TWI559085B - Photosensitive resin composition for color filter and application thereof - Google Patents

Photosensitive resin composition for color filter and application thereof Download PDF

Info

Publication number
TWI559085B
TWI559085B TW103110906A TW103110906A TWI559085B TW I559085 B TWI559085 B TW I559085B TW 103110906 A TW103110906 A TW 103110906A TW 103110906 A TW103110906 A TW 103110906A TW I559085 B TWI559085 B TW I559085B
Authority
TW
Taiwan
Prior art keywords
weight
group
parts
compound
alkali
Prior art date
Application number
TW103110906A
Other languages
Chinese (zh)
Other versions
TW201537296A (en
Inventor
許榮賓
Original Assignee
奇美實業股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 奇美實業股份有限公司 filed Critical 奇美實業股份有限公司
Priority to TW103110906A priority Critical patent/TWI559085B/en
Priority to CN201510109906.1A priority patent/CN104950571B/en
Publication of TW201537296A publication Critical patent/TW201537296A/en
Application granted granted Critical
Publication of TWI559085B publication Critical patent/TWI559085B/en

Links

Landscapes

  • Optical Filters (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Description

彩色濾光片用感光性樹脂組成物及其應用 Photosensitive resin composition for color filter and application thereof

本發明係有關一種液晶顯示器之彩色濾光片用感光性樹脂組成物及其所形成之彩色濾光片，特別是提供一種電壓保持率及耐顯影性佳之彩色濾光片用感光性樹脂組成物。 The present invention relates to a photosensitive resin composition for a color filter of a liquid crystal display and a color filter formed therefor, and more particularly to a photosensitive resin composition for a color filter excellent in voltage retention and development resistance. .

目前，彩色濾光片已被廣泛地應用在彩色液晶顯示器、彩色傳真機、彩色攝影機等應用領域。隨著彩色液晶顯示器等影像器材之市場需求日漸擴大，在彩色濾光片的製作技術上亦趨向多樣化。 At present, color filters have been widely used in applications such as color liquid crystal displays, color facsimile machines, color cameras, and the like. With the increasing market demand for image devices such as color liquid crystal displays, the production techniques of color filters are also diversified.

彩色濾光片通常可藉由染色法、印刷法、電著法或顏料分散法等方法，將紅、綠、藍等畫素形成在透明玻璃基板上製得。一般而言，為提高彩色濾光片的對比度，畫素著色層間可配置遮光層(或稱黑色矩陣)。 The color filter can be generally obtained by forming a red, green, blue or the like on a transparent glass substrate by a method such as a dyeing method, a printing method, an electrophoresis method, or a pigment dispersion method. In general, in order to improve the contrast of the color filter, a light shielding layer (or a black matrix) may be disposed between the pixel colored layers.

上述顏料分散法之製程係先將顏料分散在光硬化性樹脂中而形成著色感光性樹脂組成物，最後將該樹脂組成物形成畫素著色層。進一步而言，顏料分散法之製程， 通常係先在玻璃基板等透明支持體上，以鉻、氧化鉻等金屬或感光性樹脂遮光膜形成遮光層(black matrix)。然後，將分散有紅色顏料的感光性樹脂(彩色光阻劑)藉由旋轉塗佈方式將該感光性樹脂塗佈在透明支持體上，藉由光罩進行曝光，並於曝光後進行顯影處理即可得紅色畫素。接著，以同樣的操作方式，即重複利用塗佈、曝光、顯影之方式即可在支持體上分別製得紅、綠、藍等三色畫素。 The process of the above pigment dispersion method is to form a colored photosensitive resin composition by dispersing a pigment in a photocurable resin, and finally forming the resin composition into a pixel colored layer. Further, the process of the pigment dispersion method, Usually, a black matrix is formed on a transparent support such as a glass substrate by using a metal such as chromium or chromium oxide or a photosensitive resin light-shielding film. Then, the photosensitive resin (color resist) in which the red pigment is dispersed is applied onto the transparent support by spin coating, exposed by a photomask, and developed after exposure. You can get red pixels. Then, in the same operation mode, that is, the coating, exposure, and development can be repeatedly used to obtain three-color pixels such as red, green, and blue on the support.

近年來，彩色液晶顯示器的用途不再侷限在個人電腦上，還廣泛應用於彩色電視及各種監視螢幕上(尤其是大尺寸之彩色液晶螢幕)，所以對於液晶顯示器色彩飽和度的要求越來越高。因此，感光性樹脂組成物所含的顏料比例也越來越高，鹼可溶性樹脂與感光性單體的相對使用量變少，造成曝光後的交聯程度下降，導致耐顯影性不佳等的問題發生。 In recent years, the use of color liquid crystal displays is no longer limited to personal computers, but also widely used in color TVs and various surveillance screens (especially large-size color LCD screens), so the requirements for color saturation of liquid crystal displays are increasing. high. Therefore, the proportion of the pigment contained in the photosensitive resin composition is also higher, the relative use amount of the alkali-soluble resin and the photosensitive monomer is decreased, and the degree of crosslinking after exposure is lowered, resulting in problems such as poor developability. occur.

日本特開第2004-138950號公報所揭示之內容中，其使用特定之鹼可溶性樹脂，可以形成表面平坦的畫素著色層，圖案形狀、耐顯影性及亮度表現優異的彩色濾光片，然而此方法易導致該感光性樹脂組成物之電壓保持率過低而導致在顯示畫面時容易有殘像之缺陷存在。 In the content disclosed in Japanese Laid-Open Patent Publication No. 2004-138950, a specific color-soluble resin having a flat surface can be formed, and a color filter having excellent pattern shape, development resistance, and brightness can be formed. This method tends to cause the voltage holding ratio of the photosensitive resin composition to be too low, resulting in the occurrence of defects in the residual image when the screen is displayed.

因此，如何同時提升耐顯影性及電壓保持率，以達到目前業界的要求，為本發明所屬技術領域中努力研究之目標。 Therefore, how to simultaneously improve the development resistance and the voltage holding ratio to meet the requirements of the current industry is an object of diligent research in the technical field to which the present invention pertains.

因此，本發明之一態樣是在提供一種彩色濾光片用感光性樹脂組成物。此感光性樹脂組成物可提升彩色濾光片之電壓保持率及耐顯影性。 Therefore, an aspect of the present invention provides a photosensitive resin composition for a color filter. The photosensitive resin composition can improve the voltage retention and development resistance of the color filter.

本發明之另一態樣是在提供一種製造彩色濾光片之方法，其係利用前述之彩色濾光片用感光性樹脂組成物形成畫素層。 Another aspect of the present invention provides a method of producing a color filter which forms a pixel layer using a photosensitive resin composition for a color filter as described above.

本發明之又一態樣是在提供一種彩色濾光片，其係利用前述之方法製得。 Still another aspect of the present invention is to provide a color filter which is produced by the aforementioned method.

本發明之再一態樣是在提供一種液晶顯示裝置，其包含前述之彩色濾光片。 Still another aspect of the present invention provides a liquid crystal display device comprising the above-described color filter.

根據本發明之上述態樣，提出一種彩色濾光片用感光性樹脂組成物，此感光性樹脂組成物包含顏料(A)、鹼可溶性樹脂(B)、具有乙烯性不飽和基之化合物(C)、光起始劑(D)及有機溶劑(E)，以下析述之。 According to the above aspect of the invention, there is provided a photosensitive resin composition for a color filter comprising a pigment (A), an alkali-soluble resin (B), and a compound having an ethylenically unsaturated group (C) ), a photoinitiator (D) and an organic solvent (E), which are described below.

感光性樹脂組成物Photosensitive resin composition 顏料(A)Pigment (A)

本發明之顏料(A)可為無機顏料、有機顏料或上述顏料之任意組合。 The pigment (A) of the present invention may be an inorganic pigment, an organic pigment or any combination of the above pigments.

上述之無機顏料可為金屬氧化物或金屬錯鹽化合物等之金屬化合物。該金屬氧化物可為鐵、鈷、鋁、鎘、鉛、銅、鈦、鎂、鉻、亞鉛或銻等之金屬的氧化物，以及前述金屬的複合氧化物。 The above inorganic pigment may be a metal compound such as a metal oxide or a metal salt compound. The metal oxide may be an oxide of a metal such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, lead, or antimony, and a composite oxide of the foregoing metal.

上述之有機顏料係選自於C.I.顏料黃1，3，11，12，13，14，15，16，17，20，24，31，53，55，60，61，65， 71，73，74，81，83，93，95，97，98，99，100，101，104，106，108，109，110，113，114，116，117，119，120，126，127，128，129，138，139，150，151，152，153，154，155，156，166，167，168，175；C.I.顏料橙1，5，13，14，16，17，24，34，36，38，40，43，46，49，51，61，63，64，71，73；C.I.顏料紅1，2，3，4，5，6，7，8，9，10，11，12，14，15，16，17，18，19，21，22，23，30，31，32，37，38，40，41，42，48：1，48：2，48：3，48：4，49：1，49：2，50：1，52：1，53：1，57，57：1，57：2，58：2，58：4，60：1，63：1，63：2，64：1，81：1，83，88，90：1，97，101，102，104，105，106，108，112，113，114，122，123，144，146，149，150，151，155，166，168，170，171，172，174，175，176，177，178，179，180，185，187，188，190，193，194，202，206，207，208，209，215，216，220，224，226，242，243，245，254，255，264，265；C.I.顏料紫1，19，23，29，32，36，38，39；C.I.顏料藍1，2，15，15：3，15：4，15：6，16，22，60，66；C.I.顏料綠7，36，37；C.I.顏料棕23，25，28；以及C.I.顏料黑1，7。前述之有機顏料可單獨一種或混合複數種使用。 The above organic pigment is selected from the group consisting of C.I. Pigment Yellow 1, 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 55, 60, 61, 65, 71,73,74,81,83,93,95,97,98,99,100,101,104,106,108,109,110,113,114,116,117,119,120,126,127, 128,129,138,139,150,151,152,153,154,155,156,166,167,168,175; CI Pigment Orange 1,5,13,14,16,17,24,34,36 ,38,40,43,46,49,51,61,63,64,71,73; CI Pigment Red 1,2,3,4,5,6,7,8,9,10,11,12, 14,15,16,17,18,19,21,22,23,30,31,32,37,38,40,41,42,48:1,48:2,48:3,48:4, 49:1,49:2,50:1,52:1,53:1,57,57:1,57:2,58:2,58:4,60:1,63:1,63:2, 64:1,81:1,83,88,90:1,97,101,102,104,105,106,108,112,113,114,122,123,144,146,149,150,151, 155,166,168,170,171,172,174,175,176,177,178,179,180,185,187,188,190,193,194,202,206,207,208,209,215, 216,220,224,226,242,243,245,254,255,264,265; CI Yan Violet 1,19,23,29,32,36,38,39; CI Pigment Blue 1,2,15,15:3,15:4,15:6,16,22,60,66; CI Pigment Green 7,36,37; CI Pigment Brown 23, 25, 28; and CI Pigment Black 1,7. The aforementioned organic pigments may be used singly or in combination of plural kinds.

該顏料(A)的一次粒子之平均粒徑為10nm至200nm，較佳為20nm至150nm，更佳為30nm至130nm。 The primary particles of the pigment (A) have an average particle diameter of from 10 nm to 200 nm, preferably from 20 nm to 150 nm, more preferably from 30 nm to 130 nm.

基於後述鹼可溶性樹脂(B)之總使用量為100重量份，該顏料(A)之使用量為30重量份至300重量份，較佳 為35重量份至250重量份，更佳為40重量份至200重量份。 The pigment (A) is used in an amount of 30 parts by weight to 300 parts by weight, based on 100 parts by weight of the total amount of the alkali-soluble resin (B) to be described later. It is 35 parts by weight to 250 parts by weight, more preferably 40 parts by weight to 200 parts by weight.

必要時，該顏料(A)可選擇性地包含分散劑，其具體例，如：陽離子系、陰離子系、非離子系、兩性、聚矽氧烷系或氟系等之界面活性劑。 When necessary, the pigment (A) may optionally contain a dispersant, and specific examples thereof include a surfactant such as a cationic system, an anionic system, a nonionic system, an amphoteric group, a polyoxyalkylene group or a fluorine system.

該界面活性劑可包含但不限於聚環氧乙烷十二烷基醚、聚環氧乙烷硬脂醯醚或聚環氧乙烷油醚等之聚環氧乙烷烷基醚類；聚環氧乙烷辛基苯醚或聚環氧乙烷壬基苯醚等之聚環氧乙烷烷基苯醚類界面活性劑；聚乙二醇二月桂酸酯或聚乙二醇二硬脂酸酯等之聚乙二醇二酯類界面活性劑；山梨糖醇酐脂肪酸酯類界面活性劑；脂肪酸改質之聚酯類界面活性劑；三級胺改質之聚胺基甲酸酯類界面活性劑；信越化學工業公司製造，型號為KP之商品；Toray Dow Corning Silicon製造，型號為SF-8427之商品；共榮社油脂化學工業製造，型號為Polyflow之商品；得克姆公司(Tochem Products Co.,Ltd.)製造，型號為F-Top之商品；大日本印墨化學工業製造，型號為Megafac之產品；住友3M製造，型號為Fluorad之產品；旭硝子製造，型號為Asahi Guard或Surflon之商品。該界面活性劑可單獨一種或混合複數種使用。 The surfactant may include, but is not limited to, polyethylene oxide alkyl ethers such as polyethylene oxide lauryl ether, polyethylene oxide stearyl ether or polyethylene oxide oleyl ether; Polyethylene oxide alkyl phenyl ether surfactant such as ethylene oxide octyl phenyl ether or polyethylene oxide nonyl phenyl ether; polyethylene glycol dilaurate or polyethylene glycol distearyl Polyethylene glycol diester surfactant such as acid ester; sorbitan fatty acid ester surfactant; fatty acid modified polyester surfactant; tertiary amine modified polyurethane interface Active agent; manufactured by Shin-Etsu Chemical Co., Ltd., model KP; manufactured by Toray Dow Corning Silicon, model SF-8427; manufactured by Kyoei Oil & Fat Chemical Industry, model of Polyflow; Tochem Products Co., Ltd. manufactured by F-Top; manufactured by Dainippon Ink Chemical Industry, model Megafac; Sumitomo 3M, model Fluorad; Asahi Glass, model Asahi Guard or Surflon commodity. The surfactant may be used singly or in combination of plural kinds.

