聯苯胺、4 一重氮基一 3 -甲氧 基聯苯胺、雙（2，6 -二甲氧基苯甲基）一2，4，4 -三甲基戊基膦氧化物、二苯甲基、二苯乙二酮異丁基醚 ’ N -苯基硫吖啶酮及苯基噚英鑰高氯酸鹽。 上述具有三鹵甲基基團的化合物包括1 ，3，5 -三 (三氯曱基）一 s —三吖嗪、1 ，3 —雙（三氯甲基）一 5 -（2 -氯苯基）—s —三吖嗪、1 ，3 —雙（三氯甲 經濟部智慧財產局員工消費合作社印製 基）—5 -（4 —氯苯基）—s —三吖嗪、1 ，3 —雙（ 三氯甲基）—5— (2 -曱氧基苯基）—s —三吖嗪及1 ’ 3 -雙（三氯甲基）—5 -（4 —甲氧基苯基）—s — 三吖嗪。 在具有二苯乙二酮鍵結的化合物之中，其它光自由基 產生劑及其具有三鹵甲基基團的化合物、2 一羥基一 2 -甲基—1 一苯基丙—1 一酮、2 —甲基—（4 —甲基噻吩 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -25 - 569043 A7 B7 五、發明説明（23) (請先閱讀背面之注意事項再填寫本頁) 基）一 2 -嗎福啉基一 1 一丙—1—酮及2 —苄基一 2 -二甲氨基一 1 一（4 一嗎福啉基苯基）丁一 1 一酮爲較佳 的，因爲其所形成的圖案在顯影中難以自基質上脫落且圖 案的強度及敏感性均高。 上述光聚合起始劑可單獨使用或合倂二或更多者而使 用。 若需要，可進一步的將本發明中，至少一種化合物與 上述光聚合起始劑合倂使用，該化合物係選自由敏化劑、 硬化促進劑及內含聚合物化合物的光學交聯劑或光學敏化 劑（以下稱爲〜光學交聯/敏化劑聚合物〃）所組成的類 群。 上述敏化劑之實施例包括4，4 / 一雙（二甲氨基） 苯曱酮、4，4 / —雙（二乙氨基）苯甲酮、4 一二乙氨 基乙醯苯酮、4 一二甲氛基苯丙酮、乙基一 4 一二甲氛基 苯甲酸鹽、2 -乙基己基一 1 ，4 一二甲氨基苯甲酸鹽、 經濟部智慧財產局員工消費合作社印製 2，5 —雙（4 —二乙氨基亞苄基）環己酮、7 -二乙氨 基一 3— (4 -二乙氨基苯甲基）香豆素及4 一（二乙氨 基）查酮。 上述硬化促進劑之實施例包括鏈轉移劑如2 -氫硫基 苯并咪唑、2 -氫硫基苯并噻唑、2 -氫硫基苯并nf唑、 2 ’ 5 — 一氫硫基_1，3，4 一噻二氮1:1坐、2 -氫硫基 一 4，6 -二甲氨基吡D定、1—苯基—5 -氫硫基—1 Η —四氮唑及3 —氫硫基—4 —甲基—4Η — 1 ，2，4 — 三口坐0 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） 一 一 -26 - 569043 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（24) 此外’上述聚合物光學交聯/敏化劑爲具有可在主鏈 及/或側鏈上用作光學交聯劑及/或光學敏化劑的官能基 團之聚合物化合物。該藥劑之實施例包括4 -疊氮基苯甲 醛與聚乙烯醇之縮合物、4 -疊氮基苯甲醛與酚酚醛淸漆 樹脂之縮合物，下列之均聚物或共聚物·· 4 -丙烯醯基苯 基桂皮醯酯、1，4 一聚丁二烯及1，2 -聚丁二烯。 在此類敏化劑，硬化促進劑及聚合物光學交聯/敏化 劑之中，4，4 > —雙（二甲氨基）苯甲酮、4，4< — 雙（二乙氨基）苯甲酮及2 -氫硫基苯并噻唑爲較佳的， 因爲其所形成的圖案在顯影中難以自基質上脫落且圖案的 強度及敏感性均高。 在本發明中的光聚合起始劑特別較佳者爲二咪唑爲主 的化合物與至少一種化合物之組合物，而該化合物係選自 由下列所組成之類群：苯甲酮爲主的具有二苯乙二酮鍵結 的化合物、苯甲酮爲主的其它光自由基產生劑、苯甲酮爲 主的敏化劑及噻唑爲主的硬化促進劑。 該組合物之特別較佳的實施例包括2，2 > -雙（2 —氯苯基）_4，，5，5> —四（4 —乙氧羰基苯 基）_1 ，2 * -二咪唑/4，4 / —雙（二乙氨基）苯 甲酮之組合物、2，2 —雙（2 —氯苯基）一 4，4 一 ，5，5，—四（4 —乙氧羰基苯基）—1 ，2" -二咪 口坐/ 4，4 '一雙（二乙氨基）苯甲酮/ 2 -苄基一 2 -二甲氨基一 1 一（ 4 一嗎福啉基苯基）丁烷一 1 一酮之組 合物、2 ’ 2’ —雙（2 —氯苯基）—4，4 — ，5， 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公t ) (請先閱讀背面之注意事項再填寫本頁) -27- 569043 A7 _ B7____ 五、發明説明（25) 5 / —四（4 —乙氧羰基苯基）一 1 ，2 > —二咪唑/4 ，4 > 一雙（二乙氨基）苯甲酮/1 一羥基環己基苯基酮 之組合物、2，2 > -雙（2 -氯苯基）一 4，’ 5 ，5四（4 一乙氧羰基苯基）一 1 ，2 / —二咪唑/ 4，4 / 一雙（二甲氨基）苯曱酮/1 一羥基環己基苯基 酮/2 -氫硫基苯并噻唑之組合物、2，2 / -雙（2 ’ 4 一二氯苯基）—4，4’ ，5，5^ —四苯基一 1， 2 / —二咪唑/ 4，4 ——雙（二乙氨基）苯甲酮之組合 物、2，2 > —雙（2，4 —二溴苯基）—4，4 /，5 ，5 / - 四苯基—1 ，2 / —二咪唑/4，4 / 一雙（二 乙氨基）苯甲酮/2 —苄基一 2 —二甲氨基一1 一（4 — 嗎福啉基苯基）丁院一 1 一酮之組合物、2 ’ 2 -雙（ 2，4 —二溴苯基）—4，4 > ，5，5 / —四苯基—1 ，2 > -二咪唑/4，4 > 一雙（二乙氨基）苯甲酮/1 一羥基環己基苯基酮之組合物、及2，2 > -雙（2，4 ，6 —三氯苯基）—4，4 / ，5，5 > —四苯基—1 ， 2 / -二咪唑/4，4 > —雙（二甲氨基）苯甲酮/1 一 羥基環己基苯基酮/2 -氫硫基苯并噻唑之組合物。 本發明中，具有二苯乙二酮鍵結的化合物、其它光自 由基產生劑及其具有三鹵甲基基團的化合物之總量，宜在 8 0 w t %或更低，此係基於光聚合起始劑。的總量敏 化劑及硬化促進劑宜在8 0 w t %或更低，此係基於光 聚合起始劑。此外，聚合物光學交聯/敏化劑之含量宜在 2 〇 0重量份或更低，更佳者在1 8 0重量份或更低，此 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) ··裝·、 1T Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -14- 569043 A7 V. Description of the Invention (12) The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed the resin, especially with the monomer (in a copolymerizable form) Polymer ") polymer 〃). Contains carboxylic acids such as acrylic acid; unsaturated fumarate distillates unsaturated polyalkenyloxy esters of citric acid such as amber (2-methyloxyethyl) and (ω-end methacrylic acid) The alkali-soluble resin in the class Neiming is preferably an carboxyl group-containing unsaturated monomer, preferably an ethylenic unsaturated compound having at least one carboxyl group, which is hereinafter referred to as an unsaturated monomer containing a carboxyl group. ) And another ethylenic unsaturated monomer (hereinafter referred to as, and another unsaturated copolymer (hereinafter simply referred to as,, containing a carboxyl group) (Please read the precautions on the back before filling in this page ) Group, methyl malonic acid (, decomposition of uranyl anhydride and methyl carboxylic acid (anhydride ethyl) ester acid mono (2 propylene oxide and phthalic acid polycaprolactone. Many of which contain carboxyl groups And the soy acid, butene dihydroaconitic acid; examples include unsaturated monounsaturated unsaturated monoenoic acid, baric anhydride) such as cis acid, isobutene di); non-polymerizable dicarboxylic acid Acid mono (2-prop alpha-chloroacrylic acid and cinnamic acid, maleic anhydride, anhydride, distilled citric acid, yes Three or more carboxyl groups or mono (2-methylpropenyloxyethyl) -propenyloxyethyl) ester, succinate monoethyl) ester, phthalic acid mono (2-propenefluorene) Examples of ethylenically unsaturated monomers based on mono (2-methacryloxyethyl) esters; ester monoacrylates and 0-carboxy polycaprolactone monomers may be used alone or as another unsaturated monomer Includes aromatic vinyl compounds such as fluorene di- or more styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-ethylvinylpinene, m-methoxystyrenebenzene, P-chlorostyrene, o-methoxystyrene, p-methoxystyrene, and p-vinylbenzyl are applicable to China National Standard (CNS) A4 specifications (210X297 mm) 15 569043 A7 B7 V. Invention Note (13) (Please read the notes on the back before filling this page) Printed methyl ether and p-vinyl benzyl glyceryl ether by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs; indene (derivative) Such as indene and injene; unsaturated unsaturated esters such as acrylic acid methyl ester Ester, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, methacrylic acid N-butyl, isobutyl acrylate, isobutyl methacrylate, second butyl acrylate, second butyl methacrylate, third butyl acrylate, third butyl methacrylate, 2-hydroxyethyl acrylate , 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, formazan 2-hydroxybutyl acrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate Ester, benzyl acrylate, benzyl methacrylate, phenyl acrylate, phenyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate , Methoxytriethylene glycol methacrylate, methoxy acrylate Propylene glycol esters, methoxy dipropylene glycol methacrylates, glycerol monoacrylates, and glycerol monomethacrylates; unsaturated aminocarboxylic acid alkyl esters such as 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-methacrylate Dimethylaminopropyl, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate and 3-dimethylaminopropyl methacrylate; glycerides of unsaturated carboxylic acids Paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) -16- 569043 A7 _ B7_ V. Description of invention (14) (Please read the precautions on the back before filling out this page) Employees of Intellectual Property Bureau of the Ministry of Economic Affairs Cooperatives print glyceryl acrylate and glyceryl methacrylate; vinyl carboxylates such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate; unsaturated ethers such as vinyl methyl Ether, ethylene Diethyl ether, allyl glyceryl ether and methacryl glyceryl ether; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and vinylidene cyanide; unsaturated amines such as Acrylamide, methacrylamide, α-chloroacrylamide, N-2 -hydroxyethylacrylamide, N-2 -hydroxyethylmethacrylamine, N-hydroxymethacrylamine and N-methylolmethacrylamide; N-substituted maleimide diimide such as N-cyclohexyl maleimide diimide, N-phenyl maleimide diimide, N-ortho Hydroxyphenyl-cis-butene-diimine, N-m-hydroxyphenyl-cis-butene-diimine, N-p-hydroxyphenyl-cis-butene-diimine, N-o-methylphenyl-cis-butene Diamidine, N-m-methylphenylcisbutenediamidine, N-p-methylphenylcisbutenediamidine, N-o-methoxyphenylcisbutenediamidine Amines, N-m-methoxyphenylcis-butenedifluoreneimine and N-p-methoxyphenylcis-butenedifluoreneimine; aliphatic conjugated diene such as 1,3-butadiene, Isoprene and chloroprene; and polymers (Such as polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, and polysiloxane) with a single propylene fluorenyl group at the end of the molecular chain Or a macromonomer of a monofluorenylpropenyl group. Such unsaturated monomers can be used alone or in combination of two or more. The copolymer containing a carboxyl group is particularly preferably a copolymer of the following two (hereinafter referred to as ν, containing a carboxyl group) Copolymer (1) 〃): (This paper size applies the Chinese National Standard (CNS) A4 specification (210 X297 mm) -17- 569043 A7 __ B7____ V. Description of the invention (15) 1) Contains carboxyl groups Unsaturated monomers based on acrylic acid and / or methacrylic acid and optionally including succinate mono (2-propenyloxyethyl) ester and / or succinate mono (2-methylpropene) Ethoxyethyl) esters, and (2) at least one selected from the group consisting of styrene, methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and acrylic acid Benzyl ester, benzyl methacrylate, phenyl acrylate, phenyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate, N-phenylcis butylene diimide, polystyrene macromonomer and Polymethyl methacrylate macromonomer. Illustrative examples of carboxyl group-containing copolymers (I) include copolymers and terpolymers (hereinafter referred to as, carboxyl