鹼可溶性樹脂(B)Alkali soluble resin (B)

本發明之鹼可溶性樹脂(B)可包含第一鹼可溶性樹脂(B-1)及第二鹼可溶性樹脂(B-2)。此外，鹼可溶性樹脂(B)可選擇性地包含第三鹼可溶性樹脂(B-3)。 The alkali-soluble resin (B) of the present invention may comprise a first alkali-soluble resin (B-1) and a second alkali-soluble resin (B-2). Further, the alkali-soluble resin (B) may optionally contain a third alkali-soluble resin (B-3).

第一鹼可溶性樹脂(B-1)First alkali soluble resin (B-1)

第一鹼可溶性樹脂(B-1)係由一混合物所共聚合形成，其中該混合物包含具有受阻胺結構之乙烯性單體(b-1-1)及具有一個或一個以上羧酸基之乙烯性不飽和單體(b-1-2)。 The first alkali-soluble resin (B-1) is formed by copolymerization of a mixture comprising an ethylenic monomer (b-1-1) having a hindered amine structure and ethylene having one or more carboxylic acid groups. Sexually unsaturated monomer (b-1-2).

此外，前述之混合物可選擇性地包含具有受阻胺結構之乙烯性單體(b-1-1)與具有一個或一個以上羧酸基之乙烯性不飽和單體(b-1-2)以外之其他可共聚合之乙烯性不飽和單體(b-1-3)。 Further, the aforementioned mixture may optionally contain an ethylenic monomer (b-1-1) having a hindered amine structure and an ethylenically unsaturated monomer (b-1-2) having one or more carboxylic acid groups. Other copolymerizable ethylenically unsaturated monomers (b-1-3).

具有受阻胺結構之乙烯性單體(b-1-1)Ethylene monomer with hindered amine structure (b-1-1)

具有受阻胺結構之乙烯性單體(b-1-1)可為如下式(I)所示具有受阻胺結構之乙烯性單體： The ethylenic monomer (b-1-1) having a hindered amine structure may be an ethylenic monomer having a hindered amine structure represented by the following formula (I):

於式(I)中，X1代表氫原子、碳數為1至18之直鏈烷基、支鏈烷基或環烷基、碳數為6至20之芳香基、碳數為7至12之芳香烷基、醯基、氧自由基，或者-OX4；X4代表氫原子、碳數為1至18之直鏈烷基、支鏈烷基或環烷基、碳數為6至20之芳香基，或者碳數為7至12之芳香烷基；X2及X3各自獨立地代表甲基、乙基、苯基或互相鍵結形成碳數為4至12之脂肪族環；「＊」代表共價鍵。 In the formula (I), X 1 represents a hydrogen atom, a linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group or a cycloalkyl group, an aromatic group having 6 to 20 carbon atoms, and a carbon number of 7 to 12 An aromatic alkyl group, a mercapto group, an oxygen radical, or -OX 4 ; X 4 represents a hydrogen atom, a linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group or a cycloalkyl group, and a carbon number of 6 to 20 An aromatic group, or an aromatic alkyl group having a carbon number of 7 to 12; X 2 and X 3 each independently represent a methyl group, an ethyl group, a phenyl group or a bond to each other to form an aliphatic ring having 4 to 12 carbon atoms; *" stands for covalent bond.

當X1及X4代表碳數為1至18之直鏈烷基、支鏈 烷基或環烷基時，X1及X4可為碳數為1至18之直鏈烷基或支鏈烷基，或者碳數為3至8之環烷基，其具體例，如：甲基、乙基、正丙基、異丙基、正丁基、第三丁基、正己基、環己基、正辛基或十六烷基等。當X1代表碳數為6至20之芳香基時，其具體例可為苯基、α-萘基或β-萘基。當X1及X4代表碳數為7至12之芳香烷基時，X1及X4可為具有碳數為1至8之烷基鍵結的芳香基，且該芳香基之碳數為6至10，其具體例可為芐基、苯乙基、α-甲基芐基或2-基-2-苯基丙烷等。當X1及X4代表醯基、碳數為2至8之烷醯基或芳醯基時，其具體例可為乙醯基或苯甲醯基。 When X 1 and X 4 represent a linear alkyl group, a branched alkyl group or a cycloalkyl group having 1 to 18 carbon atoms, X 1 and X 4 may be a linear alkyl group or a branched chain having 1 to 18 carbon atoms. An alkyl group, or a cycloalkyl group having a carbon number of 3 to 8, and specific examples thereof, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-hexyl, cyclohexyl, N-octyl or hexadecyl groups. When X 1 represents an aromatic group having a carbon number of 6 to 20, a specific example thereof may be a phenyl group, an α-naphthyl group or a β-naphthyl group. When X 1 and X 4 represent an aromatic alkyl group having a carbon number of 7 to 12, X 1 and X 4 may be an aromatic group having an alkyl group having a carbon number of 1 to 8, and the carbon number of the aromatic group is 6 to 10, and specific examples thereof may be a benzyl group, a phenethyl group, an α-methylbenzyl group or a 2-yl-2-phenylpropane group. When X 1 and X 4 represent a fluorenyl group, an alkanoyl group or an aryl group having 2 to 8 carbon atoms, a specific example thereof may be an ethyl hydrazino group or a benzamidine group.

本發明之X1較佳可為氫原子、碳數為1至5之烷基或氧自由基，其中以氫原子、氧自由基及甲基為更佳。 X 1 of the present invention may preferably be a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an oxygen radical, and more preferably a hydrogen atom, an oxygen radical or a methyl group.

其次，式(I)中之X2及X3可鍵結形成脂肪環之結構，其具體例可為環戊烷或環己烷等。X2及X3較佳可為甲基。 Next, X 2 and X 3 in the formula (I) may be bonded to form an aliphatic ring structure, and specific examples thereof may be cyclopentane or cyclohexane. X 2 and X 3 may preferably be a methyl group.

具有如式(I)所示具有受阻胺結構之乙烯性單體可為具有如下式(I-1)及(I-2)所示之結構的化合物： The ethylenic monomer having a hindered amine structure as shown in the formula (I) may be a compound having a structure represented by the following formulas (I-1) and (I-2):

於式(I-1)及(I-2)中，X5及X7分別獨立地代表氫原子或甲基；X6代表伸甲基或碳數為2至5之伸烷基；X8代表如式(I)所示之結構；X9代表-CONH-＊、-SO2-、-SO2NH-＊， 其中「＊」代表與X8鍵結之共價鍵；X6較佳為伸乙基或伸丙基，以伸乙基為更佳；s為0至8之整數，以0至6為較佳。 In the formulae (I-1) and (I-2), X 5 and X 7 each independently represent a hydrogen atom or a methyl group; X 6 represents a methyl group or a C 2 to 5 alkyl group; X 8 Represents a structure as shown in formula (I); X 9 represents -CONH-*, -SO 2 -, -SO 2 NH-*, wherein "*" represents a covalent bond bonded to X 8 ; X 6 is preferred It is preferably an ethyl group or a propyl group, and an ethyl group is more preferably an extension; s is an integer of 0 to 8, preferably 0 to 6.

如式(I-1)所示具有受阻胺結構之乙烯性單體之具體例可為如下式(I-1-1)至(I-1-7)所示之結構： Specific examples of the ethylenic monomer having a hindered amine structure represented by the formula (I-1) may be the structures represented by the following formulae (I-1-1) to (I-1-7):

於式(I-1-1)至(I-1-7)中，X5之定義如前所述，在此不另贅述。 In the formulae (I-1-1) to (I-1-7), the definition of X 5 is as described above, and will not be further described herein.

如式(I-2)所示具有受阻胺結構之乙烯性單體之具體例可為如下式(I-2-1)至(I-2-4)所示之結構： Specific examples of the ethylenic monomer having a hindered amine structure represented by the formula (I-2) may be the structures represented by the following formulae (I-2-1) to (I-2-4):

於式(I-2-1)至(I-2-4)中，X7之定義如前所述，在此不另贅述。 In the formulae (I-2-1) to (I-2-4), the definition of X 7 is as described above, and will not be further described herein.

本發明具有受阻胺結構之乙烯性單體(b-1-1)可為4-甲基丙烯醯胺基-2,2,6,6-四甲基-哌啶(4-methacrylamido-2,2,6,6-tetramethylpiperidine)，或者日立化成工業株式會社製造，型號為FA-712HM[2,2,6,6-四甲基-哌啶基丙烯酸甲酯；即前述式(I-1-1)，且X5代表甲基]或FA-711MM[1,2,2,6,6-五甲基-哌啶基丙烯酸甲酯；即前述式(I-1-2)，且X5代表甲基]。 The ethylenic monomer (b-1-1) having a hindered amine structure of the present invention may be 4-methacrylamido-2,2,6,6-tetramethyl-piperidine (4-methacrylamido-2, 2,6,6-tetramethylpiperidine), or manufactured by Hitachi Chemical Co., Ltd., model FA-712HM [2,2,6,6-tetramethyl-piperidinyl acrylate; that is, the above formula (I-1- 1), and X 5 represents methyl] or FA-711MM [methyl 1,1,2,6,6-pentamethyl-piperidinyl acrylate; that is, the above formula (I-1-2), and X 5 Represents methyl].

前述具有受阻胺結構之乙烯性單體(b-1-1)可單獨一種或混合複數種使用。 The above-mentioned ethylenic monomer (b-1-1) having a hindered amine structure may be used singly or in combination of plural kinds.

基於具有受阻胺結構之乙烯性單體(b-1-1)及後述具有一個或一個以上羧酸基之乙烯性不飽和單體(b-1-2)與其他可共聚合之乙烯性不飽和單體(b-1-3)的總使用量為100重量份，該具有受阻胺結構之乙烯性單體(b-1-1)之使用量為3重量份至45重量份，較佳為4重量份至40重量份，更佳為5重量份至35重量份。 An ethylenic monomer (b-1-1) having a hindered amine structure and an ethylenically unsaturated monomer (b-1-2) having one or more carboxylic acid groups described later and other copolymerizable ethylenicity The total amount of the saturated monomer (b-1-3) used is 100 parts by weight, and the ethylenic monomer (b-1-1) having a hindered amine structure is used in an amount of from 3 parts by weight to 45 parts by weight, preferably. It is 4 parts by weight to 40 parts by weight, more preferably 5 parts by weight to 35 parts by weight.

具有一個或一個以上羧酸基之乙烯性不飽和單體(b-1-2)Ethylene unsaturated monomer having one or more carboxylic acid groups (b-1-2)

該具有一個或一個以上羧酸基之乙烯性不飽和單體(b-1-2)可包含但不限於丙烯酸、甲基丙烯酸(methacrylic acid；MAA)、丁烯酸、α-氯丙烯酸、乙基丙烯酸、肉桂酸、2-丙烯醯乙氧基丁二酸酯或2-甲基丙烯醯乙氧基丁二酸酯(2-methacryloyloxyethyl succinate monoester；HOMS)等之不飽和一元羧酸化合物；馬來酸、馬來酸酐、富馬酸、衣康酸、衣康酸酐、檸康酸或檸康酸酐等之不飽和二元羧酸(酐)化合物；三個羧酸基以上之不飽和多元羧酸(酐)化合物。前述具有一個或一個以上羧酸基之乙烯性不飽和單體(b-1-2)可單獨一種或混合複數種使用。 The ethylenically unsaturated monomer (b-1-2) having one or more carboxylic acid groups may include, but is not limited to, acrylic acid, methacrylic acid (methacrylic) Acid; MAA), crotonic acid, α-chloroacrylic acid, ethacrylic acid, cinnamic acid, 2-propenyl ethoxy succinate or 2-methacryloyl oxy succinate Succinate monoester; HOMS) unsaturated monocarboxylic acid compounds; unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid or citraconic anhydride Anhydride compound; an unsaturated polycarboxylic acid (anhydride) compound having three or more carboxylic acid groups. The above ethylenically unsaturated monomer (b-1-2) having one or more carboxylic acid groups may be used singly or in combination of plural kinds.

較佳地，該具有一個或一個以上羧酸基之乙烯性不飽和單體(b-1-2)係選自於丙烯酸、甲基丙烯酸、2-丙烯醯乙氧基丁二酸酯或2-甲基丙烯醯乙氧基丁二酸酯。其中，以2-丙烯醯乙氧基丁二酸酯或2-甲基丙烯醯乙氧基丁二酸酯為更佳。 Preferably, the ethylenically unsaturated monomer (b-1-2) having one or more carboxylic acid groups is selected from the group consisting of acrylic acid, methacrylic acid, 2-propenyl ethoxy succinate or 2 - Methacrylic oxime ethoxy succinate. Among them, 2-propylene oxime ethoxy succinate or 2-methyl propylene ethoxy succinate is more preferable.