group-containing copolymers (Ia) 〃) such as (meth) acrylic acid / Copolymer of benzyl (meth) acrylate, terpolymer of (meth) acrylic acid / styrene / (meth) acrylic acid benzyl ester, (meth) acrylic acid / benzyl (meth) acrylate / polystyrene giant Terpolymers of monomers and terpolymers of (fluorenyl) acrylic acid / benzyl (meth) acrylate / polymethylmethacrylate macromonomers; tetrapolymers (hereinafter referred to as `` containing carboxyl groups) Copolymers (Ib) 〃) such as (meth) acrylic acid / 2-hydroxyethyl (meth) acrylic acid / benzyl (meth) acrylate / polystyrene macromonomer, four polymers, (meth) acrylic acid / (Meth) 2-hydroxyethyl propionate / benzyl (meth) acrylate / polymethyl methacrylate macropolymer, four polymers, (meth) acrylic acid / styrene / benzyl (meth) acrylate Ester / N-phenylcis butadiene diimide tetrapolymer, (meth) acrylic acid / styrene / phenyl (meth) acrylate / N-phenylcis butadiene diimide Polymer and (meth) acrylic acid / glycerin paper standards are applicable to Chinese National Standard (CNS) A4 specifications (210X297) (please read the precautions on the back before filling this page) Order the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs Printed -18- 569043 A7 B7 V. Description of the invention (16) (Please read the precautions on the back before filling this page) Mono (meth) acrylate / styrene / N-phenylcis butylene diimide No. 4 polymer; No. 5 polymer (hereinafter referred to as, copolymer with carboxyl group (Ic) 〃), such as (meth) acrylic acid / styrene / (meth) acrylic acid, Intellectual Property Bureau, Ministry of Economic Affairs, Employee Consumption Cooperative Five polymers of benzyl enoate / N-phenylcis butylene diimide / polystyrene macromonomer, (meth) acrylic acid / styrene / benzyl (meth) acrylate / N-benzene Five polymers of cis-butene difluorene imide / polymethyl methacrylate macromonomer, (meth) acrylic acid / styrene / phenyl (meth) acrylate / N-phenyl maleic acid Five polymers of amine / polystyrene macromonomer, (meth) acrylic acid / styrene / (meth) acrylic acid phenyl ester / Five polymers of N-phenylcis butylene diimide / polymethyl methacrylate macromonomer, (meth) acrylic acid / glycerol mono (meth) acrylate / styrene / (fluorenyl) methacrylate Ester / N-Phenyl butene diamidimine five polymer, (meth) acrylic acid / glycerol mono (meth) acrylate / styrene / (meth) acrylic acid 2-N-hydroxyethyl ester / N-benzene Five polymers of cis-butene diimide, (meth) acrylic acid / glycerol mono (meth) acrylate / styrene / benzyl (meth) acrylate / N-phenylcis-butene— ^ Five polymers of fee, (fluorenyl) propionic acid / glycerol mono (meth) acrylate / styrene / phenyl (meth) acrylate / N-phenylcis butylene diimide five polymers, (Meth) acrylic acid / mono [2- (meth) acrylfluorenyloxyethyl] succinate / glycerol mono (meth) acrylate / styrene / N-phenylcis butylene diimide Pentapolymer, pentapolymer of (meth) acrylic acid / glycerol mono (meth) acrylate / styrene / N-phenylcis butylene diimide / polystyrene macromonomer, and (meth) acrylic acid / Glycerin mono (meth) acrylate / styrene / N- This paper size is applicable to Chinese National Standard (CNS) A4 (21 × 297 mm) -19- 569043 A7 ____ B7_ V. Description of the invention (17) (please Read the precautions on the back before filling this page) Five polymers of benzene S cis butene diimide / polymethyl methyl acrylate macromonomer; and six polymers (hereinafter referred to as, containing carboxyl groups) Copolymers (Id) ") such as (meth) acrylic acid / styrene / (meth) acrylic acid 2-ethyl acetate / benzyl (meth) acrylate / N-phenylcis butylene diimide / Six polymers of polystyrene macromonomer, (meth) acrylic acid / phenethylbenzene / (meth) acrylic acid 2-hydroxyethyl ester / (meth) acrylic acid benzyl ester / N-phenylcis butylene difluorene Six polymers of amine / polymethyl methacrylate macromonomers, (meth) acrylic acid / styrene / (fluorenyl) acrylic acid 2-hydroxyethyl ester / (meth) acrylic acid phenyl ester / N-phenylcis butylene Hexamethylene diimide / polystyrene macromonomer six polymer, (meth) acrylic acid / styrene / (meth) acrylic acid 2-hydroxyethyl ester / (fluorenyl) phenyl acrylate / N-phenylcis Butene di Imine / polymethyl methacrylate macromonomer of six polymer. The copolymerization ratio of unsaturated monomers containing carboxyl groups to copolymers containing carboxyl groups printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs should be 5 to 50 wt%, more preferably 10 to 4 0 wt%. When the copolymerization ratio of the unsaturated monomer containing a carboxyl group is less than 5 wt%, the solubility of the obtained radiation-sensitive composition in an alkaline developer may decrease, and when the copolymerization ratio is more than 5 wt% When developing with an alkaline developer, the formed pattern may fall off the substrate or its surface may be roughened. In the present invention, the Mw of the alkali-soluble resin is preferably 1,000 to 1,000, 000, and more preferably 5,000 to 1,000, 000. In the present invention, the alkali-soluble resin Resin can be used alone or in combination with two or more paper sizes. Applicable to China National Standard (CNS) A4 specifications (2 丨 〇 > < 297 mm) -20-569043 A7 B7 V. Description of the invention (18) use. (Please read the precautions on the back before filling this page) In the present invention, the content of the alkali-soluble resin should preferably be 10 to 1,000 parts by weight, and more preferably 20 to 500 parts by weight. This is based on 100 parts by weight of the toner (A). When the content of the alkali-soluble resin is less than 10 parts by weight, alkali developability may be reduced, or stains or residues of the film may be caused in areas other than the area where the pattern is formed, and when the content is higher than 1, 0 0 At 0 parts by weight, the concentration of the colorant will be relatively reduced, so that it may be difficult to achieve the target color density in the film. (C) Multifunctional monomer Monomers of the Intellectual Property Bureau, Ministry of Economic Affairs, Employee Consumption Cooperatives. Examples of polyfunctional monomers printed in the present invention include alkylene glycols such as diacrylates of ethylene glycol and propylene glycol, and methyl diacrylate. Esters; polyalkylene glycols such as polyethylene glycol and polypropylene glycol diacrylates and methyl diacrylates; polyols having 3 or more hydroxyl groups and dicarboxylic acid modified products (such as glycerol, tris (Methylolpropane, isopentaerythritol and diisopentaerythritol) polyacrylates and polymethyl acrylates; oligoacrylates and oligomethyl acrylates such as polyesters, epoxy resins, amino resins, alkyds Resins, silicone resins and spirane resins; diacrylates and methyl diacrylates of each of the following: hydroxylated polymers at both ends, such as poly-1,3-butadiene, which has hydroxyl groups at both ends, Polyisoprene having hydroxyl groups at both ends, polycaprolactone having hydroxyl groups at both ends; and tris (2-propenyloxyethyl) phosphate 'and tris (2-methyl Propylene alkoxyethyl) phosphate. Among such polyfunctional monomers, polyacrylates and polymethyl acrylates of polyhydric alcohols having 3 or more hydroxyl groups and their dicarboxylic acids are modified to the Chinese paper standard (CNS). A4 specifications (210X297 mm) -21-569043 A7 _____ B7 V. Description of the invention (19) (Please read the notes on the back before filling this page) The product is better, for example, trimethylolpropane triacrylic acid Esters, trimethylolpropane triacrylate, isopentaerythritol triacrylate, isopentaerythritol trimethacrylate, products of succinic acid modified isopentaerythritol trimethacrylate, succinic acid modified isopropyl Products of pentaerythritol trimethacrylate, isopentaerythritol tetraacrylate, isopentaerythritol tetramethacrylate, diisopentaerythritol tetraacrylate, diisopentaerythritol tetramethacrylate, two Isopentaerythritol hexaacrylate and diisopentaerythritol hexamethacrylate. Particularly preferred are trimethylolpropane triacrylate, isopentaerythritol triacrylate, and diisopentaerythritol hexaacrylate. Such polyacrylates, polyfluorenyl acrylates, and their dicarboxylic acid modified products are preferred because the resulting pattern has high strength, the surface of the pattern is particularly smooth, and in areas other than the pattern forming portion Difficult to cause stains and film residues. These polyfunctional monomers can be used alone or in combination of two or more. The content of polyfunctional monomers printed by employees' cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs in the present invention should preferably be 5 to 500 parts by weight, more preferably 20 to 300 parts by weight, which is based on 100%. Part by weight of alkali-soluble resin (B). When