基於前述具有受阻胺結構之乙烯性單體(b-1-1)、具有一個或一個以上羧酸基之乙烯性不飽和單體(b-1-2)及後述其他可共聚合之乙烯性不飽和單體(b-1-3)的總使用量為100重量份，該具有一個或一個以上羧酸基之乙烯性不飽和單體(b-1-2)之使用量為15重量份至55重量份，較佳為20重量份至50重量份，更佳為25重量份至45重量份。 An ethylenic monomer (b-1-1) having a hindered amine structure, an ethylenically unsaturated monomer having one or more carboxylic acid groups (b-1-2), and other copolymerizable ethylenic groups described later The total amount of the unsaturated monomer (b-1-3) used is 100 parts by weight, and the ethylenically unsaturated monomer (b-1-2) having one or more carboxylic acid groups is used in an amount of 15 parts by weight. To 55 parts by weight, preferably 20 parts by weight to 50 parts by weight, more preferably 25 parts by weight to 45 parts by weight.

其他可共聚合之乙烯性不飽和單體(b-1-3)Other copolymerizable ethylenically unsaturated monomers (b-1-3)

該具有受阻胺結構之乙烯性單體(b-1-1)與具有一個或一個以上羧酸基之乙烯性不飽和單體(b-1-2)以外其他可共聚合之乙烯性不飽和單體(b-1-3)可包含但不限於苯乙烯(styrene；SM)、α-甲基苯乙烯、乙烯基甲苯、對氯苯乙 烯、甲氧基苯乙烯等之芳香族乙烯基化合物；N-苯基馬來醯亞胺(N-phenylmaleimide；PMI)、N-鄰-羥基苯基馬來醯亞胺、N-間-羥基苯基馬來醯亞胺、N-對-羥基苯基馬來醯亞胺、N-鄰-甲基苯基馬來醯亞胺、N-間-甲基苯基馬來醯亞胺、N-對-甲基苯基馬來醯亞胺、N-鄰-甲氧基苯基馬來醯亞胺、N-間-甲氧基苯基馬來醯亞胺、N-對-甲氧基苯基馬來醯亞胺、N-環己基馬來醯亞胺等之馬來醯亞胺化合物；丙烯酸甲酯(methyl acrylate；MA)、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-羥基乙酯、甲基丙烯酸-2-羥基乙酯、丙烯酸-2-羥基丙酯、甲基丙烯酸-2-羥基丙酯、丙烯酸-3-羥基丙酯、甲基丙烯酸-3-羥基丙酯、丙烯酸-2-羥基丁酯、甲基丙烯酸-2-羥基丁酯、丙烯酸-3-羥基丁酯、甲基丙烯酸-3-羥基丁酯、丙烯酸-4-羥基丁酯、甲基丙烯酸-4-羥基丁酯、丙烯酸烯丙酯、甲基丙烯酸烯丙酯、丙烯酸苯甲酯、甲基丙烯酸苯甲酯(benzyl methacrylate；BzMA)、丙烯酸苯酯、甲基丙烯酸苯酯、丙烯酸三乙二醇甲氧酯、甲基丙烯酸三乙二醇甲氧酯、甲基丙烯酸十二烷基酯、甲基丙烯酸十四烷基酯、甲基丙烯酸十六烷基酯、甲基丙烯酸十八烷基酯、甲基丙烯酸二十烷基酯、甲基丙烯酸二十二烷基酯、丙烯酸雙環戊烯基氧化 乙酯(dicyclopentenyloxyethyl acrylate；DCPOA)等之不飽和羧酸酯化合物；丙烯酸-N,N-二甲基胺基乙酯、甲基丙烯酸-N,N-二甲基胺基乙酯、丙烯酸-N,N-二乙基胺基丙酯、甲基丙烯酸-N,N-二甲基胺基丙酯、丙烯酸-N,N-二丁基胺基丙酯、N-甲基丙烯酸異-丁基胺基乙酯；丙烯酸環氧丙基酯、甲基丙烯酸環氧丙基酯等之不飽和羧酸環氧丙基酯化合物；乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯等之羧酸乙烯酯化合物；乙烯基甲醚、乙烯基***、烯丙基環氧丙基醚、甲代烯丙基環氧丙基醚等之不飽和醚化合物；丙烯腈、甲基丙烯腈、α-氯丙烯腈、氰化亞乙烯等之腈化乙烯基化合物；丙烯醯胺、甲基丙烯醯胺、α-氯丙烯醯胺、N-羥乙基丙烯醯胺、N-羥乙基甲基丙烯醯胺等之不飽和醯胺化合物；1,3-丁二烯、異戊二烯、氯化丁二烯等之脂肪族共軛二烯化合物。前述其他可共聚合之乙烯性不飽和單體(b-1-3)可單獨一種或混合複數種使用。 The ethylenic monomer (b-1-1) having a hindered amine structure and the ethylenically unsaturated ethylenic unsaturated monomer other than the ethylenically unsaturated monomer (b-1-2) having one or more carboxylic acid groups The monomer (b-1-3) may include, but is not limited to, styrene (SM), α-methylstyrene, vinyl toluene, p-chlorophenylethyl An aromatic vinyl compound such as a olefin or a methoxy styrene; N-phenylmaleimide (PMI), N-o-hydroxyphenylmaleimide, N-m-hydroxyl Phenylmaleimide, N-p-hydroxyphenylmaleimide, N-o-methylphenylmaleimide, N-m-methylphenylmaleimide, N -p-Methylphenylmaleimide, N-o-methoxyphenylmaleimide, N-m-methoxyphenylmaleimide, N-p-methoxy a maleic imine compound such as phenylmaleimide or N-cyclohexylmaleimide; methyl acrylate (MA), methyl methacrylate, ethyl acrylate, methacrylic acid Ester, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, Second butyl acrylate, second butyl methacrylate, third butyl acrylate, third butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, acrylic acid-2- Hydroxypropyl ester, A 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate Ester, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, methacrylic acid Benzyl methacrylate (BzMA), phenyl acrylate, phenyl methacrylate, triethylene glycol methacrylate, triethylene glycol methacrylate, dodecyl methacrylate, A Tetradecyl acrylate, cetyl methacrylate, octadecyl methacrylate, eicosyl methacrylate, behenyl methacrylate, dicyclopentenyl acrylate Oxidation An unsaturated carboxylic acid ester compound such as dicyclopentenyloxyethyl acrylate (DCPOA); N-N-dimethylaminoethyl acrylate, N-N-dimethylaminoethyl methacrylate, acrylic acid-N , N-diethylaminopropyl propyl ester, N,N-dimethylaminopropyl methacrylate, N-N-dibutylaminopropyl acrylate, iso-butyl N-methyl methacrylate Aminoethyl ester; unsaturated carboxylic acid glycidyl ester compound such as glycidyl acrylate or glycidyl methacrylate; carboxylic acid such as vinyl acetate, vinyl propionate or vinyl butyrate Vinyl ester compound; unsaturated ether compound such as vinyl methyl ether, vinyl ethyl ether, allyl epoxypropyl ether, methallyl epoxypropyl ether; acrylonitrile, methacrylonitrile, α-chloride A nitrile vinyl compound such as acrylonitrile or vinyl cyanide; acrylamide, methacrylamide, α-chloropropenylamine, N-hydroxyethyl acrylamide, N-hydroxyethyl methacrylate An unsaturated decylamine compound such as an amine; an aliphatic conjugated diene compound such as 1,3-butadiene, isoprene or chlorinated butadiene. The other copolymerizable ethylenically unsaturated monomer (b-1-3) may be used singly or in combination of plural kinds.

較佳地，該其他可共聚合之乙烯性不飽和單體(b-1-3)係選自於苯乙烯、N-苯基馬來醯亞胺、丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸-2-羥基乙酯、甲基丙烯酸-2-羥基乙酯、丙烯酸苯甲酯、甲基丙烯酸苯甲酯、丙烯酸雙環戊烯基氧化乙酯或上述化合物之任意混合。 Preferably, the other copolymerizable ethylenically unsaturated monomer (b-1-3) is selected from the group consisting of styrene, N-phenylmaleimide, methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, dicyclopentenyl acrylate or any combination of the above.

基於前述具有受阻胺結構之乙烯性單體(b-1-1)、具有一個或一個以上羧酸基之乙烯性不飽和單體(b-1-2)及其他可共聚合之乙烯性不飽和單體(b-1-3)的總使用量為100重量份，該其他可共聚合之乙烯性不飽和單體(b-1-3)之使 用量為0重量份至82重量份，較佳為10重量份至70重量份，更佳為20重量份至60重量份。 Based on the aforementioned ethylenic monomer (b-1-1) having a hindered amine structure, an ethylenically unsaturated monomer (b-1-2) having one or more carboxylic acid groups, and other copolymerizable ethylenicity The total amount of the saturated monomer (b-1-3) used is 100 parts by weight, and the other copolymerizable ethylenically unsaturated monomer (b-1-3) The amount is from 0 part by weight to 82 parts by weight, preferably from 10 parts by weight to 70 parts by weight, more preferably from 20 parts by weight to 60 parts by weight.

若鹼可溶性樹脂(B)不使用前述第一鹼可溶性樹脂(B-1)時，所製得之面板於長時間之驅動下易產生離子，而降低電壓保持率。 When the alkali-soluble resin (B) does not use the aforementioned first alkali-soluble resin (B-1), the resulting panel is prone to generate ions under a long period of driving, and the voltage holding ratio is lowered.

第二鹼可溶性樹脂(B-2)Second alkali soluble resin (B-2)

第二鹼可溶性樹脂(B-2)係由第一混合物反應獲得，該第一混合物包含具有至少兩個環氧基之環氧化合物(b-2-1)，以及具有至少一個羧酸基與至少一個乙烯性不飽和基之化合物(b-2-2)。 The second alkali-soluble resin (B-2) is obtained by a reaction of a first mixture comprising an epoxy compound (b-2-1) having at least two epoxy groups, and having at least one carboxylic acid group and At least one ethylenically unsaturated group compound (b-2-2).

此外，該第一混合物可選擇性地包含羧酸酐化合物(b-2-3)、具有環氧基之化合物(b-2-4)或上述材料之任意組合。 Further, the first mixture may optionally contain a carboxylic anhydride compound (b-2-3), a compound having an epoxy group (b-2-4), or any combination of the above materials.

具有至少兩個環氧基之環氧化合物(b-2-1)Epoxy compound having at least two epoxy groups (b-2-1)

該具有至少兩個環氧基之環氧化合物(b-2-1)包含如下式(II)所示之化合物、如下式(III)所示之化合物或上述材料之任意混合： The epoxy compound (b-2-1) having at least two epoxy groups includes a compound represented by the following formula (II), a compound represented by the following formula (III) or any mixture of the above materials:

於式(II)中，Y1、Y2、Y3及Y4分別獨立地代表氫原子、 鹵原子、碳數為1至5之烷基或烷氧基，或者碳數為6至12之芳香基或芳烷基。 In the formula (II), Y 1 , Y 2 , Y 3 and Y 4 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms or an alkoxy group, or a carbon number of 6 to 12 Aromatic or aralkyl.

如前述式(II)所示之化合物可由雙酚茀型化合物(bisphenol fluorene)與鹵化環氧丙烷(epihalohydrin)進行反應而得。 The compound represented by the above formula (II) can be obtained by reacting a bisphenol fluorene with a halogenated propylene oxide (epihalohydrin).

上述之雙酚茀型化合物的具體例可為9,9-雙(4-羥基苯基)茀[9,9-bis(4-hydroxyphenyl)fluorine]、9,9-雙(4-羥基-3-甲基苯基)茀(9,9-bis(4-hydroxy-3-methylphenyl)fluorene)、9,9-雙(4-羥基-3-氯苯基)茀(9,9-bis(4-hydroxy-3-chlorophenyl)fluorene)、9,9-雙(4-羥基-3-溴苯基)茀(9,9-bis(4-hydroxy-3-bromophenyl)fluorene)、9,9-雙(4-羥基-3-氟苯基)茀(9,9-bis(4-hydroxy-3-fluorophenyl)fluorene)、9,9-雙(4-羥基-3-甲氧基苯基)茀(9,9-bis(4-hydroxy-3-methoxyphenyl)fluorene)、9,9-雙(4-羥基-3,5-二甲基苯基)茀(9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene)、9,9-雙(4-羥基-3,5-二氯苯基)茀(9,9-bis(4-hydroxy-3,5-dichlorophenyl)fluorene)、9,9-雙(4-羥基-3,5-二溴苯基)茀(9,9-bis(4-hydroxy-3,5-dibromophenyl)fluorene)，或上述化合物之任意組合。 Specific examples of the above bisphenol quinone type compound may be 9,9-bis(4-hydroxyphenyl)fluorine, 9,9-bis(4-hydroxy-3). -Methylphenyl)fluorene (9,9-bis(4-hydroxy-3-methylphenyl)fluorene), 9,9-bis(4-hydroxy-3-chlorophenyl)fluorene (9,9-bis (4) -hydroxy-3-chlorophenyl)fluorene), 9,9-bis(4-hydroxy-3-bromophenyl)fluorene, 9,9-double (9,9-bis(4-hydroxy-3-fluorophenyl)fluorene), 9,9-bis(4-hydroxy-3-methoxyphenyl)anthracene ( 9,9-bis(4-hydroxy-3-methoxyphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene (9,9-bis(4-hydroxy-3) ,5-dimethylphenyl)fluorene), 9,9-bis(4-hydroxy-3,5-dichlorophenyl)fluorene, 9, 9-9-bis(4-hydroxy-3,5-dibromophenyl)fluorene, or any combination of the above compounds.

前述鹵化環氧丙烷(epihalohydrin)之具體例可包含 但不限於3-氯-1,2-環氧丙烷(epichlorohydrin)或3-溴-1,2-環氧丙烷(epibromohydrin)或上述化合物之任意組合。 Specific examples of the aforementioned epihalohydrin may include However, it is not limited to 3-chloro-1,2-epoxyhydrin or 3-bromo-1,2-epoxyhydrin (epibromohydrin) or any combination of the above compounds.

具有環氧基之雙酚茀型化合物的具體例可包含新日鐵化學公司(Nippon steel chemical Co.,Ltd)製造，型號為ESF-300的商品；大阪天然氣公司(Osaka Gas Co.,Ltd)製造，型號為PG-100或EG-210之商品；短信科技公司(S.M.S Technology Co.,Ltd)製造，型號為SMS-F9PhPG、SMS-F9CrG或SMS-F914PG之商品。 Specific examples of the bisphenol quinone type compound having an epoxy group may include a product of the model ESF-300 manufactured by Nippon Steel Chemical Co., Ltd.; Osaka Gas Co., Ltd. Manufactured by PG-100 or EG-210; manufactured by SMS Technology Co., Ltd., model of SMS-F9PhPG, SMS-F9CrG or SMS-F914PG.

於式(III)中，該R1至R14分別獨立地代表氫原子、鹵素原子、碳數為1至8之烷基或碳數為6至15之芳香基，且n代表0至10之整數。 In the formula (III), R 1 to R 14 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or an aromatic group having 6 to 15 carbon atoms, and n represents 0 to 10 Integer.

如前述式(III)所示之化合物可在鹼金屬氫氧化物之存在下，使用如下式(III-1)所示之化合物與鹵化環氧丙烷進行反應： The compound represented by the above formula (III) can be reacted with a halogenated propylene oxide in the presence of an alkali metal hydroxide using a compound represented by the following formula (III-1):

於式(III-1)中，R1至R14及n的定義分別如前所述，在此不另贅述。 In the formula (III-1), R 1 to R 14 and n are each as defined above, and are not described herein.

如式(III-1)所示之化合物的合成方法係先在酸觸媒的存在下，將如下式(III-2)所示之化合物與酚(phenol)類化合物進行縮合反應，以形成如式(III-1)所示之化合物。然後，加入過量之鹵化環氧丙烷，以使鹵化環氧丙烷與如式(III-1)所示之化合物進行脫鹵化氫反應(dehydrohalogenation)，即可獲得如式(III)所示之化合物： The method for synthesizing the compound represented by the formula (III-1) is a condensation reaction of a compound represented by the following formula (III-2) with a phenol compound in the presence of an acid catalyst to form, for example, a compound of the formula (III-1). Then, an excess of the halogenated propylene oxide is added to subject the halogenated propylene oxide to a dehydrohalogenation reaction with a compound of the formula (III-1) to obtain a compound of the formula (III):

於式(III-2)中，R3至R6之定義如前所述，在此不另贅述；R15及R16分別獨立地代表鹵素原子，或者碳數為1至6之烷基或烷氧基。上述之鹵素原子可為氯原子或溴原子。烷基較佳為甲基、乙基或第三丁基。烷氧基較佳為甲氧基或乙氧基。 In the formula (III-2), R 3 to R 6 are as defined above and will not be further described herein; R 15 and R 16 each independently represent a halogen atom or an alkyl group having 1 to 6 carbon atoms or Alkoxy. The above halogen atom may be a chlorine atom or a bromine atom. The alkyl group is preferably a methyl group, an ethyl group or a tert-butyl group. The alkoxy group is preferably a methoxy group or an ethoxy group.

前述之酚類化合物的具體例可包含但不限於酚(phenol)、甲酚(cresol)、乙酚(ethylphenol)、正丙酚(n-propylphenol)、異丁酚(isobutylphenol)、第三丁酚(t-butylphenol)、辛酚(octylphenol)、壬基苯酚(nonylphenol)、茬酚(xylenol)、甲基丁基苯酚(methylbutylphenol)、二第三丁基酚(di-t-butylphenol)、乙烯苯酚(vinylphenol)、丙烯苯酚(propenylphenol)、乙炔苯酚(ethinylphenol)、環戊苯酚(cyclopentylphenol)、環己基酚 (cyclohexylphenol)或環己基甲酚(cyclohexylcresol)等。該酚類化合物可單獨一種或混合複數種使用。 Specific examples of the aforementioned phenolic compound may include, but are not limited to, phenol, cresol, ethylphenol, n-propylphenol, isobutylphenol, and third butanol. (t-butylphenol), octylphenol, nonylphenol, xylenol, methylbutylphenol, di-t-butylphenol, vinylphenol (vinylphenol), propenylphenol, ethinylphenol, cyclopentylphenol, cyclohexylphenol (cyclohexylphenol) or cyclohexylcresol (cyclohexylcresol) and the like. The phenolic compound may be used singly or in combination of plural kinds.

基於上述如式(III-2)所示之化合物的使用量為1莫耳，酚類化合物之使用量為0.5莫耳至20莫耳，較佳為2莫耳至15莫耳。 The compound represented by the above formula (III-2) is used in an amount of 1 mol, and the phenol compound is used in an amount of 0.5 mol to 20 mol, preferably 2 mol to 15 mol.

酸觸媒的具體例可包含鹽酸、硫酸、對甲苯磺酸(p-toluenesulfonic acid)、草酸(oxalic acid)、三氟化硼(boron trifluoride)、無水氯化鋁(aluminium chloride anhydrous)或氯化鋅(zinc chloride)等之化合物。酸觸媒較佳為對甲苯磺酸、硫酸、鹽酸或上述化合物之任意混合。 Specific examples of the acid catalyst may include hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, oxalic acid, boron trifluoride, aluminum chloride anhydrous or chlorinated. a compound such as zinc chloride. The acid catalyst is preferably p-toluenesulfonic acid, sulfuric acid, hydrochloric acid or any combination of the above compounds.

上述酸觸媒之使用量雖無特別的限制。但基於上述如式(III-2)所示之化合物的使用量為100重量百分比，酸觸媒的使用量較佳為0.1重量百分比至30重量百分比。 The amount of the above acid catalyst used is not particularly limited. However, the use amount of the compound represented by the above formula (III-2) is 100% by weight, and the acid catalyst is preferably used in an amount of from 0.1% by weight to 30% by weight.

上述的縮合反應可在無溶劑或是在有機溶劑的存在下進行。該有機溶劑的具體例可包含但不限於甲苯(toluene)、二甲苯(xylene)或甲基異丁基酮(methyl isobutyl ketone)等之有機溶劑。上述的有機溶劑可單獨一種或混合複數種使用。 The above condensation reaction can be carried out in the absence of a solvent or in the presence of an organic solvent. Specific examples of the organic solvent may include, but are not limited to, an organic solvent such as toluene, xylene or methyl isobutyl ketone. The above organic solvents may be used singly or in combination of plural kinds.

基於如式(III-2)所示之化合物及酚類的總使用量為100重量百分比，有機溶劑之使用量為50重量百分比至300重量百分比，較佳為100重量百分比至250重量百分比。此外，上述的縮合反應的操作溫度為40℃至180℃，且縮合反應的操作時間為1小時至8小時。 The total amount of the compound and the phenol used as shown in the formula (III-2) is 100% by weight, and the organic solvent is used in an amount of 50% by weight to 300% by weight, preferably 100% by weight to 250% by weight. Further, the above condensation reaction has an operation temperature of 40 ° C to 180 ° C, and the condensation reaction has an operation time of 1 hour to 8 hours.

在完成上述的縮合反應後，可進行中和處理或水洗 處理。該中和處理是將反應後之溶液的pH值調整為3至7，較佳為5至7。該水洗處理可使用中和劑來進行，且該中和劑為鹼性物質，其具體例，如：氫氧化鈉(sodium hydroxide)或氫氧化鉀(potassium hydroxide)等之鹼金屬氫氧化物；氫氧化鈣(calcium hydroxide)或氫氧化鎂(magnesium hydroxide)等之鹼土類金屬氫氧化物；二伸乙三胺(diethylene triamine)、三伸乙四胺(triethylenetetramine)、苯胺(aniline)或苯二胺(phenylene diamine)等之有機胺；氨(ammonia)、磷酸二氫鈉(sodium dihydrogen phosphate)或上述化合物的任意組合。上述的中和劑可單獨一種或混合複數種使用。上述的水洗處理可採用習知方法進行，例如在反應後的溶液中加入含中和劑的水溶液，並且反覆進行萃取即可。 After the above condensation reaction is completed, it can be neutralized or washed. deal with. The neutralization treatment adjusts the pH of the solution after the reaction to 3 to 7, preferably 5 to 7. The water washing treatment can be carried out using a neutralizing agent, and the neutralizing agent is a basic substance, and specific examples thereof include an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide; An alkaline earth metal hydroxide such as calcium hydroxide or magnesium hydroxide; diethylene triamine, triethylenetetramine, aniline or benzodiazepine An organic amine such as phenylene diamine; ammonia, sodium dihydrogen phosphate or any combination of the above. The above neutralizing agents may be used singly or in combination of plural kinds. The above water washing treatment can be carried out by a conventional method, for example, by adding an aqueous solution containing a neutralizing agent to the solution after the reaction, and carrying out the extraction repeatedly.

進行前述之中和處理或水洗處理後，可藉由減壓加熱處理餾除未反應的酚類及溶劑，並進行濃縮。如此一來，便可獲得如式(III-1)所示的化合物。 After the neutralization treatment or the water washing treatment, the unreacted phenols and the solvent can be distilled off by a reduced pressure heat treatment, and concentrated. In this way, a compound represented by the formula (III-1) can be obtained.

上述之鹵化環氧丙烷的具體例可包含但不限於3-氯-1,2-環氧丙烷、3-溴-1,2-環氧丙烷或上述化合物的任意組合。在進行上述的脫鹵化氫反應之前，可預先添加或於反應過程中添加氫氧化鈉、氫氧化鉀等之鹼金屬氫氧化物。上述的脫鹵化氫反應的操作溫度可為20℃至120℃，且其操作時間可為1小時至10小時。 Specific examples of the above halogenated propylene oxide may include, but are not limited to, 3-chloro-1,2-epoxypropane, 3-bromo-1,2-epoxypropane or any combination of the above compounds. An alkali metal hydroxide such as sodium hydroxide or potassium hydroxide may be added in advance or added to the reaction before the dehydrohalogenation reaction. The above dehydrohalogenation reaction may be carried out at a temperature of from 20 ° C to 120 ° C and may be operated for from 1 hour to 10 hours.

在一實施例中，上述脫鹵化氫反應中所添加的鹼金屬氫氧化物亦可為其水溶液。在此實施例中，將上述的鹼 金屬氫氧化物水溶液連續添加至脫鹵化氫反應系統內的同時，可於減壓或常壓下，連續蒸餾出水及鹵化環氧丙烷，藉以除去水，並且可將鹵化環氧丙烷連續地回流至反應系統內。 In one embodiment, the alkali metal hydroxide added in the dehydrohalogenation reaction may also be an aqueous solution thereof. In this embodiment, the above base is The aqueous metal hydroxide solution is continuously added to the dehydrohalogenation reaction system, and water and halogenated propylene oxide can be continuously distilled off under reduced pressure or normal pressure to remove water, and the halogenated propylene oxide can be continuously refluxed to Inside the reaction system.

上述的脫鹵化氫反應進行前，亦可添加氯化四甲銨(tetramethyl ammonium chloride)、溴化四甲銨(tetramethyl ammonium bromide)或三甲基苄基氯化銨(trimethyl benzyl ammonium chloride)等之四級銨鹽作為觸媒，並且在50℃至150℃下，反應1小時至5小時，加入鹼金屬氫氧化物或其水溶液。接著，於20℃至120℃的溫度下，反應1小時至10小時，以進行脫鹵化氫反應。 Before the above dehydrohalogenation reaction is carried out, tetramethyl ammonium chloride, tetramethyl ammonium bromide or trimethyl benzyl ammonium chloride may be added. The quaternary ammonium salt is used as a catalyst, and is reacted at 50 ° C to 150 ° C for 1 hour to 5 hours, and an alkali metal hydroxide or an aqueous solution thereof is added. Next, the reaction is carried out at a temperature of from 20 ° C to 120 ° C for 1 hour to 10 hours to carry out a dehydrohalogenation reaction.

基於上述如式(III-1)所示之化合物中的羥基總當量為1當量，鹵化環氧丙烷之使用量為1當量至20當量，較佳為2當量至10當量。基於上述如式(III-1)所示之化合物中的羥基總當量為1當量，前述脫鹵化氫反應中添加的鹼金屬氫氧化物的使用量為0.8當量至15當量，較佳為0.9當量至11當量。 The halogenated propylene oxide is used in an amount of 1 equivalent to 20 equivalents, preferably 2 equivalents to 10 equivalents, based on the total equivalent of the hydroxyl group in the compound represented by the above formula (III-1). The total amount of hydroxyl groups in the compound represented by the above formula (III-1) is 1 equivalent, and the amount of the alkali metal hydroxide added in the dehydrohalogenation reaction is 0.8 to 15 equivalents, preferably 0.9 equivalents. Up to 11 equivalents.