the content of the polyfunctional monomer is less than 5 parts by weight, the strength and surface smoothness of the pattern may be reduced, and when the content is more than 500 parts by weight, the alkali developability may be reduced, or in areas other than the pattern-forming portion It may cause contamination and film residue. In the present invention, a part of the above-mentioned multifunctional monomer may be substituted with a monofunctional monomer. Examples of monofunctional monomers include unsaturated monomers containing carboxyl groups, and other unsaturated monomers listed in alkali-soluble resins (B). This paper applies Chinese National Standard (CNS) A4 specifications. (210X297 mm) -22- 569043 A7 B7 V. Description of the invention (20) 2-hydroxy-3 -phenoxypropyl acrylate, 2-hydroxy-3 -phenoxypropyl methacrylate and if commercially available Product M-5 3 0 0 (trade name (please read the precautions on the back before filling out this page), manufactured by Toagosei Chemical Industry Co., Ltd.). Among such monofunctional monomers, mono (2-propenyloxyethyl) succinate, mono (2-methacryloxyethyl) succinate, and ω-carboxyl are preferred. Polycaprolactone monoacrylate (M-5 3 0 0), ω-carboxy polycaprolactone monomethacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, acrylic acid Dimethoxydipropylene glycol, methoxydipropylene glycol methacrylate, 2-hydroxy-3 -phenoxypropyl acrylate and 2-hydroxy-3 -phenoxypropyl methacrylate. The above monofunctional monomers It can be used alone or in combination of two or more. The content of the monofunctional monomer is preferably 90 wt% or less, and more preferably 50 wt% or less. This is based on a polyfunctional monomer. Total body and monofunctional monomer. (D) Photopolymerization starter printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. In the present invention, the photopolymerization initiator is a compound, which can form activated species through degradation or removal of the bond under exposure, and It can initiate the polymerization of the above-mentioned multifunctional monomer (C) and optionally used as a monofunctional monomer, such as radical polymerization, anion polymerization or cationic polymerization. Examples of the photopolymerization initiator include compounds mainly composed of diimidazole, compounds having a diphendione bond, other photo-radical generators, and the paper standard applicable to China National Standard (CNS) A4 (210X297) (Mm) -23 · 569043 Α7 B7 V. Description of the invention (21) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs with its dihalomethyl group compound. The diimidazole-based compounds include 2 2 —bis ( 2 — chlorophenyl) — 4 4 5 5 5 〆 — tetra (4 —ethoxycarbonylphenyl) — 1 2 1 —diimidazole 2 2 — bis (2 —bromophenyl) — 4 4 5 5 〆 — tetra (4 —ethoxy Wi m phenyl) — 1, 2 —diimidazole> 2 2 〆 — bis (2 —chlorophenyl) — 4 5 4 5 5 9 5 — tetraphenyl — 1 2 〆 — di Imidazole% 2 2 〆—bis (2, 4 —dichlorophenyl) — 4, 4, 5, 5 — tetraphenyl — 1 5 2 — diimidazole 2, 2 〆 — bis (2 4 5 6 — trichlorobenzene Base) — 4 4 5 5 〆 — Tetraphenyl — 1 5 2 — — diimidazole 2 2 — bis (2 —bromophenyl) — 4 4 〆5 5 — tetraphenyl — 1 2 〆 — diimidazole., 2 9 2 > — bis ( 2 9 4 —dibromophenyl) — 4 > 4 5 5 〆—tetraphenyl— 1 2 〆—diimidazole and 2 2 —bis (2 j 4 6 —tribromophenyl) — 4 > 4, 5 5 —Tetraphenyl — 1, 2 > — Diimidazole. Such diimidazole-based compounds have excellent solubility in solvents, and will not form foreign substances such as undissolved products and precipitates. Sensitivity and high contrast can sufficiently promote the hardening reaction with a small amount of energy through exposure5 and it will not cause hardening reaction in the unexposed parts. Therefore, the coating film can be divided into insoluble developers after the exposure. The hardened part in it and its unhardened part with barrel solubility in the developer Therefore, it is possible to form an excellent pattern without missing parts and side erosion. The above compounds with diphendione bond and other light white products (please read the precautions on the back first) (Fill in this page) This paper size applies Chinese National Standard (CNS) A4 (210 × 297 mm) -24- 569043 A7 B7 V. Description of the invention (22) (Please read the notes on the back before filling this page) 2-hydroxy-1, 2-methyl-1, 1-phenylpropanyl, 1-one, 1- (4-isopropylphenyl), 2-hydroxy-1, 2-methylpropanyl, 1-one, 4- (2- Hydroxyethoxy) phenyl- (2-hydroxy-2 -propyl) ketone, 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, 2-methyl 1- (4-methylthienyl) -1 2-morpholinyl-1, 1-propan-1-one, 2-benzyl-2 2-dimethylamino-1 1- (4-morpholinylphenyl) butyl — 1-ketone, benzophenone, 3,3-mono-dimethyl-4 4-methoxybenzophenone, 2,4-diethylsulfanil Cinnamon, 4-azidobenzaldehyde, 4-azidoacetophenone, 4-azidobenzylideneacetophenone, azidofluorene, 4-diazobenzidine, 4-diazonium -4-monomethoxybenzidine, 4 -diazo-3-methoxybenzidine, bis (2,6-dimethoxybenzyl)-2,4,4-trimethylpentyl Phosphine oxide, benzhydryl, diacetophenone isobutyl ether 'N-phenylthioacridone and phenylsulfonium perchlorate. The above-mentioned compound having a trihalomethyl group includes 1,3,5-tris (trichlorofluorenyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2-chlorobenzene Base) — s —triazine, 1, 3 — (printed base of the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs of Trichloromethyl) — 5 — (4-chlorophenyl) — s — triazine, 1, 3 —Bis (trichloromethyl) -5— (2-methoxyphenyl) —s—triazine and 1 ′ 3-bis (trichloromethyl) —5— (4-methoxyphenyl) —S — Triazine. Among the compounds having a diphendione bond, other photoradical generating agents and compounds having a trihalomethyl group, 2-monohydroxy-2-methyl-1 monophenylpropan-1 monoketone 2, 2-Methyl- (4-Methylthiophene) This paper is sized to the Chinese National Standard (CNS) A4 (210X297 mm) -25-569043 A7 B7 V. Description of the invention (23) (Please read the notes on the back first (Fill in this page again) Base) 1-Morpholinyl-1 1-propan-1-one and 2-benzyl-2 2-dimethylamino-1 1- (4-Morpholinylphenyl) butan-1 1 Ketones are preferred because the patterns they form are difficult to fall off from the substrate during development and the strength and sensitivity of the patterns are high. The above-mentioned photopolymerization initiators can be used alone or in combination of two or more. If necessary, in the present invention, at least one compound may be further used in combination with the above photopolymerization initiator, and the compound is selected from the group consisting of a sensitizer, a hardening accelerator, and an optical cross-linking agent or an optical compound containing a polymer compound. A group of sensitizers (hereinafter referred to as ~ crosslinking / sensitizer polymer 〃). Examples of the above sensitizers include 4, 4/1 bis (dimethylamino) benzophenone, 4, 4 /-bis (diethylamino) benzophenone, 4-diethylamino ethyl acetophenone, 4- Dimethylaminophenylacetone, ethyl-4 dimethylaminobenzoate, 2-ethylhexyl-1,4-dimethylaminobenzoate, printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 2 , 5-bis (4-diethylaminobenzylidene) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzyl) coumarin and 4-di (diethylamino) chalconone. Examples of the above-mentioned hardening accelerator include chain transfer agents such as 2-hydrothiobenzimidazole, 2-hydrothiobenzothiazole, 2-hydrothiobenzonfazole, 2 '5-monohydrothio_1 , 3,4 Monothiadiazepine 1: 1, 2-hydrothio- 4,6-dimethylaminopyridine, 1-phenyl-5 -hydrothio-1, hydrazone -tetrazole and 3- Hydrosulphan — 4 —methyl — 4Η — 1, 2, 4 — three mouths 0 This paper size applies to China National Standard (CNS) A4 specifications (210 × 297 mm) 1-1-26-569043 A7 B7 Intellectual Property Bureau, Ministry of Economic Affairs Printed by an employee consumer cooperative V. Description of the invention (24) In addition, the above-mentioned polymer optical cross-linking / sensitizing agent is a material having an optical cross-linking agent and / or an optical sensitizer that can be used on the main chain and / or side chain. Polymer compounds with functional groups. Examples of the agent include a condensate of 4-azidobenzaldehyde and polyvinyl alcohol, a condensate of 4-azidebenzaldehyde and phenol novolac resin, and the following homopolymers or copolymers ·· 4- Allyl phenyl cinnamate, 1,4-polybutadiene and 1,2-polybutadiene. Among such sensitizers, hardening accelerators, and polymer optical cross-linking / sensitizers, 4,4 > —bis (dimethylamino) benzophenone, 4,4 < —bis (diethylamino) Benzophenone and 2-hydrothiobenzothiazole are preferred because the patterns formed by them are difficult to fall off from the substrate during development, and the intensity and sensitivity of the patterns are high. The photopolymerization initiator in the present invention is particularly preferably a combination of a diimidazole-based