為了使上述的脫鹵化氫反應順利進行，亦可添加甲醇或乙醇等之醇類溶劑。此外，脫鹵化氫反應亦可使用二甲碸(dimethyl sulfone)或二甲亞碸(dimethyl sulfoxide)等之非質子性(aprotic)的極性溶劑來進行反應。在使用醇類溶劑的情況下，基於鹵化環氧丙烷的總使用量為100重量百分比，醇類的使用量為2重量百分比至20重量百分比，較佳為4重量百分比至15重量百分比。在使用非質子性的極性 溶劑的情況下，基於鹵化環氧丙烷的總使用量為100重量百分比，非質子性之極性溶劑的使用量為5重量百分比至100重量百分比，較佳為10重量百分比至90重量百分比。 In order to smoothly carry out the above-described dehydrohalogenation reaction, an alcohol solvent such as methanol or ethanol may be added. Further, the dehydrohalogenation reaction can also be carried out using an aprotic polar solvent such as dimethyl sulfone or dimethyl sulfoxide. In the case of using an alcohol solvent, the total amount of the halogenated propylene oxide used is 100% by weight, and the alcohol is used in an amount of 2% by weight to 20% by weight, preferably 4% by weight to 15% by weight. Using aprotic polarity In the case of a solvent, the total use amount of the halogenated propylene oxide is 100% by weight, and the aprotic polar solvent is used in an amount of 5 to 100% by weight, preferably 10 to 90% by weight.

完成脫鹵化氫反應後，可選擇性地進行水洗處理。然後，利用減壓蒸餾的方式，例如於溫度為110℃至250℃且壓力小於1.3kPa[10毫米汞柱(mmHg)]之環境中，去除鹵化環氧丙烷、醇類及非質子性的極性溶劑。 After the completion of the dehydrohalogenation reaction, the water washing treatment can be selectively carried out. Then, the halogenated propylene oxide, the alcohol and the aprotic polarity are removed by means of vacuum distillation, for example, in an environment having a temperature of 110 ° C to 250 ° C and a pressure of less than 1.3 kPa [10 mm Hg). Solvent.

為了避免所製得之環氧樹脂具有加水分解性的鹵素，可將甲苯或甲基異丁基酮(methyl isobutyl ketone)等溶劑以及氫氧化鈉或氫氧化鉀等鹼金屬氫氧化物水溶液加至脫鹵化氫反應後的溶液中，並再次進行脫鹵化氫反應。在脫鹵化氫反應中，基於上述如式(III-1)所示之化合物中的羥基總當量為1當量，鹼金屬氫氧化物之使用量為0.01莫耳至0.3莫耳，較佳為0.05莫耳至0.2莫耳。上述脫鹵化氫反應之操作溫度為50℃至120℃，且操作時間為0.5小時至2小時。 In order to prevent the obtained epoxy resin from having a hydrolyzable halogen, a solvent such as toluene or methyl isobutyl ketone and an aqueous alkali metal hydroxide solution such as sodium hydroxide or potassium hydroxide may be added to The dehydrohalogenation reaction is carried out again in the solution after the dehydrohalogenation reaction. In the dehydrohalogenation reaction, the total hydroxyl group equivalent weight in the compound represented by the above formula (III-1) is 1 equivalent, and the alkali metal hydroxide is used in an amount of 0.01 mol to 0.3 mol, preferably 0.05. Moor to 0.2 m. The above dehydrohalogenation reaction has an operating temperature of 50 ° C to 120 ° C and an operation time of 0.5 hours to 2 hours.

當完成脫鹵化氫反應後，鹽類係藉由過濾及水洗等步驟去除。此外，利用減壓蒸餾的方式除去甲苯或甲基異丁基酮等之溶劑，即可得到如式(III)所示之化合物。上述如式(III)所示之化合物的具體例可包含但不限於日本化藥公司製造，型號為NC-3000、NC-3000H、NC-3000S及NC-3000P之商品。 When the dehydrohalogenation reaction is completed, the salts are removed by filtration, washing, and the like. Further, a solvent such as toluene or methyl isobutyl ketone is removed by distillation under reduced pressure to obtain a compound represented by the formula (III). Specific examples of the compound represented by the above formula (III) may include, but are not limited to, those manufactured by Nippon Kayaku Co., Ltd., and models of NC-3000, NC-3000H, NC-3000S, and NC-3000P.

具有至少一個羧酸基與至少一個乙烯性不飽和基之化合物(b-2-2)a compound having at least one carboxylic acid group and at least one ethylenically unsaturated group (b-2-2)

具有至少一個羧酸基及至少一個乙烯性不飽和基之化合物(b-2-2)的具體例係選自於由下述(1)至(3)所組成之群組：(1)丙烯酸、甲基丙烯酸、2-甲基丙烯醯氧乙基丁二酸(2-methacryloyloxyethylbutanedioic acid)、2-甲基丙烯醯氧丁基丁二酸、2-甲基丙烯醯氧乙基己二酸、2-甲基丙烯醯氧丁基己二酸、2-甲基丙烯醯氧乙基六氫鄰苯二甲酸、2-甲基丙烯醯氧乙基馬來酸、2-甲基丙烯醯氧丙基馬來酸、2-甲基丙烯醯氧丁基馬來酸、2-甲基丙烯醯氧丙基丁二酸、2-甲基丙烯醯氧丙基己二酸、2-甲基丙烯醯氧丙基四氫鄰苯二甲酸、2-甲基丙烯醯氧丙基鄰苯二甲酸、2-甲基丙烯醯氧丁基鄰苯二甲酸或2-甲基丙烯醯氧丁基氫鄰苯二甲酸；(2)由具有羥基之(甲基)丙烯酸酯與二元羧酸化合物反應而得之化合物，其中二元羧酸化合物包含己二酸、丁二酸、馬來酸或鄰苯二甲酸；及(3)由具有羥基之(甲基)丙烯酸酯與後述之羧酸酐化合物(b-2-3)反應而得的半酯化合物，其中具有羥基之(甲基)丙烯酸酯包含2-羥基乙基丙烯酸酯[(2-hydroxyethyl)acrylate]、2-羥基乙基甲基丙烯酸酯[(2-hydroxyethyl)methacrylate]、2-羥基丙基丙烯酸酯[(2-hydroxypropyl)acrylate]、2-羥基丙基甲基丙烯酸酯[(2-hydroxypropyl)methacrylate]、4-羥基丁基丙烯酸酯[(4-hydroxybutyl)acrylate]、4-羥基丁基甲基丙烯酸酯[(4-hydroxybutyl)methacrylate]或季戊四醇三甲基丙烯酸酯等。 Specific examples of the compound (b-2-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group are selected from the group consisting of (1) to (3): (1) acrylic acid , methacrylic acid, 2-methacryloyloxyethylbutanedioic acid, 2-methylpropenyloxybutyl succinic acid, 2-methylpropenyl oxyethyl adipate, 2-methylpropenyloxybutyl adipate, 2-methylpropenyloxyethylhexahydrophthalic acid, 2-methylpropenyloxyethyl maleic acid, 2-methylpropenyloxypropane Kamalyx, 2-methylpropenyloxybutyl maleic acid, 2-methylpropenyloxypropyl succinic acid, 2-methylpropenyloxypropyl adipate, 2-methylpropene oxime Oxypropyl propyl tetrahydrophthalic acid, 2-methyl propylene oxypropyl phthalic acid, 2-methyl propylene oxy butyl phthalic acid or 2-methyl propylene oxy butyl hydrogen phthalate a dicarboxylic acid; (2) a compound obtained by reacting a (meth) acrylate having a hydroxyl group with a dicarboxylic acid compound, wherein the dicarboxylic acid compound comprises adipic acid, succinic acid, maleic acid or phthalic acid Formic acid; and (3) by having a hydroxyl group ( a half ester compound obtained by reacting an acrylate with a carboxylic anhydride compound (b-2-3) described later, wherein the (meth) acrylate having a hydroxyl group comprises 2-hydroxyethyl acrylate ], 2-hydroxyethylmethacrylate [2-hydroxyethyl) methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate [(2-hydroxypropyl] Methacrylate], 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate or pentaerythritol trimethacrylate.

羧酸酐化合物(b-2-3)Carboxylic anhydride compound (b-2-3)

羧酸酐化合物(b-2-3)可選自於由後述之(1)與(2)所組成的群組：(1)丁二酸酐(butanedioic anhydride)、順丁烯二酸酐(maleic anhydride)、衣康酸酐(Itaconic anhydride)、鄰苯二甲酸酐(phthalic anhydride)、四氫鄰苯二甲酸酐(tetrahydrophthalic anhydride)、六氫鄰苯二甲酸酐(hexahydrophthalic anhydride)、甲基四氫鄰苯二甲酸酐、甲基六氫鄰苯二甲酸酐、甲基橋亞甲基四氫鄰苯二甲酸酐(methyl endo-methylene tetrahydro phthalic anhydride)、氯茵酸酐(chlorendic anhydride)、戊二酸酐或偏三苯甲酸酐(1,3-dioxoisobenzofuran-5-carboxylic anhydride)等之二元羧酸酐化合物；以及(2)二苯甲酮四甲酸二酐(benzophenone tetracarboxylic dianhydride；BTDA)、雙苯四甲酸二酐或雙苯醚四甲酸二酐等之四元羧酸酐化合物。 The carboxylic anhydride compound (b-2-3) may be selected from the group consisting of (1) and (2) described later: (1) butanedioic anhydride, maleic anhydride , Itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride Methyl anhydride, methyl hexahydrophthalic anhydride, methyl endo-methylene tetrahydro phthalic anhydride, chlorendic anhydride, glutaric anhydride or partial a dicarboxylic anhydride compound such as 1,3-dioxoisobenzofuran-5-carboxylic anhydride; and (2) benzophenone tetracarboxylic dianhydride (BTDA), benzhydric acid dianhydride or A tetracarboxylic anhydride compound such as diphenyl ether tetracarboxylic dianhydride.

具有環氧基之化合物(b-2-4)Compound having an epoxy group (b-2-4)

具有環氧基之化合物(b-2-4)可選自於甲基丙烯酸環氧丙酯、3,4-環氧基環己基甲基丙烯酸酯、具有不飽和基之縮水甘油醚化合物、具有環氧基之不飽和化合物或上述化合物的任意組合。 The epoxy group-containing compound (b-2-4) may be selected from the group consisting of glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, a glycidyl ether compound having an unsaturated group, and An epoxy group unsaturated compound or any combination of the above compounds.

上述具有不飽和基之縮水甘油醚化合物可包含長瀨化成工業株式會社製造，型號為Denacol EX-111、EX-121 Denacol、Denacol EX-141、Denacol EX-145、Denacol EX-146、Denacol EX-171或Denacol EX-192等之商品。 The above glycidyl ether compound having an unsaturated group may be manufactured by Nagase Chemical Co., Ltd., model No. Denacol EX-111, EX-121 Denacol, Denacol EX-141, Denacol EX-145, Denacol EX-146, Denacol EX- 171 or Denacol EX-192 and other products.

該第二鹼可溶性樹脂(B-2)可為具有至少二個環氧基之環氧化合物(b-2-1)與具有至少一個羧酸基及至少一個 乙烯性不飽和基之化合物(b-2-2)進行聚合反應所形成之具有羥基的反應產物，其中具有至少二個環氧基之環氧化合物(b-2-1)包含如式(II)所示之化合物、如式(III)所示之化合物或上述材料之任意混合。接著，將羧酸酐化合物(b-2-3)加至反應溶液中，以進行聚合反應。基於上述含羥基的反應產物的羥基之總當量數為1當量，羧酸酐化合物(b-2-3)所具有之酸酐基的當量數為0.4當量至1當量，較佳為0.75當量至1當量。當使用多個羧酸酐化合物(b-2-3)時，此些羧酸酐化合物可於反應中依序添加或同時添加。當使用二元羧酸酐化合物及四元羧酸酐化合物來作為羧酸酐化合物(b-2-3)時，二元羧酸酐化合物及四元羧酸酐化合物的莫耳比為1/99至90/10，較佳為5/95至80/20。上述反應的操作溫度可為50℃至130℃。 The second alkali-soluble resin (B-2) may be an epoxy compound (b-2-1) having at least two epoxy groups and having at least one carboxylic acid group and at least one a reaction product having a hydroxyl group formed by a polymerization reaction of the ethylenically unsaturated group compound (b-2-2), wherein the epoxy compound (b-2-1) having at least two epoxy groups contains the formula (II) a compound shown, a compound of the formula (III) or any combination of the above materials. Next, a carboxylic anhydride compound (b-2-3) is added to the reaction solution to carry out a polymerization reaction. The number of equivalents of the hydroxyl group of the hydroxy group-containing reaction product is 1 equivalent, and the number of equivalents of the acid anhydride group of the carboxylic anhydride compound (b-2-3) is from 0.4 equivalents to 1 equivalent, preferably from 0.75 equivalents to 1 equivalent. . When a plurality of carboxylic anhydride compounds (b-2-3) are used, such carboxylic anhydride compounds may be added sequentially or simultaneously in the reaction. When a dicarboxylic anhydride compound and a tetracarboxylic anhydride compound are used as the carboxylic anhydride compound (b-2-3), the molar ratio of the dicarboxylic anhydride compound and the tetracarboxylic anhydride compound is from 1/99 to 90/10. Preferably, it is from 5/95 to 80/20. The above reaction can be operated at a temperature of from 50 ° C to 130 ° C.