compound and at least one compound, and the compound is selected from the group consisting of: benzophenone-based diphenyl Ethylenedione-bonded compounds, benzophenone-based other photo radical generators, benzophenone-based sensitizers, and thiazole-based hardening accelerators. Particularly preferred examples of the composition include 2,2 > -bis (2-chlorophenyl) _4,5,5 > -tetrakis (4-ethoxycarbonylphenyl) _1,2 * -diimidazole / 4,4 / —Bis (diethylamino) benzophenone composition, 2,2-bis (2-chlorophenyl) -4,4,5,5, —tetra (4-ethoxycarbonylbenzene -1, 2 "-Dimidal mouthpiece / 4, 4 'one bis (diethylamino) benzophenone / 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl ) Butane-1, 1-ketone composition, 2 '2'-bis (2-chlorophenyl) -4,4-, 5, This paper size is applicable to China National Standard (CNS) A4 specification (210X297mmt) ( Please read the notes on the back before filling this page) -27- 569043 A7 _ B7____ V. Description of the invention (25) 5 / —tetrakis (4 —ethoxycarbonylphenyl) 1,2 > —diimidazole / 4 4,4 > a composition of bis (diethylamino) benzophenone / 1 monohydroxycyclohexylphenyl ketone, 2,2 > -bis (2-chlorophenyl) -4, '5,5tetra ( 4 monoethoxycarbonylphenyl) -1, 2 /-diimidazole / 4, 4/1 double (two Amino) benzophenone / 1 monohydroxycyclohexylphenyl ketone / 2-hydrothiobenzobenzothiazole composition, 2, 2 /-bis (2 '4 dichlorophenyl) -4, 4', 5 , 5 ^ —tetraphenyl-1, 2 / —diimidazole / 4,4 —bis (diethylamino) benzophenone composition, 2,2 > —bis (2,4-dibromophenyl) ) —4,4 /, 5,5 / -tetraphenyl-1, 2 / —diimidazole / 4,4 / —bis (diethylamino) benzophenone / 2—benzyl-1—dimethylamino-1 1 mono (4-morpholinylphenyl) butanone-1 monoketone composition, 2 '2-bis (2,4-dibromophenyl) -4,4 >, 5,5 / -tetra Phenyl-1,2 > -diimidazole / 4,4 > composition of monobis (diethylamino) benzophenone / 1 monohydroxycyclohexylphenyl ketone, and 2,2 > -bis (2 , 4,6-trichlorophenyl) -4,4 /, 5,5 > --tetraphenyl-1, 2 / -diimidazole / 4,4 > --bis (dimethylamino) benzophenone / 1 A composition of monohydroxycyclohexylphenyl ketone / 2-hydrothiobenzothiazole. In the present invention, the total amount of the compound having a diphendione bond, other photo radical generators, and a compound having a trihalomethyl group is preferably 80 wt% or less, which is based on light Polymerization initiator. The total amount of sensitizer and hardening accelerator should be 80 wt% or less, which is based on the photopolymerization initiator. In addition, the content of the polymer optical cross-linking / sensitizing agent should be 2000 parts by weight or less, and more preferably 180 parts by weight or less. This paper size applies the Chinese National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling this page) ····

、1T 經濟部智慧財產局員工消費合作社印製 -28 - 569043 A7 ___ B7_ 五、發明説明（26) 係基於1 0 0重量份的二咪唑爲主的化合物。 (請先閲讀背面之注意事項再填寫本頁) 本發明中，光聚合起始劑之含量宜在0 . 〇 1至 5 0 0重量份，更佳者在1至3 0 0重量份，特別地宜在 1 0至2 0 0重量份，此係基於1 〇 〇重量份的多官能基 單體（C )之總量，且視需要可使用單官能基單體。當光 聚合起始劑之含量小於〇 _ 〇 1重量份，經由曝光的硬化 將變得不完全而導致份的圖案可能會缺掉的或失去的，或 圖案可能有側侵鈾。當其含量大於5 0 0重量份，在顯影 中所形成圖案可能自基質上脫落，或在除了圖案形成部分 之外的區域中可能造成沾污與膜殘餘。 添加劑 在本發明中的輻射敏感性組合物可視需要而含有各種 添加劑。 經濟部智慧財產局員工消費合作社印製 該添加劑包括聚合物化合物如聚乙烯醇、聚乙二醇單 烷基醚或聚（氟烷基丙烯酸酯）；非離子性、陽離子性或 陰離子性界面活性劑；黏著促進劑如乙烯基三甲氧基矽烷 、乙烯基三乙氧基矽烷、乙烯基三（2 -曱氧基乙氧基） 矽烷、N -（2 -氨基乙基）一 3 -氨基丙基曱基二甲氧 基矽烷、N- (2 —氨基乙基）-3 -氨基丙基三甲氧基 矽烷、3 -氨基丙基三乙氧基矽烷、3 -縮水甘油氧基丙 基三甲氧基矽烷，3 -縮水甘油氧基丙基甲基二甲氧基矽 烷、2 -（3，4 一環氧基環己基）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 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐) 一 -29 - 569043 A7 B7____ 五、發明説明（27) (請先閱讀背面之注意事項再填寫本頁) 、3 -甲基丙烯基氧基丙基三甲氧基矽烷或3 -氫硫基丙 基三甲氧基矽烷；抗氧化劑如2，2 -硫雙（4 一甲基一 6 -第三丁基酚）或2，6 -二一第三丁基酚；紫外線吸 收劑如2-（3-第三丁基一5-甲基一2-羥基苯基） - 5 -氯苯并三唑或烷氧基苯甲酮；及凝結預防劑如聚丙 烯酸鈉。 在本發明中的輻射敏感性組合物宜含有有機酸以進一 步改良所形成的塗覆膜在鹼性顯影劑之中的溶解度，且於 顯影之後抑制未溶解的產物之存在，當該鹼可溶解的樹脂 (B )爲具有羧基基團的樹脂。 該有機酸較佳者爲脂肪族的羧酸或內含苯基基團的羧 酸。 經濟部智慧財產局員工消費合作社印製 上述脂肪族的羧酸之實施例包括單羧酸如甲酸、乙酸 、丙酸、丁酸、戊酸、叔戊酸、己酸、二乙基乙酸、庚酸 及辛酸；二羧酸如草酸、丙二酸、琥珀酸、戊二酸、己二 酸、庚二酸、軟木酸酸、壬二酸、癸二酸、十二烷二酸、 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、環己烷二羧酸、分解烏頭酸、蒸餾檸檬酸 、順丁烯二酸、反丁烯二酸及甲基反丁烯二酸；及三羧酸 如丙三羧酸、烏頭酸及樟腦酸。 上述內含苯基基團的羧酸例如爲具有直接鍵結至苯基 基團的羧基基團之芳香族羧酸，或其具有經由碳鏈而鍵結 至苯基基團的羧基基團之羧酸。 內含苯基基團的羧酸之說明性實施例包括芳香族單_ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） ' " 一 -30- 569043 A 7 ___ B7 五、發明説明（28) (請先閲讀背面之注意事項再填寫本頁) 酸如苯甲酸、曱苯酸、茴香酸、苯連三酸及菜基酸；芳香 族二羧酸如鄰酞酸、間酞酸及對酞酸；其具有三或更多羧 基基團的芳香族多羧酸如偏苯三酸、苯三酸、苯偏四用酸 及焦苯六羧酸；苯基乙酸、氫阿托酸、氫肉桂酸、扁桃酸 、苯基琥珀酸、阿托酸、肉桂酸、肉桂叉酸、香豆酸及傘 形花酸。 在此類有機酸之中，脂肪族的二羧酸及芳香族二羧酸 如丙二酸、己二酸、分解烏頭酸、蒸餾檸檬酸、反丁烯二 酸、甲基反丁烯二酸及鄰酞酸爲較佳的，此係基於鹼溶解 度，在如下記述的溶劑之中的溶解度、及在除了圖案形成 部分之外的區域中預防沾污及其類似者。 上述有機酸可單獨使用或合倂二或更多者而使用。 有機酸之含量宜在10 Wt%或更低，更佳者在1 w t %或更低，此係基於輻射敏感性組合物。當有機酸之 含量大於1 0 wt%，所形成圖案對基質之黏著可能降 低。 經濟部智慧財產局員工消費合作社印製 由以下方法對厚度在5 // m的2 0 // m點狀圖案測量 侵鈾速率，在本發明中的輻射敏感性組合物之侵蝕速率爲 30或更低，較佳者爲一60至+30 %，更佳者 爲 —40至+20 %，特別較佳者爲—30至+1 0%。 測量侵蝕速率之方法； 如展示於圖1中的點狀圖案，測量頂端寬度爲> a 〃 ，與由圖案底部算起高度（L)的1/2高度位置之寬度 爲〜b 〃 ，而計算由以下公式定義的侵蝕速率。 本紙張尺度適用中.國國家標準（CNS) A4規格（210x297公釐） " -31 - 569043 A7 __B7 _ 五、發明説明（29) 侵餓速率（％) = (a — b) x l〇〇/a (請先閲讀背面之注意事項再填寫本頁) 當由本發明的輻射敏感性組合物所形成的厚度在5 /zm的2 0 點狀圖案之侵蝕速率滿足上述需求，甚至 若使顯影條件嚴苛到可有效地移除在導孔中殘餘物，當濾 色器及間隙壁及/或黑色基質形成在用於薄膜電晶體（ T F T )彩色液晶顯示裝置的驅動基質上，可預防作爲間 隙壁或黑色基質的圖案發生過度侵蝕，且可有效地預防摩 擦布被圖案捕獲部分與預防圖案分離。 本發明的輻射敏感性組合物之乾燥膜的光學密度（ 〇D値）宜在0 · 5或更多，更佳者爲0 _ 6或更多，大 幅更佳者爲0 · 7或更多，特別地宜在〇 . 8或更多，以 每1 // m計。 溶劑 經濟部智慧財產局員工消費合作社印製 本發明的輻射敏感性組合物包含上述著色劑（A )、 鹼可溶解的樹脂（B )、多官能基單體（C )及光聚合起 始劑（D )作爲基本成分，以及上述添加劑作爲選擇的成 分。宜經由在適合溶劑之中溶解除了顏料之外的上述成分 而製作液體組合物。 任何溶劑均可接受的，只要其可分散或溶解成分（A )至（D )及添加劑成分，不與此類成分反應且具有適合 的揮發性。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） — -32- 569043 A7 B7_____ 五、發明説明（30) (請先聞讀背面之注意事項再填寫本頁} 經濟部智慧財產局員工消費合作社印製 該溶劑之說明性實施例包括（聚）伸烷基二醇單院基 醚類如乙二醇單甲基醚、乙二醇單乙醚、乙二醇單正丙基 醚、乙二醇單正丁基醚、二甘醇單甲基醚、二甘醇單乙醚 、二甘醇單正丙基醚、二甘醇單正丁基醚、三甘醇單甲基 醚、三甘醇單乙醚、丙二醇單甲基醚、丙二醇單乙醚、丙 二醇單正丙基醚、丙二醇單正丁基醚、二丙二醇單甲基醚 、二丙二醇單乙醚、二丙二醇單正丙基醚、二丙二醇單正 丁基醚、三丙二醇單甲基醚及三丙二醇單乙醚；（聚）伸 烷基二醇單烷基醚乙酸酯如乙二醇單甲基醚乙酸酯、乙二 醇單乙醚乙酸酯、二甘醇單甲基醚乙酸酯、二甘醇單乙醚 乙酸酯、丙二醇單甲基醚乙酸酯及丙二醇單乙醚乙酸酯； 其它醚類如二甘醇乙醚、二甘醇甲基乙醚、二甘醇乙醚及 四氫呋喃；酮如曱基乙基酮、甲基異丁基酮、環己酮、2 -庚酮及3 -庚酮；乳酸烷酯類如2 -羥基丙酸甲酯及2 -羥基丙酸乙酯；其它酯類如2 -羥基- 2 -甲基丙酸甲 酯、2 —羥基一 2 -甲基丙酸乙酯、3 —甲氧基丙酸甲酯 、3 -曱氧基丙酸乙酯、3 —乙氧基丙酸甲酯、3 —乙氧 基丙酸乙酯、乙氧基乙酸乙酯、羥基乙酸乙酯、2 -羥基 一 3 —甲基丁酸甲酯、乙酸3 —甲基一3 —甲氧基丁酯、 乙酸4 一甲氧基丁酯、丙酸3 —甲基一 3 —甲氧基丁酯、 乙酸乙酯、乙酸正丙酯、乙酸異丙酯、乙酸正丁酯、乙酸 異丁酯、乙酸正戊酯、乙酸異戊酯、丙酸正丁酯、丁酸乙 酯、丁酸正丙酯、丁酸異丙酯、丁酸正丁酯、丙酮酸曱酯 、丙酮酸乙酯、丙酮酸正丙酯、乙醯乙酸甲酯、乙醯乙酸 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） — -33- 569043 A7 B7 五、發明説明（31) (請先閲讀背面之注意事項再填寫本頁) 乙酯及2 -酮基丁酸乙酯；芳香族烴類如甲苯及二甲苯； 及羧酸醯胺如N -甲基吡咯烷酮、N，N -二甲基甲醯胺 及N，N —二甲基乙醯胺。 此類溶劑可單獨使用或合倂二或更多者而使用。 此外，高沸點溶劑如苄基乙醚、二-正己基醚、丙酮 基丙酮、異佛爾酮，己酸、辛酸、1一辛醇、1一壬醇、 苯甲醇、乙酸苄酯、苯甲酸乙酯、草酸二乙酯、順丁烯二 酸二乙酯、r 一丁內酯、碳酸乙烯酯、碳酸丙烯酯或乙二 醇單苯基醚乙酸酯，可與這些溶劑合倂使用。 上述高沸點溶劑可單獨使用或合倂二或更多者而使用 〇 經濟部智慧財產局員工消費合作社印製 在此類之中溶劑，丙二醇單甲基醚、乙二醇單甲基醚 乙酸酯、丙二醇單曱基醚乙酸酯、丙二醇單乙醚乙酸酯、 二甘醇乙醚、環己酮、2 -庚酮、3 —庚酮、2 -羥基丙 酸乙酯、4 一甲氧基乙酸丁酯、丙酸3 —甲基一 3 —甲氧 基丁酯、3 -甲氧基丙酸乙酯、3 —乙氧基丙酸甲酯、3 -乙氧基丙酸乙酯、乙酸正丁酯、乙酸異丁酯、乙酸正戊 酯、乙酸異戊酯、丙酸正丁酯、丁酸乙酯、丁酸異丙酯、 丁酸正丁酯及丙酮酸乙酯爲較佳的，此係基於溶解度，顏 料可分散性且可塗覆性。r -丁內酯可較佳地作爲高沸點 溶劑。 溶劑之含量宜在100至10，000重量份’更佳 者在5 0 0至5，0 0 0重量份，此係基於1 〇 〇重量份 的鹼可溶解的樹脂（B )。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -34 - 569043 A7 B7 五、發明説明（32) 趾邀壁及黑色基質之形成方法 (請先閲讀背面之注意事項再填寫本頁) 接著描述由本發明的輻射敏感性組合物形成間隙壁及 黑色基質之方法。 將液體輻射敏感性組合物施用於驅動基材用於薄膜電 晶體（T F T )彩色液晶顯示裝置（以下稱爲、、T F T驅 動基材〃），且作預烘烤而揮發溶劑，以形成塗層膜。之 後’經由光罩將此塗覆膜曝光，以形成預先決定圖案，使 用鹼性顯影劑作顯影以溶解且移除塗層膜未受影響的部分 ’且然後宜作後烘烤以形成預先決定間隙壁圖案。 將該液體輻射敏感性組合物施用於T F T驅動基材上 ’可使用適合的塗覆技藝如旋轉塗覆、澆鑄塗覆或滾動塗 覆。 於乾燥之後，塗層之厚度宜在〇·1至lOem，更 佳者爲0 . 2至7 · 0//m，大幅更佳者爲〇 . 5至 6 . 0 // m 〇 於後烘烤之後的塗層膜厚度宜在〇 · 5至1 〇 u m 經濟部智慧財產局員工消費合作社印製 ’更佳者在1至8 //m，大幅更佳者在2至6 //m。 用以形成間隙壁的輻射線，係選自可見光輻射線、紫 外線、遠紫外線、電子束及X -輻射線。該輻射線之波長 宜在190至450 nm。 該輻射線之曝光能量宜在1 0至1 〇，0 〇 〇 j / m 2 〇 上述鹼性顯影劑宜爲下列者之水溶液··碳酸鈉、氫氧 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -35- 569043 A7 B7 __ 五、發明説明（33) 化鈉、氫氧化鉀、四甲基氫氧化銨、膽鹼、1 ’ 8〜二吖 雙環—〔5 . 4 . 01 — 7 —十一*焼嫌或1 ’ 5 — 一 11 丫雙 環—〔4.3.0〕— 5 - 壬烯。 可將合適量的水溶性有機溶劑如甲醇或乙醇、或界面 活性劑加入上述鹼性顯影劑中。塗層膜於使用鹼性顯影劑 作顯影之後，宜在水淸洗。 該項顯影可爲沖洗顯影、噴灑顯影、浸泡顯影、槳式 顯影，針對顯影條件，宜在常溫下執行顯影5至3 〇 〇秒 0 爲了由本發明的輻射敏感性組合物形成黑色基質，將 具有如上述形成之間隙壁或不帶有間隙壁的丁 F T驅動基 材，採用如間隙壁之相同方法而形成黑色基質。當間隙壁 與黑色基質形成在相同的T F T驅動基材上，間隙壁可在 黑色基質之前或於黑色基質之後形成，或可與黑色基質同 時形成。 具有如上述形成之間隙壁及/或黑色基質的T F T驅 動基材，極度可用於彩色液晶顯示裝置、色彩影像擷取元 素、色彩感應器及其類似者。 實施例 以下實施例提供用於進一步說明本發明之目的，但並 非作爲限制。 實施例1 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 一 一 -36- (請先閱讀背面之注意事項再填寫本頁) 馨裝. -訂 經濟部智慧財產局員工消費合作社印製 569043 A7 __ B7_ 五、發明説明（34) (請先閲讀背面之注意事項再填寫本頁) 將1 0 0重量份的碳黑、3 0重量份的硫酸鋇及3 0 重量份的氨基甲酸酯爲主的分散劑（Disperbyk— 1 8 2 )作爲著色劑（A) ，5 0重量份的甲基丙烯酸/甲基丙 烯酸2 -羥乙酯/甲基丙烯酸苄酯/聚苯乙烯巨單體之四 聚合物（重量比例·· 1 5/1 5/6 0 / 1 0，= 25，000)作爲鹼可溶解的樹脂（B) ，40重量份 的二異戊四醇六丙烯酸酯作爲多官能基單體（C )，1 〇 重量份的2，2，—雙（2 —氯苯基）—4，4，，5， 5 / —四（4一乙氧羰基苯基）—1 ，2 / —二咪唑、 1 0重量份的4，4 > 一雙（二乙氨基）苯甲酮及20重 量份的2 —苄基一 2 —二甲氨基一 1 一（4 一嗎福啉基苯 基）丁一 1 一酮作爲光聚合起始劑（D)，及1，500 重量份的3 -乙氧基丙酸乙酯作爲溶劑混合在一起，以製 備液體輻射敏感性組合物（I )。 經濟部智慧財產局員工消費合作社印製 經由旋轉塗覆器將液體組合物（I )施用於T F T驅 動基材，且於9 0°C預烘烤4分鐘以形成6 . 7//m -厚 的塗覆膜。之後，經由光罩，使用高壓汞燈，將此基質冷 卻至室溫且曝光至2，000 J/m2的波長爲365 n m的紫外線。然後，於2 3 °C，將此基質浸入在 0 · 0 4 w t %的氫氧化鉀水溶液之中1分鐘以顯影塗 層膜，在超純水中淸洗且以空氣乾燥。其後，於2 5 0 °C 將其作後烘烤3 0分鐘，以在T F T驅動基材上形成厚度 在5 // m的2 0 // m黑色點狀間隙壁圖案。 當使用所得到T F T驅動基材在組裝的顯示板上作顯 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -37 - 569043 A 7 _B7_____ 五、發明説明（35) 示測試，未觀察到顯示失效如影像黏著。 此外，所得到T F T驅動基材上之未受影響部分未觀 察到在殘餘物與沾污，未觀察到圖案分離及缺掉的及失去 部分的圖案，且該圖案具有高的膜硬度與卓越的表面平滑 性。 當計算形成在彼厚度在5 // m的2 0 // m黑色點狀圖 案上之侵鈾速率，其爲1 0 %。 自液體組合物（I )形成的乾燥塗覆膜的光學密度（ 〇D 値）〇 . 67 每 l//m。 可經由將1 w t %在此使用的氨基甲酸酯爲主的分 散液溶解在上述成分（B )至（D )及溶劑的混合物之中 而製備一溶液，且經由旋轉塗覆器將此溶液施用於表面有 1 T ◦膜形成在其上的玻璃基質上，其乾燥之後的厚度爲 6 //m，於8 0°C預烘烤1 0分鐘，用波長爲3 6 5 n m的紫外線2，0 0 0曝光J /m 2，且然後後於 2 2 0 °C烘烤1小時。將此基質與另一具有I τ ◦膜形成 在表面上的玻璃基質組裝，且將液晶射入介於二基質之間 的空間以製作液晶小室，且然後於1 〇 〇。<3退火1小時。 於6 0 °C將所得到液晶小室測量滯留時間爲1 6 . 7 ms，其電壓保持爲86 %。 實施例2 將140重量份的C . I ·顏料紅色I??、go重 量份的C . I ·顏料藍色1 5 : 4、3 0重量份的硫酸鋇 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 一一 -38- (請先閲讀背面之注意事項再填寫本頁) 訂 經濟部智慧財產局員工消費合作社印製 569043 A7 —______ B7_ 五、發明説明（36) 及6 0重量份的氨基甲酸酯爲主的分散劑（Disperbyk -1 8 2 ;商品名）作爲著色劑（a ) ，5 0重量份的甲基 丙烯酸/甲基丙烯酸2 -羥乙酯/甲基丙烯酸苄酯/聚苯 乙Μ巨單體之四聚合物（重量比例：1 5//1 5/6 〇/ 10 ’Mw=25,〇〇〇)作爲鹼可溶解的樹脂（Β) ’ 4 0重量份的二異戊四醇六丙烯酸酯作爲多官能基單體 (C) ，1〇重量份的2，2，—雙（2 —氯苯基）一 4 ’ 4一 ’5’ 5 > —四（4 一乙氧羰基苯基）—1 ，2 一 一二咪唑、1 〇重量份的4，4 > —雙（二乙氨基）苯甲 酮及20重量份的2 —苄基—2 -二甲氨基—1— (4 一 嗎福啉基苯基）丁烷- 1 一酮作爲光聚合起始劑（D )， 及1，5 0 0重量份的3 -乙氧基丙酸乙酯作爲溶劑，經 混合在一起而製備液體輻射敏感性組合物（I I )。 經由旋轉塗覆器將液體組合物（I I )施用於T F 丁 驅動基材上，且於90 t預烘烤4分鐘，以形成7 . 0 // m -厚的塗覆膜。之後，採用如在實施例中1相同方法 中形成間隙壁圖案。 當在使用所得到的T F T驅動基材組裝的顯示板土作 顯示測試製，未觀察到顯示失效如影像黏著。 此外，在所得到的T F T驅動基材上未受影響部分， 未觀察到殘餘物與沾污，使未觀察到圖案分離與缺掉的及 失去部分的圖案，且該圖案具有高膜硬度與卓越的表面平 滑性。 當計算所形成厚度在5 //m之2 0 //m的黑色點狀圖 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁} ··裝· -訂 經濟部智慧財產局員工消費合作社印製 -39- 569043 A7 _____ B7_ _ 五、發明説明（37) 案之侵蝕速率，其爲5 %。 形成自液體組合物（I I )的乾燥塗覆膜之光學密度 (〇D値）爲0 . 72每l//m。 實施例3 採用如在實施例1中相同方法液體輻射敏感性組合物 (I I I )，除 了使用 Disperbyk— 1 7 0 (商品名）代 替Disperbyk— 1 8 2作爲氨基甲酸酯爲主的分散劑。之 後，採用如在實施例1中相同方法中形成間隙壁圖案，除 了使用液體組合物（I I I )代替液體組合物（I )。 當在使用所得到的T F 丁驅動基材組裝的顯示板上執 行顯示測試，未觀察到顯示失效如影像黏著。 此外，在所得到T F T驅動基材上未受影響部分未觀 察到殘餘物與沾污，而未觀察到圖案分離及缺掉的及失去 部分的圖案，且該圖案更具有高膜硬度及卓越的表面平滑 性。 當針對所形成的彼厚度在5 # m 的2 0 // m黑色點 狀圖案之侵蝕速率’其計算値爲一 1 2 %。 當採用如在實施例1中相同方法測量中在此使用的該 氨基甲酸酯爲主的分散劑之電壓保持。其値爲9 2 實施例4 採用如在實施例1中相同方法中製備液體輻射敏感性 組合物（IV)，除了使用〇丨3?〇]^71^-165(商品名 本紙張尺度適用中國國家標準（CNS ) A4規格（210x297公羡）" " -40- (請先閲讀背面之注意事項再填寫本頁) .·裝· -訂 經濟部智慧財產局員工消費合作社印製 569043 A7 B7 五、發明説明（38) )而代替Disperbyk— 1 8 2作爲氨基甲酸酯爲主的分散 劑。之後，採用如在實施例1中相同方法形成間隙壁圖案 ’除了比液體組合物（I V )代替液體組合物（I )而使 用。 當在使用所得到的T F T驅動基材組裝的顯示板上執 行顯示測試，未觀察到顯示失效如影像黏著。 此外，在所得到T F T驅動基材上未受影響部分未觀 察到殘餘物與沾污，而未觀察到圖案分離及缺掉的及失去 部分的圖案，且該圖案更具有高膜硬度及卓越的表面平滑 性。 當針對所形成的彼厚度在5 μ m 的2 Ο // m黑色點 狀圖案之侵鈾速率，其計算値爲- 3 %。 當採用如在實施例1中相同方法測量中在此使用的該 氨基甲酸酯爲主的分散劑之電壓保持。。 當採用如在實施例1中相同方法測量中在此使用的該 氨基甲酸酯爲主的分散劑之電壓保持，其爲 87 %。 比較例1 採用如在實施例1中相同方法中製備液體輻射敏感性 組合物（i )，除了使用聚乙烯亞胺-聚酯爲主的分散劑 (商品名：Solsperse 24000,由Zeneca公司製作）代替 D i s p e r b y k — 1 8 2作爲分散劑。之後，採用如在實施例 1中相同方法中，形成間隙壁圖案除了使用液體組合物（ i )而代替液體組合物（I )。 本紙張尺度適用中國國家標準（CNS ) Α4規格（21〇χ297公釐） (請先閱讀背面之注意事項再填寫本頁) C.Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs of 1T -28-569043 A7 ___ B7_ V. Description of the Invention (26) is based on 100 parts by weight of diimidazole-based compounds. (Please read the precautions on the back before filling this page) In the present invention, the content of the photopolymerization initiator should preferably be from 0.01 to 500 parts by weight, more preferably from 1 to 300 parts by weight, particularly The content is preferably from 10 to 200 parts by weight, which is based on the total amount of the polyfunctional monomer (C) of 100 parts by weight, and a monofunctional monomer may be used as necessary. When the content of the photopolymerization initiator is less than 〇 〇 〇 1 part by weight, the hardening through exposure will become incomplete and the pattern of the part may be missing or lost, or the pattern may have side invasion of uranium. When the content is more than 500 parts by weight, the pattern formed during development may be detached from the substrate, or stains and film residues may be caused in areas other than the pattern forming portion. Additives The radiation-sensitive composition in the present invention may contain various additives as necessary. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs This additive includes polymer compounds such as polyvinyl alcohol, polyethylene glycol monoalkyl ether or poly (fluoroalkyl acrylate); non-ionic, cationic or anionic interfacial activity Agents; adhesion promoters such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropyl N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane Silane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-monoepoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxy Silane, 3 -chloropropyltrimethoxysilane The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 1-29-569043 A7 B7____ V. Description of the invention (27) (Please read the notes on the back first Fill out this page again), 3-Methacryloxypropyltrimethoxysilane, or 3-Hydroxy Thiopropyltrimethoxysilane; antioxidants such as 2,2-thiobis (4-methyl-6-tert-butylphenol) or 2,6-di-tertiary-butylphenol; UV absorbers such as 2 -(3-third butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole or alkoxybenzophenone; and a coagulation preventive agent such as sodium polyacrylate. The radiation-sensitive composition in the present invention preferably contains an organic acid to further improve the solubility of the formed coating film in an alkaline developer, and to suppress the presence of undissolved products after development, when the alkali is soluble The resin (B) is a resin having a carboxyl group. The organic acid is preferably an aliphatic carboxylic acid or a carboxylic acid containing a phenyl group. Examples of the above-mentioned aliphatic carboxylic acids printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, tert-valeric acid, hexanoic acid, diethylacetic acid, heptane Acids and caprylic acids; dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, soft wood acid, azelaic acid, sebacic acid, dodecanedioic acid, methylpropane Diacid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, cyclohexanedicarboxylic acid, decomposed aconitic acid, distilled citric acid, maleic acid, fumaric acid Adipic acid and methyl fumaric acid; and tricarboxylic acids such as malonic acid, aconitic acid, and camphoric acid. The phenyl group-containing carboxylic acid is, for example, an aromatic carboxylic acid having a carboxyl group directly bonded to a phenyl group, or an carboxylic acid having a carboxyl group bonded to a phenyl group via a carbon chain. carboxylic acid. Illustrative examples of carboxylic acids containing phenyl groups include aromatic mono- _ This paper size applies Chinese National Standard (CNS) A4 (210X 297 mm) '" -30- 569043 A 7 ___ B7 5 2. Description of the invention (28) (Please read the notes on the back before filling out this page) Acids such as benzoic acid, benzoic acid, anisic acid, phthalic acid, and acetic acid; aromatic dicarboxylic acids such as phthalic acid, Isophthalic acid and terephthalic acid; aromatic polycarboxylic acids with three or more carboxyl groups such as trimellitic acid, trimellitic acid, trimellitic acid and pyromellitic acid; phenylacetic acid, hydrogen Atropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, cinnamic acid, coumaric acid and umbellic acid. Among such organic acids, aliphatic dicarboxylic acids and aromatic dicarboxylic acids such as malonic acid, adipic acid, decomposed aconitic acid, distilled citric acid, fumaric acid, methyl fumaric acid Phthalic acid and phthalic acid are preferred, and are based on alkali solubility, solubility in solvents described below, and prevention of staining and the like in areas other than the pattern-forming portion. These organic acids may be used alone or in combination of two or more. The organic acid content should preferably be 10 Wt% or less, more preferably 1 Wt% or less, based on the radiation-sensitive composition. When the content of the organic acid is more than 10 wt%, the adhesion of the formed pattern to the substrate may be reduced. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs on the uranium invasion rate measured on a 2 0 // m dot pattern with a thickness of 5 // m. The erosion rate of the radiation-sensitive composition in the present invention is 30 or It is lower, preferably 60 to + 30%, more preferably -40 to + 20%, and particularly preferably -30 to + 10%. Method for measuring erosion rate; as shown in the dotted pattern in Fig. 1, the width of the top end of the measurement is > a 〃, and the width at the height of 1/2 of the height (L) from the bottom of the pattern is ~ b ，, and Calculate the erosion rate defined by the following formula. This paper size is applicable. National National Standard (CNS) A4 specification (210x297 mm) " -31-569043 A7 __B7 _ V. Description of the invention (29) Starvation rate (%) = (a — b) xl〇〇 / a (Please read the precautions on the back before filling this page) When the erosion rate of the 20 dot pattern with a thickness of 5 / zm formed by the radiation-sensitive composition of the present invention meets the above requirements, even if the development conditions are made It is severe enough to effectively remove the residue in the guide hole. When the color filter and the spacer and / or the black matrix are formed on the driving matrix for a thin film transistor (TFT) color liquid crystal display device, it can be prevented from acting as a gap. The pattern of the wall or the black matrix is excessively eroded, and it is possible to effectively prevent the rubbing cloth from being separated from the pattern by the pattern capturing portion. The optical density (〇D 値) of the dried film of the radiation-sensitive composition of the present invention is preferably 0. 