第二鹼可溶性樹脂(B-2)可為具有至少二個環氧基之環氧化合物(b-2-1)與具有至少一個羧酸基及至少一個乙烯性不飽和基之化合物(b-2-2)進行反應所形成之具有羥基的反應產物，其中具有至少二個環氧基之環氧化合物(b-2-1)可為如式(II)及式(III)所示的化合物。接著，藉由添加羧酸酐化合物(b-2-3)、具有環氧基之化合物(b-2-4)或上述兩者的組合至反應溶液中，以進行聚合反應。基於如式(II)及式(III)所示之化合物中的環氧基的總當量數為1當量，上述具有至少一個羧酸基及至少一個乙烯性不飽和基之化合物(b-2-2)的酸價當量數為0.8當量至1.5當量，較佳為0.9當量至1.1當量。基於上述具有羥基之反應產物的羥基之總使 用量為100莫耳百分比，羧酸酐化合物(b-2-3)之使用量為10莫耳百分比至100莫耳百分比，較佳為20莫耳百分比至100莫耳百分比，更佳為30莫耳百分比至100莫耳百分比。 The second alkali-soluble resin (B-2) may be an epoxy compound (b-2-1) having at least two epoxy groups and a compound having at least one carboxylic acid group and at least one ethylenically unsaturated group (b- 2-2) a reaction product having a hydroxyl group formed by the reaction, wherein the epoxy compound (b-2-1) having at least two epoxy groups may be a compound represented by the formula (II) and the formula (III) . Next, a polymerization reaction is carried out by adding a carboxylic anhydride compound (b-2-3), a compound having an epoxy group (b-2-4), or a combination of the two to the reaction solution. The total number of equivalents of the epoxy group in the compound represented by the formula (II) and the formula (III) is 1 equivalent, and the above compound having at least one carboxylic acid group and at least one ethylenically unsaturated group (b-2- The acid number equivalent of 2) is from 0.8 equivalents to 1.5 equivalents, preferably from 0.9 equivalents to 1.1 equivalents. Based on the total number of hydroxyl groups of the above reaction product having a hydroxyl group The amount used is 100 mole percent, and the carboxylic anhydride compound (b-2-3) is used in an amount of 10 mole percent to 100 mole percent, preferably 20 mole percent to 100 mole percent, more preferably 30 moles. Percentage to 100% of the percentage.

製備上述的第二鹼可溶性樹脂(B-2)時，為了縮短反應時間，一般會添加鹼性化合物至反應溶液中，以作為反應觸媒。該反應觸媒可包含但不限於三苯基膦(triphenyl phosphine)、三苯基銻(triphenyl stibine)、三乙胺(triethylamine)、三乙醇胺(triethanolamine)、氯化四甲基銨(tetramethylammonium chloride)或氯化苄基三乙基銨(benzyltriethylammonium chloride)等。該反應觸媒可單獨一種或混合複數種來使用。 When the second alkali-soluble resin (B-2) described above is prepared, in order to shorten the reaction time, a basic compound is generally added to the reaction solution as a reaction catalyst. The reaction catalyst may include, but is not limited to, triphenyl phosphine, triphenyl stibine, triethylamine, triethanolamine, tetramethylammonium chloride. Or benzyltriethylammonium chloride or the like. The reaction catalyst may be used singly or in combination of plural kinds.

基於上述具有至少二個環氧基之環氧化合物(b-2-1)與具有至少一個羧酸基及至少一個乙烯性不飽和基之化合物(b-2-2)的總使用量為100重量份，該反應觸媒之使用量為0.01重量份至10重量份，較佳為0.3重量份至5重量份。 The total amount of the epoxy compound (b-2-1) having at least two epoxy groups and the compound (b-2-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group is 100. The reaction catalyst is used in an amount of from 0.01 part by weight to 10 parts by weight, preferably from 0.3 part by weight to 5 parts by weight, per part by weight.

其次，為了控制聚合度，反應可添加聚合抑制劑(polymerization inhibitor)至反應溶液中。聚合抑制劑可包含甲氧基酚(methoxyphenol)、甲基氫醌(methylhydroquinone)、氫醌(hydroquinone)、2,6-二第三丁基對甲酚(2,6-di-t-butyl-p-cresol)或吩噻嗪(phenothiazine)等。聚合抑制劑可單獨一種或混合複數種使用。 Secondly, in order to control the degree of polymerization, a reaction inhibitor may be added to the reaction solution. The polymerization inhibitor may comprise methoxyphenol, methylhydroquinone, hydroquinone, 2,6-di-t-butyl-p-butyl- (2,6-di-t-butyl- P-cresol) or phenothiazine. The polymerization inhibitor may be used singly or in combination of plural kinds.

基於上述具有至少二個環氧基之環氧化合物(b-2-1)與具有至少一個羧酸基及至少一個乙烯性不飽和基之化合物(b-2-2)的總使用量為100重量份，該聚合抑制劑的使用 量為0.01重量份至10重量份，較佳為0.1重量份至5重量份。 The total amount of the epoxy compound (b-2-1) having at least two epoxy groups and the compound (b-2-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group is 100. Parts by weight, use of the polymerization inhibitor The amount is from 0.01 part by weight to 10 parts by weight, preferably from 0.1 part by weight to 5 parts by weight.

製備第二鹼可溶性樹脂(B-2)時，聚合反應溶劑可選擇性地被使用。聚合反應溶劑可包含乙醇、丙醇、異丙醇、丁醇、異丁醇、2-丁醇、己醇或乙二醇等之醇類溶劑；甲乙酮或環己酮等之酮類溶劑；甲苯或二甲苯等之芳香族烴類溶劑；賽珞素(cellosolve)或丁基賽珞素(butyl cellosolve)等之賽珞素類溶劑；卡必妥(carbitol)或丁基卡必妥(butyl carbitol)等之卡必妥類溶劑；丙二醇單甲醚(propylene glycol monomethyl ether)等之丙二醇烷基醚類溶劑；二丙二醇單甲醚[di(propylene glycol)methyl ether]等之多丙二醇烷基醚[poly(propylene glycol)alkyl ether]類溶劑；醋酸乙酯、醋酸丁酯、乙二醇單***醋酸酯(ethylene glycol monoethyl ether acetate)或丙二醇單甲醚醋酸酯(propylene glycol methyl ether acetate)等之醋酸酯類溶劑；乳酸乙酯(ethyl lactate)或乳酸丁酯(butyl lactate)等之乳酸烷酯(alkyl lactate)類溶劑；或二烷基二醇醚類溶劑。該聚合反應溶劑可單獨一種或混合複數種來使用。 When the second alkali-soluble resin (B-2) is prepared, a polymerization solvent can be selectively used. The polymerization solvent may include an alcohol solvent such as ethanol, propanol, isopropanol, butanol, isobutanol, 2-butanol, hexanol or ethylene glycol; a ketone solvent such as methyl ethyl ketone or cyclohexanone; toluene; Or an aromatic hydrocarbon solvent such as xylene; a cellophane solvent such as cellosolve or butyl cellosolve; carbitol or butyl carbitol a solvent such as a carbaryl solvent; a propylene glycol alkyl ether solvent such as propylene glycol monomethyl ether; a polypropylene glycol alkyl ether such as dipropylene glycol monoether [di(propylene glycol) methyl ether] Poly(propylene glycol) alkyl ether] solvent; acetic acid such as ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate or propylene glycol methyl ether acetate An ester solvent; an alkyl lactate solvent such as ethyl lactate or butyl lactate; or a dialkyl glycol ether solvent. The polymerization solvent may be used singly or in combination of plural kinds.

第二鹼可溶性樹脂(B-2)的酸價為50毫克KOH/克至200毫克KOH/克，較佳為60毫克KOH/克至150毫克KOH/克。 The acid value of the second alkali-soluble resin (B-2) is from 50 mgKOH/g to 200 mgKOH/g, preferably from 60 mgKOH/g to 150 mgKOH/g.

當鹼可溶性樹脂(B)不使用第二鹼可溶性樹脂(B-2)時，所製得之彩色濾光片用感光性樹脂組成物具有耐顯影性不佳之缺陷。 When the alkali-soluble resin (B) does not use the second alkali-soluble resin (B-2), the photosensitive resin composition for a color filter obtained has a defect of poor development resistance.

當前述第一鹼可溶性樹脂(B-1)與第二鹼可溶性樹脂(B-2)之重量比為10/90至90/10時，所製得之彩色濾光片用感光性樹脂組成物具有較佳之耐顯影性。 When the weight ratio of the first alkali-soluble resin (B-1) to the second alkali-soluble resin (B-2) is from 10/90 to 90/10, the photosensitive resin composition for a color filter obtained is obtained. It has better developability.

第三鹼可溶性樹脂(B-3)Third alkali soluble resin (B-3)

第三鹼可溶性樹脂(B-3)係由一混合物所共聚合而成，其中該混合物包含具有一個或一個以上羧酸基之乙烯性不飽和單體(b-3-1)，以及前述具有一個或一個以上羧酸基之乙烯性不飽和單體(b-3-1)以外之其他可共聚合之乙烯性不飽和單體(b-3-2)。 The third alkali-soluble resin (B-3) is obtained by copolymerizing a mixture, wherein the mixture contains an ethylenically unsaturated monomer (b-3-1) having one or more carboxylic acid groups, and the foregoing a copolymerizable ethylenically unsaturated monomer (b-3-2) other than one or more carboxylic acid group-containing ethylenically unsaturated monomers (b-3-1).

具有一個或一個以上羧酸基之乙烯性不飽和單體(b-3-1)Ethylene unsaturated monomer having one or more carboxylic acid groups (b-3-1)

該具有一個或一個以上羧酸基之乙烯性不飽和單體(b-3-1)係相同於前述具有一個或一個以上羧酸基之乙烯性不飽和單體(b-1-2)相同，故在此不另贅述。 The ethylenically unsaturated monomer (b-3-1) having one or more carboxylic acid groups is the same as the above-mentioned ethylenically unsaturated monomer (b-1-2) having one or more carboxylic acid groups. Therefore, I will not repeat them here.

其他可共聚合之乙烯性不飽和單體(b-3-2)Other copolymerizable ethylenically unsaturated monomers (b-3-2)

該其他可共聚合之乙烯性不飽和單體(b-3-2)係相同於前述該具有受阻胺結構之乙烯性單體(b-1-1)與具有一個或一個以上羧酸基之乙烯性不飽和單體(b-1-2)以外其他可共聚合之乙烯性不飽和單體(b-1-3)，在此不另贅述。 The other copolymerizable ethylenically unsaturated monomer (b-3-2) is the same as the aforementioned ethylenic monomer (b-1-1) having a hindered amine structure and having one or more carboxylic acid groups. Other copolymerizable ethylenically unsaturated monomers (b-1-3) other than the ethylenically unsaturated monomer (b-1-2) are not described herein.

具有乙烯性不飽和基之化合物(C)Compound having ethylenically unsaturated group (C)

該具有乙烯性不飽和基之化合物(C)是指具有至少一個乙烯性不飽和基之不飽和化合物或具有2個或2個以上之乙烯性不飽和基之不飽和化合物。 The compound (C) having an ethylenically unsaturated group means an unsaturated compound having at least one ethylenically unsaturated group or an unsaturated compound having two or more ethylenically unsaturated groups.

該具有至少一個乙烯性不飽和基之不飽和化合物 可包含但不限於丙烯醯胺、丙烯醯嗎啉、甲基丙烯醯嗎啉、丙烯酸-7-胺基-3,7-二甲基辛酯、甲基丙烯酸-7-胺基-3,7-二甲基辛酯、異丁氧基甲基丙烯醯胺、異丁氧基甲基甲基丙烯醯胺、丙烯酸異冰片基氧乙酯、甲基丙烯酸異冰片基氧乙酯、丙烯酸異冰片酯、甲基丙烯酸異冰片酯、丙烯酸-2-乙基己酯、甲基丙烯酸-2-乙基己酯、乙基二甘醇丙烯酸酯、乙基二甘醇甲基丙烯酸酯、第三辛基丙烯醯胺、第三辛基甲基丙烯醯胺、二丙酮丙烯醯胺、二丙酮甲基丙烯醯胺、丙烯酸二甲胺基酯、甲基丙烯酸二甲胺基酯、丙烯酸十二烷基酯、甲基丙烯酸十二烷基酯、丙烯酸二環戊烯氧乙酯、甲基丙烯酸二環戊烯氧乙酯、丙烯酸二環戊烯酯、甲基丙烯酸二環戊烯酯、N,N-二甲基丙烯醯胺、N,N-二甲基甲基丙烯醯胺、丙烯酸四氯苯酯、甲基丙烯酸四氯苯酯、丙烯酸-2-四氯苯氧基乙酯、甲基丙烯酸-2-四氯苯氧基乙酯、丙烯酸四氫糠酯、甲基丙烯酸四氫糠酯、丙烯酸四溴苯酯、甲基丙烯酸四溴苯酯、丙烯酸-2-四溴苯氧基乙酯、甲基丙烯酸-2-四溴苯氧基乙酯、丙烯酸-2-三氯苯氧基乙酯、甲基丙烯酸-2-三氯苯氧基乙酯、丙烯酸三溴苯酯、甲基丙烯酸三溴苯酯、丙烯酸-2-三溴苯氧基乙酯、甲基丙烯酸-2-三溴苯氧基乙酯、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、乙烯基己內醯胺、N-乙烯基皮酪烷酮、丙烯酸苯氧基乙酯、甲基丙烯酸苯氧基乙酯、丙烯酸五氯苯酯、甲基丙烯酸五氯苯酯、丙烯酸五溴苯酯、甲基丙烯酸五溴苯酯、聚單丙烯酸 乙二醇酯、聚單甲基丙烯酸乙二醇酯、聚單丙烯酸丙二醇酯、聚單甲基丙烯酸丙二醇酯、丙烯酸冰片酯或甲基丙烯酸冰片酯等。 The unsaturated compound having at least one ethylenically unsaturated group It may include, but is not limited to, acrylamide, propylene morpholine, methacryl morpholine, acrylate-7-amino-3,7-dimethyloctyl methacrylate, methacrylic acid-7-amino-3,7 - dimethyloctyl ester, isobutoxymethyl acrylamide, isobutoxymethyl methacrylamide, isobornyl oxyethyl acrylate, isobornyl oxyethyl methacrylate, isobornyl acrylate Ester, isobornyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, ethyl diglycol acrylate, ethyl diglycol methacrylate, third octyl Acrylamide, trioctylmethacrylamide, diacetone acrylamide, diacetone methacrylamide, dimethylamino acrylate, dimethylamino methacrylate, dodecyl acrylate Ester, dodecyl methacrylate, dicyclopentene oxyethyl acrylate, dicyclopentene oxyethyl methacrylate, dicyclopentenyl acrylate, dicyclopentenyl methacrylate, N, N -Dimethyl acrylamide, N,N-dimethyl methacrylamide, tetrachlorophenyl acrylate, tetrachlorophenyl methacrylate, 2-tetrachlorophenoxy acrylate Ester, 2-tetrachlorophenoxyethyl methacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, tetrabromophenyl acrylate, tetrabromophenyl methacrylate, 2-tetrabromo acrylate Phenoxyethyl ester, -2-tetrabromophenoxyethyl methacrylate, 2-trichlorophenoxyethyl acrylate, 2-trichlorophenoxyethyl methacrylate, tribromobenzene acrylate Ester, tribromophenyl methacrylate, 2-tribromophenoxyethyl acrylate, 2-tribromophenoxyethyl methacrylate, 2-hydroxyethyl acrylate, methacrylic acid-2- Hydroxyethyl ester, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, vinyl caprolactam, N-vinyl tyrosinone, phenoxyethyl acrylate, phenoxy methacrylate Ethyl ethyl ester, pentachlorophenyl acrylate, pentachlorophenyl methacrylate, pentabromophenyl acrylate, pentabromophenyl methacrylate, polymonoacrylic acid Ethylene glycol ester, polyethylene monomethacrylate, poly propylene glycol monoacrylate, poly propylene glycol monomethacrylate, borneol acrylate or borneol methacrylate.

前述具有至少一個乙烯性不飽和基之不飽和化合物可單獨一種或混合複數種使用。 The above unsaturated compound having at least one ethylenically unsaturated group may be used singly or in combination of plural kinds.

該具有2個或2個以上乙烯性不飽和基之不飽和化合物包含但不限於乙二醇二丙烯酸酯、乙二醇二甲基丙烯酸酯、二丙烯酸二環戊烯酯、二甲基丙烯酸二環戊烯酯、三甘醇二丙烯酸酯、四甘醇二丙烯酸酯、四甘醇二甲基丙烯酸酯、三(2-羥乙基)異氰酸酯二丙烯酸酯、三(2-羥乙基)異氰酸酯二甲基丙烯酸酯、三(2-羥乙基)異氰酸酯三丙烯酸酯、三(2-羥乙基)異氰酸酯三甲基丙烯酸酯、己內酯改質之三(2-羥乙基)異氰酸酯三丙烯酸酯、己內酯改質之三(2-羥乙基)異氰酸酯三甲基丙烯酸酯、三丙烯酸三羥甲基丙酯、三甲基丙烯酸三羥甲基丙酯、環氧乙烷(以下簡稱EO)改質之三丙烯酸三羥甲基丙酯、EO改質之三甲基丙烯酸三羥甲基丙酯、環氧丙烷(以下簡稱PO)改質之三丙烯酸三羥甲基丙酯、PO改質之三甲基丙烯酸三羥甲基丙酯、三甘醇二丙烯酸酯、三甘醇二甲基丙烯酸酯、新戊二醇二丙烯酸酯、新戊二醇二甲基丙烯酸酯、1,4-丁二醇二丙烯酸酯、1,4-丁二醇二甲基丙烯酸酯、1,6-己二醇二丙烯酸酯、1,6-己二醇二甲基丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇三甲基丙烯酸酯、季戊四醇四丙烯酸酯、季戊四醇四甲基丙烯酸酯、聚酯二丙烯酸酯、聚酯二甲基丙烯酸酯、聚乙二醇二 丙烯酸酯、聚乙二醇二甲基丙烯酸酯、二季戊四醇六丙烯酸酯(dipentaerythritol hexaacrylate；DPHA)、二季戊四醇六甲基丙烯酸酯、二季戊四醇五丙烯酸酯、二季戊四醇五甲基丙烯酸酯、二季戊四醇四丙烯酸酯、二季戊四醇四甲基丙烯酸酯、己內酯改質之二季戊四醇六丙烯酸酯、己內酯改質之二季戊四醇六甲基丙烯酸酯、己內酯改質之二季戊四醇五丙烯酸酯、己內酯改質之二季戊四醇五甲基丙烯酸酯、四丙烯酸二三羥甲基丙酯、四甲基丙烯酸二三羥甲基丙酯、EO改質之雙酚A二丙烯酸酯、EO改質之雙酚A二甲基丙烯酸酯、PO改質之雙酚A二丙烯酸酯、PO改質之雙酚A二甲基丙烯酸酯、EO改質之氫化雙酚A二丙烯酸酯、EO改質之氫化雙酚A二甲基丙烯酸酯、PO改質之氫化雙酚A二丙烯酸酯、PO改質之氫化雙酚A二甲基丙烯酸酯、PO改質之甘油三丙酸酯、EO改質之雙酚F二丙烯酸酯、EO改質之雙酚F二甲基丙烯酸酯、酚醛聚縮水甘油醚丙烯酸酯、酚醛聚縮水甘油醚甲基丙烯酸酯，或者日本東亞合成株式會社製造，型號為TO-1382之商品等。 The unsaturated compound having 2 or more ethylenically unsaturated groups includes, but is not limited to, ethylene glycol diacrylate, ethylene glycol dimethacrylate, dicyclopentenyl diacrylate, and dimethacrylic acid Cyclopentenyl ester, triethylene glycol diacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, tris(2-hydroxyethyl)isocyanate diacrylate, tris(2-hydroxyethyl)isocyanate Dimethacrylate, tris(2-hydroxyethyl)isocyanate triacrylate, tris(2-hydroxyethyl)isocyanate trimethacrylate, caprolactone modified tris(2-hydroxyethyl)isocyanate Acrylate, caprolactone modified tris(2-hydroxyethyl)isocyanate trimethacrylate, trimethylolpropyl triacrylate, trimethylolpropyl trimethacrylate, ethylene oxide (below EO) is a modified trimethylol propyl triacrylate, EO modified trimethylol propyl trimethacrylate, propylene oxide (hereinafter referred to as PO) modified trimethylol propyl triacrylate, PO modified trimethylol propyl trimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate Neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol Acrylate, 1,6-hexanediol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, polyester diacrylate, polyester Acrylate, polyethylene glycol II Acrylate, polyethylene glycol dimethacrylate, dipentaerythritol hexaacrylate (DPHA), dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethyl acrylate, dipentaerythritol Acrylate, dipentaerythritol tetramethacrylate, caprolactone modified dipentaerythritol hexaacrylate, caprolactone modified dipentaerythritol hexamethacrylate, caprolactone modified dipentaerythritol pentaacrylate, Lactone modified dipentaerythritol pentamethyl acrylate, ditrimethylol propyl tetraacrylate, ditrimethylol propyl tetramethacrylate, EO modified bisphenol A diacrylate, EO modified Bisphenol A dimethacrylate, PO modified bisphenol A diacrylate, PO modified bisphenol A dimethacrylate, EO modified hydrogenated bisphenol A diacrylate, EO modified hydrogenation Bisphenol A dimethacrylate, PO modified hydrogenated bisphenol A diacrylate, PO modified hydrogenated bisphenol A dimethacrylate, PO modified triglyceride, EO modified double Phenol F diacrylic acid , The EO modified bisphenol F dimethacrylate, novolac polyglycidyl ether acrylate, a phenolic polyglycidyl ether methacrylate, or Toagosei Co., Ltd. of Japan, TO-1382 Model of commodities.

該具有乙烯性不飽和基之化合物(C)較佳係選自於三丙烯酸三羥甲基丙酯、EO改質之三丙烯酸三羥甲基丙酯、PO改質之三丙烯酸三羥甲基丙酯、季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯、二季戊四醇六丙烯酸酯、二季戊四醇五丙烯酸酯、二季戊四醇四丙烯酸酯、己內酯改質之二季戊四醇六丙烯酸酯、四丙烯酸二三羥甲基丙酯、PO改質之甘油三丙酸酯或上述材料之任意組合。 The ethylenically unsaturated group-containing compound (C) is preferably selected from trimethylolpropyl triacrylate, EO-modified trimethylolpropyl triacrylate, and PO-modified trishydroxymethyl triacrylate. Propyl ester, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, caprolactone modified dipentaerythritol hexaacrylate, ditrimethylol tetraacrylate Propyl ester, PO modified triglyceride or any combination of the above.

基於前述鹼可溶性樹脂(B)之總使用量為100重量份，該具有乙烯性不飽和基之化合物(C)的使用量為60重量份至600重量份，較佳為80重量份至500重量份，更佳為100重量份至400重量份。 The compound (C) having an ethylenically unsaturated group is used in an amount of 60 parts by weight to 600 parts by weight, preferably 80 parts by weight to 500 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resin (B). More preferably, it is 100 parts by weight to 400 parts by weight.

光起始劑(D)Photoinitiator (D)

本發明之光起始劑(D)可為O-醯基肟(oxime)化合物、三嗪(triazine)化合物、苯乙烷酮(acetophenone)化合物、二咪唑(biimidazole)化合物或二苯甲酮(benzophenone)化合物等。該光起始劑(D)可單獨一種或混合複數種使用。 The photoinitiator (D) of the present invention may be an O-oxime compound, a triazine compound, an acetophenone compound, a biimidazole compound or a benzophenone ( Benzophenone) and the like. The photoinitiator (D) may be used singly or in combination of plural kinds.

該O-醯基肟化合物可包含但不限於1-[4-(苯基硫代)苯基]-庚烷-1,2-二酮-2-(O-苯醯基肟)、1-[4-(苯基硫代)苯基]-辛烷-1,2-二酮-2-(O-苯醯基肟)、1-[4-(苯醯基)苯基]-庚烷-1,2-二酮-2-(O-苯醯基肟)、1-[9-乙基-6-(2-甲基苯醯基)-9H-咔唑-3-基]-乙烷酮-1-(O-乙醯基肟)、1-[9-乙基-6-(3-甲基苯醯基)-9H-咔唑-3-基]-乙烷酮1-(O-乙醯基肟)、1-[9-乙基-6-苯醯基-9H-咔唑-3-基]-乙烷酮1-(O-乙醯基肟)、乙烷酮-1-[9-乙基-6-(2-甲基-4-四氫呋喃基苯醯基)-9H-咔唑-3-基]-1-(O-乙醯基肟)、乙烷酮-1-[9-乙基-6-(2-甲基-5-四氫吡喃基苯醯基)-9H-咔唑-3-基]-1-(O-乙醯基肟)、乙烷酮-1-[9-乙基-6-(2-甲基-4-四氫呋喃基甲氧基苯醯基)-9H-咔唑-3-基]-1-(O-乙醯基肟)、乙烷酮-1-[9-乙基-6-(2-甲基-5-四氫呋喃基甲氧基苯醯基)-9H-咔唑-3-基]-1-(O-乙醯基肟)、乙烷酮-1-[9-乙基-6-{2-甲基-4-(2,2-二甲基-1,3-二氧雜戊環基)苯醯基}-9H-咔唑-3-基]-1-(O-乙 醯基肟)，或乙烷酮-1-[9-乙基-6-{2-甲基-4-(2,2-二甲基-1,3-二氧雜戊環基)甲氧基苯醯基}-9H-咔唑-3-基]-1-(O-乙醯基肟)等。前述之O-醯基肟化合物可單獨一種或混合複數種使用。 The O-mercaptopurine compound may include, but is not limited to, 1-[4-(phenylthio)phenyl]-heptane-1,2-dione-2-(O-benzoinhydrazino), 1- [4-(phenylthio)phenyl]-octane-1,2-dione-2-(O-phenylhydrazinyl), 1-[4-(phenylhydrazino)phenyl]-heptane -1,2-dione-2-(O-phenylhydrazinium), 1-[9-ethyl-6-(2-methylphenylhydrazino)-9H-indazol-3-yl]-B Alkanone-1-(O-ethylindenyl), 1-[9-ethyl-6-(3-methylphenylindenyl)-9H-indazol-3-yl]-ethanone 1-( O-acetinyl), 1-[9-ethyl-6-benzoin-9H-indazol-3-yl]-ethane ketone 1-(O-acetamidoxime), ethane ketone- 1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylbenzoyl)-9H-indazol-3-yl]-1-(O-ethylindenyl), ethane ketone- 1-[9-ethyl-6-(2-methyl-5-tetrahydropyranylphenyl)-9H-indazol-3-yl]-1-(O-ethylindenyl), B Alkanone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylmethoxyphenyl)-9H-indazol-3-yl]-1-(O-ethylindenyl) Ethyl ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylmethoxyphenyl)-9H-indazol-3-yl]-1-(O-B Ethyl ketone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)phenyl fluorenyl }-9H-carbazol-3-yl]-1-(O- 醯 肟 肟, or ethane ketone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxy Benzobenzyl}-9H-carbazol-3-yl]-1-(O-ethylindenyl) and the like. The above O-indenyl ruthenium compounds may be used singly or in combination of plural kinds.