5 or more, more preferably 0_6 or more, and much more preferably 0. 7 or more. , Particularly preferably 0.8 or more, per 1 // m. The radiation-sensitive composition printed by the employee cooperative of the Intellectual Property Bureau of the Ministry of Solvent Economy includes the above-mentioned colorant (A), alkali-soluble resin (B), polyfunctional monomer (C), and photopolymerization initiator (D) as a basic component, and the above-mentioned additives as selected components. The liquid composition is preferably prepared by dissolving the above-mentioned components other than the pigment in a suitable solvent. Any solvent is acceptable as long as it can disperse or dissolve ingredients (A) to (D) and additive ingredients, does not react with such ingredients and has suitable volatility. This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) — -32- 569043 A7 B7_____ V. Description of Invention (30) (Please read the notes on the back before filling this page} Intellectual Property Bureau, Ministry of Economic Affairs Illustrative examples of the printing of this solvent by employee consumer cooperatives include (poly) alkylene glycol monobasic ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, Ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol Glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, two Propylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether and tripropylene glycol monoethyl ether; (poly) alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol mono Diethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propane Glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; other ethers such as diethylene glycol ether, diethylene glycol methyl ether, diethylene glycol ether and tetrahydrofuran; ketones such as fluorenyl ethyl ketone, methyl Isobutyl ketone, cyclohexanone, 2-heptanone and 3-heptanone; alkyl lactates such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; other esters such as 2-hydroxy-2- Methyl methylpropionate, ethyl 2-hydroxy- 2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, Ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-3-methylbutyrate, acetic acid 3-methyl-3-methoxybutyl, acetic acid 4 Monomethoxybutyl, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl acetate Ester, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, ethyl pyruvate, ethyl pyruvate, n-propyl pyruvate Esters, methyl ethyl acetate,醯 Acetate This paper is sized for Chinese National Standard (CNS) A4 (210X297 mm) — -33- 569043 A7 B7 V. Description of the invention (31) (Please read the precautions on the back before filling this page) Ethyl acetate and 2 -Ethyl ketobutyrate; aromatic hydrocarbons such as toluene and xylene; and carboxylic acid amines such as N-methylpyrrolidone, N, N-dimethylformamide and N, N-dimethylacetamidine Amine. Such solvents can be used alone or in combination with two or more. In addition, high boiling point solvents such as benzyl ether, di-n-hexyl ether, acetone acetone, isophorone, hexanoic acid, caprylic acid, 1 Monooctanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, r monobutyrolactone, ethylene carbonate, propylene carbonate or ethyl Diol monophenyl ether acetate can be used in combination with these solvents. The above-mentioned high-boiling-point solvents can be used alone or in combination of two or more of them. The employees' cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs print these solvents. Propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetic acid. Ester, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol ether, cyclohexanone, 2-heptanone, 3-heptanone, ethyl 2-hydroxypropionate, 4-monomethoxy Butyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, acetic acid N-butyl, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, isopropyl butyrate, n-butyl butyrate and ethyl pyruvate are preferred This is based on solubility, pigment dispersibility and coatability. r-Butyrolactone is preferred as a high boiling point solvent. The content of the solvent is preferably 100 to 10,000 parts by weight ', more preferably 500 to 5,000 parts by weight, based on 1,000 parts by weight of the alkali-soluble resin (B). This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) -34-569043 A7 B7 V. Description of the invention (32) Method of forming toe wall and black matrix (Please read the precautions on the back before filling in this (Page) Next, a method for forming a partition wall and a black matrix from the radiation-sensitive composition of the present invention is described. The liquid radiation-sensitive composition is applied to a driving substrate for a thin film transistor (TFT) color liquid crystal display device (hereinafter referred to as a TFT driving substrate), and the solvent is volatilized as a pre-baking to form a coating layer. membrane. Then 'expose this coating film through a photomask to form a predetermined pattern, use an alkaline developer for development to dissolve and remove the unaffected part of the coating film' and then post-bake to form a predetermined pattern Gap wall pattern. Applying this liquid radiation-sensitive composition to a T F T driven substrate can be performed using a suitable coating technique such as spin coating, cast coating or roll coating. After drying, the thickness of the coating should be in the range of 0.1 to 10em, more preferably 0.2 to 7. 0 // m, and much more preferably 0.5 to 6. 0 // m 〇 after baking The thickness of the coating film after baking should be in the range of 0.5 to 10um. The "better" is printed by the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs in the range of 1 to 8 // m, and the substantially better is in the range of 2 to 6 // m. The radiation used to form the barrier is selected from the group consisting of visible radiation, ultraviolet radiation, extreme ultraviolet, electron beams, and X-radiation. The wavelength of this radiation is preferably 190 to 450 nm. The exposure energy of the radiation should be in the range of 10 to 10,000j / m2. The above-mentioned alkaline developer should be an aqueous solution of the following: · Sodium carbonate, hydrogen and oxygen. The Chinese paper standard (CNS) A4 specifications (210X297 mm) -35- 569043 A7 B7 __ V. Description of the invention (33) Sodium chloride, potassium hydroxide, tetramethylammonium hydroxide, choline, 1 '8 ~ diazine bicyclic— [5. 4 01 — 7 — eleven * suspicion or 1 '5 — a 11 yambicyclic — [4.3.0] — 5-nonene. A suitable amount of a water-soluble organic solvent such as methanol or ethanol, or a surfactant may be added to the above-mentioned alkaline developer. After the coating film is developed with an alkaline developer, it should be washed in water. This development can be developed by rinsing, spraying, immersion, and paddle. According to the developing conditions, it is suitable to perform the development at normal temperature for 5 to 300 seconds. In order to form a black matrix from the radiation-sensitive composition of the present invention, The black matrix formed as described above or the T-FT driving substrate without a gap is formed by the same method as the gap. When the partition wall is formed on the same TF driving substrate as the black matrix, the partition wall may be formed before or after the black matrix, or may be formed simultaneously with the black matrix. The TFT driving substrate having the partition wall and / or the black matrix formed as described above is extremely useful for a color liquid crystal display device, a color image capturing element, a color sensor, and the like. Examples The following examples are provided for the purpose of further illustrating the invention, but are not intended to be limiting. Example 1 This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -11-36- (Please read the precautions on the back before filling this page) Printed by the cooperative 569043 A7 __ B7_ V. Description of the invention (34) (Please read the precautions on the back before filling this page) Put 100 parts by weight of carbon black, 30 parts by weight of barium sulfate and 30 parts by weight of As a colorant (A), a urethane-based dispersant (Disperbyk—182) is used, and 50 parts by weight of methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate / polystyrene Macromonomer four polymers (weight ratio: 1 5/1 5/6 0/1 0, = 25,000) as alkali-soluble resin (B), 40 parts by weight of diisopentaerythritol hexaacrylic acid Esters are polyfunctional monomers (C), 10 parts by weight of 2,2, -bis (2-chlorophenyl) -4,4,5,5 / -tetra (4-ethoxycarbonylphenyl) —1, 2 / —diimidazole, 10 parts by weight of 4, 4 > bis (diethylamino) benzophenone and 20 parts by weight of 2-benzyl-1 2-dimethylamino-1 1-1 (4-monomorpholinylphenyl) butan-1 monoketone was used as a photopolymerization initiator (D), and 1,500 parts by weight of ethyl 3-ethoxypropionate were mixed together as a solvent to prepare a liquid Radiation-sensitive composition (I). Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the liquid composition (I) was applied to the TFT driving substrate via a spin coater, and pre-baked at 90 ° C for 4 minutes to form 6.7 // m -thickness Coating film. Thereafter, the substrate was cooled to room temperature through a photomask using a high-pressure mercury lamp and exposed to ultraviolet light having a wavelength of 365 n m at 2,000 J / m2. Then, the substrate was immersed in a 0. 04 w t% potassium hydroxide aqueous solution at 2 3 ° C for 1 minute to develop a coating film, rinsed in ultrapure water, and air-dried. Thereafter, it was post-baked at 250 ° C for 30 minutes to form a 2 0 / m black dot-shaped gap wall pattern with a thickness of 5 // m on the T F T driving substrate. When the obtained TFT driver substrate is used for display on the assembled display board, the paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -37-569043 A 7 _B7_____ 5. The description of the invention (35) shows the test, No display failure such as image sticking was observed. In addition, no residues and stains were observed on the unaffected portion of the obtained TFT driving substrate, and patterns of pattern separation and missing and missing portions were not observed, and the pattern had high film hardness and excellent Surface smoothness. When calculating the rate of uranium invasion on a 2 0 // m black dot pattern with a thickness of 5 // m, it is 10%. The optical density (ODD) of the dry coating film formed from the liquid composition (I) was 0.67 per l // m. A solution can be prepared by dissolving 1 wt% of the urethane-based dispersion in the mixture of the above-mentioned components (B) to (D) and the solvent, and this solution is prepared by a spin coater 1 T applied on the surface of the substrate. The film is formed on a glass substrate with a thickness of 6 // m after drying. It is pre-baked at 80 ° C for 10 minutes, with ultraviolet light with a wavelength of 3 6 5 nm. 2 , 0 0 0 exposure J / m 2, and then baked at 2 2 ° C for 1 hour. This substrate was assembled with another glass substrate having an I τ film formed on the surface, and liquid crystal was injected into the space between the two substrates to make a liquid crystal cell, and then at 100. < 3 annealing for 1 hour. The measured retention time of the obtained liquid crystal cell at 60 ° C was 16.7 ms, and the voltage was maintained at 86%. Example 2 140 parts by weight of C.I. Pigment Red I ??, go parts by weight of C.I. Pigment Blue 15: 4, 30 parts by weight of barium sulfate. The paper dimensions are applicable to Chinese national standards (CNS ) A4 specification (210X297mm)-One-38- (Please read the notes on the back before filling out this page) Order printed by the Intellectual Property Bureau Employee Consumer Cooperative of the Ministry of Economic Affairs 569043 A7 —______ B7_ 5. Description of the invention (36) and 60 parts by weight of a urethane-based dispersant (Disperbyk-1 8 2; trade name) as a colorant (a), 50 parts by weight of methacrylic acid / 2-hydroxyethyl methacrylate / formaldehyde Four polymers of benzyl acrylate / polystyrene macromonomer (weight ratio: 1 5 // 1 5/6 〇 / 10 'Mw = 25, 〇〇〇) as alkali-soluble resin (B)' 40 parts by weight of diisopentaerythritol hexaacrylate as the polyfunctional monomer (C), 10 parts by weight of 2,2, -bis (2-chlorophenyl)-4 '4-'5' 5 > --tetrakis (4-ethoxycarbonylphenyl) -1,2imidazole, 10 parts by weight of 4,4 >-bis (diethylamino) benzophenone and 20 parts by weight of 2-benzyl —2-dimethylamino-1- (4-monomorpholinylphenyl) butane-1one as a photopolymerization initiator (D), and 1,500 parts by weight of 3-ethoxypropane Ethyl acetate was used as a solvent and mixed together to prepare a liquid radiation-sensitive composition (II). The liquid composition (I I) was applied to a TF driven substrate through a spin coater and pre-baked at 90 t for 4 minutes to form a 7. 0 // m-thick coating film. Thereafter, the partition wall pattern is formed in the same method as in Example 1. When the display panel assembled using the obtained TFT driving substrate was used as a display test system, no display failure such as image sticking was observed. In addition, in the unaffected part of the obtained TFT driving substrate, no residues and stains were observed, no pattern separation and missing and missing part patterns were observed, and the pattern had high film hardness and excellent Surface smoothness. When calculating the black dots with a thickness of 5 // m to 2 0 // m, the paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling in this page } ····· Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-39- 569043 A7 _____ B7_ _ V. The erosion rate of the case of the invention (37) is 5%. Formed from the liquid composition (II) The optical density (ODD) of the dry coating film was 0.72 per l // m. Example 3 A liquid radiation sensitive composition (III) was used in the same manner as in Example 1, except that Disperbyk-1 was used. 7 0 (trade name) instead of Disperbyk— 1 8 2 as a urethane-based dispersant. Thereafter, a partition wall pattern was formed in the same method as in Example 1, except that the liquid composition (III) was used instead of the liquid. Composition (I). When a display test was performed on a display panel assembled using the obtained TF driver substrate, no display failure such as image sticking was observed. In addition, the unaffected portion on the obtained TFT driver substrate was not affected. Observed residues and stains Smear without pattern separation and missing and missing part of the pattern, and the pattern has high film hardness and excellent surface smoothness. When the thickness of the formed 5 # m 2 0 // m The erosion rate of the black dot-like pattern is' calculated to be 12%. When the urethane-based dispersant used here is measured in the same manner as in Example 1, the voltage is maintained. Its 値 is 9 2 Example 4 A liquid radiation-sensitive composition (IV) was prepared in the same method as in Example 1, except that 〇 丨 3? 〇] ^ 71 ^ -165 (brand name paper size applies Chinese national standards ( CNS) A4 size (210x297 public envy) " " -40- (Please read the precautions on the back before filling out this page). ···· Order printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Consumer Cooperatives 569043 A7 B7 V. Description of the invention (38)) instead of Disperbyk-1 2 2 as a urethane-based dispersant. Thereafter, the partition wall pattern was formed using the same method as in Example 1 except that the liquid composition (IV) was used instead of liquid组合 物 （I）。 When using A display test was performed on the obtained TFT driving substrate assembled display board, and no display failure such as image sticking was observed. In addition, no residue and contamination were observed on the unaffected portion of the obtained TFT driving substrate, and no Pattern separation and missing and missing patterns are observed, and the pattern has higher film hardness and excellent surface smoothness. When the black dot-like pattern with a thickness of 5 μm is formed for each of them, the thickness is 5 μm. The rate of uranium invasion is calculated to be -3% plutonium. The voltage maintenance of the urethane-based dispersant used here was measured when measured in the same manner as in Example 1. . The voltage retention of the urethane-based dispersant used here measured in the same method as in Example 1 was 87%. Comparative Example 1 A liquid radiation-sensitive composition (i) was prepared in the same manner as in Example 1, except that a polyethyleneimine-polyester-based dispersant was used (trade name: Solsperse 24000, manufactured by Zeneca) Instead of Disperbyk — 1 8 2 as dispersant. Thereafter, in the same method as in Example 1, the partition wall pattern was formed except that the liquid composition (i) was used instead of the liquid composition (I). This paper size applies to Chinese National Standard (CNS) A4 specification (21 × 297 mm) (Please read the precautions on the back before filling this page) C.

、1T 經濟部智慧財產局員工消費合作社印製 -41 - 569043 A7 B7 五、發明説明（39) 當在使用所得到的T F T驅動基材所組裝的顯示板上 執行顯示測試，發生影像黏著。 當針對所形成的彼厚度在5 // m的2 0 // m黑色點狀 圖案之侵鈾速率，其計算値爲3 5 %。 當採用如在實施例1中相同方法測量中在此使用的該 氨基甲酸酯爲主的分散劑之電壓保持，其爲7 1 %。 如上所述，本發明的輻射敏感性組合物特色在於其所 形成圖案之侵蝕速率低，甚至於嚴格的顯影條件之下可預 防圖案過度的侵鈾，該圖案難以反向逐漸變得尖細，可有 效地預防摩擦布被圖案捕獲與預防圖案分離，而不會發生 顯示失效如影像黏著，該圖案具有高的膜硬度與卓越的表 面平滑性，膜殘餘物與沾污難以發生在未受影響部分的基 質上，且在顯影中圖案對基質有卓越的黏著。因此，該輻 射敏感性組合物可極有利地用以在用於薄膜電晶體（ T F T )彩色液晶顯示裝置的驅動基質上形成間隙壁及/ 或黑色基質。 可有效地預防摩擦布被圖案捕獲與圖案分離，而不會 發生顯示失效如影像黏著，該圖案具有高的膜硬度與卓越 的表面平滑性，膜殘餘物與沾污難以發生在未受影響部分 的基質上，且在顯影中圖案對基質有卓越的黏著。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) 訂 經濟部智慧財產局員工消費合作社印製 -42-Printed by 1T Consumer Intellectual Property Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs -41-569043 A7 B7 V. Description of Invention (39) When a display test is performed on a display board assembled using the obtained TFT driving substrate, image sticking occurs. For the rate of uranium invasion of the formed 2 0 // m black dot-like pattern with a thickness of 5 // m, the plutonium is calculated to be 35%. The voltage retention of the urethane-based dispersant used here measured in the same method as in Example 1 was 71%. As mentioned above, the radiation-sensitive composition of the present invention is characterized by a low erosion rate of the pattern formed, and even under severe development conditions, it can prevent excessive uranium invasion of the pattern, which is difficult to gradually become tapered in the opposite direction. It can effectively prevent the friction cloth from being captured by the pattern and prevent the pattern from separating without display failure such as image sticking. The pattern has high film hardness and excellent surface smoothness, and film residues and stains are difficult to occur without being affected. Part of the substrate, and the pattern has excellent adhesion to the substrate during development. Therefore, the radiation-sensitive composition can be very advantageously used to form a partition wall and / or a black matrix on a driving substrate for a thin film transistor (T F T) color liquid crystal display device. It can effectively prevent the friction cloth from being captured and separated by the pattern without display failure such as image adhesion. The pattern has high film hardness and excellent surface smoothness, and film residues and stains are difficult to occur in unaffected parts. On the substrate, and the pattern has excellent adhesion to the substrate during development. This paper size applies to China National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling out this page) Order Printed by the Intellectual Property Bureau Staff Consumer Cooperatives -42-

Claims (1)

569043 經濟部智慧財產局員工消費合作社印製 年日修正 六、申請專利範圍 巧 第9 1 1 1 225 1號專利申請案 中文申請專利範圍修正本 民國92年2月14曰修正 1 ·一種輻射敏感性組合物，（1 )此組合物包含（A ) 內含顏料的著色劑、（B )鹼可溶解的樹脂、（C )多官 會巨基單體及（D )光聚合起始劑，（2 )此組合物所形成 的20μηι點狀圖案之侵蝕速率在30 %或以下，及（3 )此 組合物用以在薄膜電晶體（TFT )彩色液晶顯示裝置用之 驅雲力基質上形成間隙壁及/或黑色基質，其中內含在著色 劑（A)中的顏料係經由具有氨基曱酸酯鍵結的分散劑所 分散。 ^ 2.如申請專利範圍第1項之輻射敏感性組合物，其中 著色劑（A )含有C.I.顏料紅色177及C.I·顏料藍色15 : 4 及/或C.I.顏料藍色15 : 6。 3·如申請專利範圍第丨項之輻射敏感性組合物，其中 具有氨基甲酸酯鍵結的分散劑其電壓保持係爲8 0 %或以 上。 4·如申請專利範圍第丨項之輻射敏感性組合物，其中 著色劑（A )含有碳黑及/或至少二種有機顏料。 5·如申請專利範圍第丨項之輻射敏感性組合物，其中 著色劑（A )進一步含有增量劑顏料。 6.如申請專利範圍第1項之輻射敏感性組合物，其中 鹼可溶解的樹脂（B )係至少一種選自由內含羧基基團的 共聚物（la)、內含羧基基團的共聚物（lb)、內含羧基 本蛾<張尺度適用中國國家標準TCNS ) A4規格（210X297公ϋ " "" Λ __ (請先聞讀背面之注意事項再填寫本頁)569043 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Date of Amendment VI. Application for Patent Range No. 9 1 1 1 225 No. 1 Patent Application Chinese Application for Amendment of Patent Range Amendment February 14, 1992 Amendment 1 · A radiation sensitive (1) This composition contains (A) a pigment-containing coloring agent, (B) an alkali-soluble resin, (C) a polyfunctional macromonomer, and (D) a photopolymerization initiator, (2) the erosion rate of the 20 μηι dot pattern formed by the composition is 30% or less, and (3) the composition is used to form on a cloud driving matrix for a thin film transistor (TFT) color liquid crystal display device The partition wall and / or the black matrix in which the pigment contained in the colorant (A) is dispersed via a dispersant having a carbamate bond. ^ 2. The radiation-sensitive composition according to item 1 of the patent application scope, wherein the colorant (A) contains C.I. Pigment Red 177 and C.I. Pigment Blue 15: 4 and / or C.I. Pigment Blue 15: 6. 3. The radiation-sensitive composition according to item 丨 of the application, wherein the voltage retention of the dispersant having a urethane bond is 80% or more. 4. The radiation-sensitive composition according to item 丨 of the patent application scope, wherein the colorant (A) contains carbon black and / or at least two organic pigments. 5. The radiation-sensitive composition according to item 丨 of the patent application scope, wherein the colorant (A) further contains an extender pigment. 6. The radiation-sensitive composition according to item 1 of the patent application scope, wherein the alkali-soluble resin (B) is at least one selected from the group consisting of a copolymer containing a carboxyl group (la) and a copolymer containing a carboxyl group. (Lb), Containing carboxyl moth < Zhang scale is applicable to Chinese national standard TCNS) A4 specification (210X297 male " " " Λ __ (Please read the precautions on the back before filling this page) 569043 A8 B8 C8 D8 々、申請專利範圍 2 基團的共聚物（Ic )及內含羧基基團的共聚物（Ic〇所組 成之類群者。 7 ·如申請專利範圍第1項之輻射敏感性組合物，其中 多官能基單體（C)係至少一種選自由三羥甲基丙烷三丙 烯酸酯、異戊四醇三丙烯酸酯及二異戊四醇六丙烯酸酯所 組成之類群者。 8. 如申請專利範圍第1項之輻射敏感性組合物，其中 光聚合起始劑（D )爲二咪唑爲主的化合物與至少一種選 自由具有二苯乙醇酮鍵結之二苯甲酮爲主的化合物、·另一 二苯甲酮爲主的光自由基產生劑、二苯甲酮爲主的敏化劑 、及噻唑爲主的硬化促進劑所組成類群者之組合。 9. 如申請專利範圍第1項之輻射敏感性組合物，其所 形成的乾燥塗覆膜之光學密度（〇D値）爲每iMm 〇.5或 以上。 C 讀先閱·«背ls、w>i意 _^-«球萬4|、 經濟部智慧財產局員工消費合作社印製 一張 紙 I本 準 摞 家 國 國 中 用 適 一嫠 公 7 9 2 X569043 A8 B8 C8 D8 々, a group consisting of a patent-applicable copolymer (Ic) and a carboxyl group-containing copolymer (Ic0). 7 • Radiation sensitivity as described in the first patent application The composition, wherein the polyfunctional monomer (C) is at least one selected from the group consisting of trimethylolpropane triacrylate, isopentaerythritol triacrylate, and diisopentaerythritol hexaacrylate. 8. For example, the radiation-sensitive composition according to item 1 of the patent application range, wherein the photopolymerization initiator (D) is a compound mainly composed of diimidazole and at least one selected from the group consisting of benzophenone having a diphenethanolone bond. A combination of a compound, another benzophenone-based photoradical generator, a benzophenone-based sensitizer, and a thiazole-based hardening accelerator. 9. If the scope of patent application The radiation-sensitive composition of item 1, the optical density (〇D 値) of the dry coating film formed is 0.5 or more per iMm. C Read First Read «Back ls, w > i 意 _ ^ -«Qiuwan 4 |, Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs One piece of paper I, quasi-country-use, medium-use, suitable for public use 7 9 2 X
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Cited By (1)

* Cited by examiner, † Cited by third party
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TWI407216B (en) * 2004-08-09 2013-09-01 Dongjin Semichem Co Ltd Photosensitive resin composition for spacer

Families Citing this family (10)

* Cited by examiner, † Cited by third party
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JP2005316388A (en) 2004-03-30 2005-11-10 Jsr Corp Radiation sensitive composition for color filter, color filter and color liquid crystal display
KR101212138B1 (en) * 2005-08-26 2012-12-14 엘지디스플레이 주식회사 Liquid Crystal Display and Method for Manufacturing the Same
JP4745093B2 (en) * 2006-03-17 2011-08-10 東京応化工業株式会社 Black photosensitive composition
JP4715575B2 (en) * 2006-03-20 2011-07-06 Ｊｓｒ株式会社 Radiation sensitive resin composition for spacer, spacer and liquid crystal display element
KR101313538B1 (en) * 2006-04-06 2013-10-01 주식회사 동진쎄미켐 Negative photosensitive resin composition
SG137817A1 (en) * 2006-05-29 2007-12-28 Jsr Corp Radiation sensitive composition for forming a colored layer, color filter and color liquid crystal display device
JP4706559B2 (en) * 2006-05-29 2011-06-22 Ｊｓｒ株式会社 Radiation-sensitive composition for forming colored layer, color filter, and color liquid crystal display element
JP2011197599A (en) * 2010-03-24 2011-10-06 Dainippon Printing Co Ltd Color filter, method of manufacturing the same, and liquid crystal display device having the same
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Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3277732B2 (en) * 1994-11-24 2002-04-22 ソニー株式会社 Color display
JP3867177B2 (en) * 1997-04-30 2007-01-10 Ｊｓｒ株式会社 Radiation sensitive composition for color filter
JPH1138225A (en) * 1997-07-17 1999-02-12 Jsr Corp Radiation sensitive composition for color filter
JPH11149153A (en) * 1997-11-14 1999-06-02 Jsr Corp Radiation sensitive composition for black resist
JP3951396B2 (en) * 1997-12-12 2007-08-01 日立化成工業株式会社 Photosensitive film for resin spacer formation
JPH11337949A (en) * 1998-05-28 1999-12-10 Hitachi Chem Co Ltd Photosensitive film for forming colored resin spacer
JP3940535B2 (en) * 1998-11-30 2007-07-04 Ｊｓｒ株式会社 Radiation sensitive composition for black resist
JP3726556B2 (en) * 1999-05-24 2005-12-14 Ｊｓｒ株式会社 Preparation method of radiation sensitive composition for color filter
JP2002167404A (en) * 2000-11-29 2002-06-11 Sumitomo Chem Co Ltd Colored photosensitive composition
JP5010780B2 (en) * 2001-03-23 2012-08-29 Ｊｓｒ株式会社 Radiation sensitive composition for color liquid crystal display device and color liquid crystal display device

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI407216B (en) * 2004-08-09 2013-09-01 Dongjin Semichem Co Ltd Photosensitive resin composition for spacer

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