該三嗪化合物可包含但不限於2,4-雙(三氯甲基)-6-(對-甲氧基)苯乙烯基-s-三嗪[2,4-Bis(trichloromethyl)-6-(p-methoxy)styryl-s-triazine]、2,4-雙(三氯甲基)-6-(1-對-二甲基胺基苯基-1,3-丁二烯基)-s-三嗪[2,4-Bis(trichloromethyl)-6-(1-p-dimethylaminophenyl-1,3-butadienyl)-s-triazine]或2-三氯甲基-4-胺基-6-對-甲氧基苯乙烯基-s-三嗪[2-trichloromethyl-4-amino-6-(p-methoxy)styryl-s-triazine]等。前述之三嗪化合物可單獨一種或混合複數種使用。 The triazine compound may include, but is not limited to, 2,4-bis(trichloromethyl)-6-(p-methoxy)styryl-s-triazine [2,4-Bis(trichloromethyl)-6- (p-methoxy)styryl-s-triazine], 2,4-bis(trichloromethyl)-6-(1-p-dimethylaminophenyl-1,3-butadienyl)-s -Triazine [2,4-Bis(trichloromethyl)-6-(1-p-dimethylaminophenyl-1,3-butadienyl)-s-triazine] or 2-trichloromethyl-4-amino-6-pair- Methoxystyryl-s-triazine [2-trichloromethyl-4-amino-6-(p-methoxy)styryl-s-triazine] and the like. The above triazine compounds may be used singly or in combination of plural kinds.

該苯乙烷酮化合物可包含但不限於對二甲胺苯乙烷酮、α,α’-二甲氧基氧化偶氮苯乙烷酮、2,2’-二甲基-2-苯基苯乙烷酮、對-甲氧基苯乙烷酮、2-甲基-1-(4-甲基硫代苯基)-2-嗎啉-1-丙酮或2-苄基-2-N,N-二甲胺-1-(4-嗎啉苯基)-1-丁酮等。前述之苯乙烷酮化合物可單獨一種或混合複數種使用。 The acetophenone compound may include, but is not limited to, p-dimethylacetonone, α,α'-dimethoxyoxyazopropenone, 2,2'-dimethyl-2-phenyl Ethyl ketone, p-methoxyacetophenone, 2-methyl-1-(4-methylthiophenyl)-2-morpholine-1-propanone or 2-benzyl-2-N , N-dimethylamine-1-(4-morpholinylphenyl)-1-butanone and the like. The above-mentioned acetophenone compounds may be used singly or in combination of plural kinds.

該二咪唑化合物可包含但不限於2,2’-雙(鄰-氯苯基)-4,4’,5,5’-四苯基二咪唑、2,2’-雙(鄰-氟苯基)-4,4’,5,5’-四苯基二咪唑、2,2’-雙(鄰-甲基苯基)-4,4’,5,5’-四苯基二咪唑、2,2’-雙(鄰-甲氧基苯基)-4,4’,5,5’-四苯基二咪唑、2,2’- 雙(鄰-乙基苯基)-4,4’,5,5’-四苯基二咪唑、2,2’-雙(對-甲氧基苯基)-4,4’,5,5’-四苯基二咪唑、2,2’-雙(2,2’,4,4’-四甲氧基苯基)-4,4’,5,5’-四苯基二咪唑、2,2’-雙(2-氯苯基)-4,4’,5,5’-四苯基二咪唑或2,2’-雙(2,4-二氯苯基)-4,4’,5,5’-四苯基二咪唑等。前述之二咪唑化合物可單獨一種或混合複數種使用。 The diimidazole compound may include, but is not limited to, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-fluorobenzene) -4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-methylphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-methoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'- Bis(o-ethylphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(p-methoxyphenyl)-4,4',5,5 '-Tetraphenyldiimidazole, 2,2'-bis(2,2',4,4'-tetramethoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2 , 2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole or 2,2'-bis(2,4-dichlorophenyl)-4,4' , 5,5'-tetraphenyldiimidazole and the like. The above-mentioned diimidazole compounds may be used singly or in combination of plural kinds.

該二苯甲酮化合物可包含但不限於噻噸酮、2,4-二乙基噻噸酮、噻噸酮-4-碸、二苯甲酮、4,4’-雙(二甲胺)二苯甲酮或4,4’-雙(二乙胺)二苯甲酮等。前述之二苯甲酮化合物可單獨一種或混合複數種使用。 The benzophenone compound may include, but is not limited to, thioxanthone, 2,4-diethylthioxanthone, thioxanthone-4-oxime, benzophenone, 4,4'-bis(dimethylamine) Benzophenone or 4,4'-bis(diethylamine) benzophenone. The aforementioned benzophenone compounds may be used singly or in combination of plural kinds.

該光起始劑(D)較佳可為1-[4-(苯基硫代)苯基]-辛烷-1,2-二酮-2-(O-苯醯基肟)、1-[9-乙基-6-(2-甲基苯醯基)-9H-咔唑-3-基]-乙烷酮-1-(O-乙醯基肟)、乙烷酮-1-[9-乙基-6-(2-甲基-4-四氫呋喃基甲氧基苯醯基)-9H-咔唑-3-基]-1-(O-乙醯基肟)、乙烷酮-1-[9-乙基-6-{2-甲基-4-(2,2-二甲基-1,3-二氧雜戊環基)甲氧基苯醯基}-9H-咔唑-3-基]-1-(O-乙醯基肟)、2,4-雙(三氯甲基)-6-(對-甲氧基)苯乙烯基-s-三嗪、2-苄基-2-N,N-二甲胺-1-(4-嗎啉苯基)-1-丁酮、2,2’-雙(2,4-二氯苯基)-4,4’,5,5’-四苯基二咪唑[2,2’-bis(2,4-dichlorophenyl)-4,4’,5,5’-tetraphenyl-1,2’-bii midazole]、4,4’-雙(二乙胺)二苯甲酮或上述材料之任意組合。 The photoinitiator (D) is preferably 1-[4-(phenylthio)phenyl]-octane-1,2-dione-2-(O-phenylhydrazinyl), 1- [9-Ethyl-6-(2-methylphenylindenyl)-9H-indazol-3-yl]-ethanone-1-(O-acetamidoxime), ethane ketone-1-[ 9-Ethyl-6-(2-methyl-4-tetrahydrofurylmethoxyphenyl)]-9H-indazol-3-yl]-1-(O-ethylindenyl), ethane ketone- 1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzoquinone}-9H-carbazole 3-yl]-1-(O-acetamidoxime), 2,4-bis(trichloromethyl)-6-(p-methoxy)styryl-s-triazine, 2-benzyl Benzyl-2-N,N-dimethylamine-1-(4-morpholinylphenyl)-1-butanone, 2,2'-bis(2,4-dichlorophenyl)-4,4', 5,5'-bis(2,4-dichlorophenyl-4,4',5,5'-tetraphenyl-1,2'-bii midazole], 4,4' - bis(diethylamine)benzophenone or any combination of the above.

在不影響感光性樹脂組成物之物性下，本發明之感光性樹脂組成物可進一步添加該光起始劑(D)以外之起始 劑。該起始劑之具體例，如：α-二酮(α-diketone)化合物、酮醇(acyloin)化合物、酮醇醚(acyloin ether)化合物、醯膦氧化物(acylphosphineoxide)化合物、醌(quinone)化合物、具有鹵素之化合物或過氧化物等。 The photosensitive resin composition of the present invention may further contain an initiator other than the photoinitiator (D) without affecting the physical properties of the photosensitive resin composition. Agent. Specific examples of the initiator include, for example, an α-diketone compound, a acyloin compound, a acyloin ether compound, an acylphosphine oxide compound, and a quinone. a compound, a compound having a halogen, a peroxide, or the like.

該α-二酮化合物可包含但不限於苯偶醯(benzil)或乙醯基(acetyl)系化合物等。前述之α-二酮化合物可單獨一種或混合複數種使用。 The α-diketone compound may include, but is not limited to, a benzil or an ethenyl (acetyl) compound or the like. The above α-diketone compounds may be used singly or in combination of plural kinds.

該酮醇化合物可包含但不限於二苯乙醇酮(benzoin)等。前述之酮醇化合物可單獨一種或混合複數種使用。 The ketol compound may include, but is not limited to, benzoin or the like. The aforementioned ketol compounds may be used singly or in combination of plural kinds.

該酮醇醚化合物可包含但不限於二苯乙醇酮甲醚(benzoin methylether)、二苯乙醇酮***(benzoin ethylether)或二苯乙醇酮異丙醚(benzoin isopropyl ether)等。前述之酮醇醚化合物可單獨一種或混合複數種使用。 The ketol ether compound may include, but is not limited to, benzoin methylether, benzoin ethylether or benzoin isopropyl ether. The aforementioned ketol ether compounds may be used singly or in combination of plural kinds.

該醯膦氧化物化合物可包含但不限於2,4,6-三甲基苯醯二苯基膦氧化物(2,4,6-trimethyl-benzoyl diphenylphosphineoxide)或雙-(2,6-二甲氧基苯醯)-2,4,4-三甲基苯基膦氧化物[bis-(2,6-dimethoxy-benzoyl)-2,4,4-trimethylbenzyl phosphineoxide]等。前述之醯膦氧化物化合物可單獨一種或混合複數種使用。 The ruthenium phosphine oxide compound may include, but is not limited to, 2,4,6-trimethyl-benzoyl diphenylphosphine oxide or bis-(2,6-dimethyl Bismuth(2,6-dimethoxy-benzoyl-2,4,4-trimethylbenzyl phosphineoxide) and the like. The above fluorinated phosphine oxide compounds may be used singly or in combination of plural kinds.

該醌類化合物可包含但不限於蒽醌(anthraquinone)、1,4-萘醌(1,4-naphthoquinone)等。前述之醌類化合物可單獨一種或混合複數種使用。 The terpenoid compound may include, but is not limited to, anthraquinone, 1,4-naphthoquinone, and the like. The above-mentioned terpenoids may be used singly or in combination of plural kinds.

該具有鹵素之化合物可包含但不限於苯醯甲基氯 (phenacyl chloride)、三溴甲基苯碸(tribromomethyl phenylsulfone)或三(三氯甲基)-s-三嗪[tris(trichloromethyl)-s-triazine]等。前述具有鹵素之化合物可單獨一種或混合複數種使用。 The halogen-containing compound may include, but is not limited to, benzoquinone methyl chloride (phenacyl chloride), tribromomethyl phenylsulfone or tris(trichloromethyl)-s-triazine. The above halogen-containing compounds may be used singly or in combination of plural kinds.

該過氧化物可包含但不限於二-第三丁基過氧化物(di-tertbutylperoxide)等。前述之過氧化物可單獨一種或混合複數種使用。 The peroxide may include, but is not limited to, di-tertbutylperoxide or the like. The foregoing peroxides may be used singly or in combination of plural kinds.

基於前述鹼可溶性樹脂(B)之總使用量為100重量份，該光起始劑(D)之使用量為10重量份至100重量份，較佳為15重量份至90重量份，更佳為20重量份至80重量份。 The photoinitiator (D) is used in an amount of 10 parts by weight to 100 parts by weight, preferably 15 parts by weight to 90 parts by weight, based on 100 parts by weight of the total amount of the alkali-soluble resin (B). It is 20 parts by weight to 80 parts by weight.

有機溶劑(E)Organic solvent (E)

本發明之有機溶劑(E)可包含但不限於乙二醇甲醚、乙二醇***、二甘醇甲醚、二甘醇***、二甘醇正丙醚、二甘醇正丁醚、三甘醇甲醚、三甘醇***、丙二醇甲醚、丙二醇***、一縮二丙二醇甲醚、一縮二丙二醇***、一縮二丙二醇正丙醚、一縮二丙二醇正丁醚、二縮三丙二醇甲醚或二縮三丙二醇***等之(聚)亞烷基二醇單烷醚類溶劑；乙二醇甲醚醋酸酯、乙二醇***醋酸酯、丙二醇甲醚醋酸酯(propylene glycol methyl ether acetate；PGMEA)或丙二醇***醋酸酯等之(聚)亞烷基二醇單烷醚醋酸酯類溶劑；二甘醇二甲醚、二甘醇甲***、二甘醇二***或四氫呋喃等之其他醚類溶劑；甲乙烷酮、環己酮、2-庚酮或3-庚酮等之酮類溶劑；2-羥基丙酸甲酯或2-羥基丙酸乙酯 等之乳酸烷酯類溶劑；2-羥基-2-甲基丙酸甲酯、2-羥基-2-甲基丙酸乙酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯(ethyl 3-ethoxypropionate；EEP)、乙氧基乙酸乙酯、羥基乙酸乙酯、2-羥基-3-甲基丁酸甲酯、3-甲基-3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基丙酸酯、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、丙酮酸甲酯、丙酮酸乙酯、丙酮酸正丙酯、乙醯乙酸甲酯、乙醯乙酸乙酯或2-甲氧基丁酸乙酯等之其他酯類溶劑；甲苯或二甲苯等之芳香族碳氫化合物類溶劑；N-甲基吡咯烷酮、N,N-二甲基甲醯胺或N,N-二甲基乙醯胺等醯胺類溶劑。 The organic solvent (E) of the present invention may include, but is not limited to, ethylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol n-propyl ether, diethylene glycol n-butyl ether, triethylene glycol Methyl ether, triethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, dipropylene glycol methyl ether, dipropylene glycol diethyl ether, dipropylene glycol n-propyl ether, dipropylene glycol n-butyl ether, tripropylene glycol methyl ether Or (poly)alkylene glycol monoalkyl ether solvent such as tripropylene glycol diethyl ether; ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate (PGMEA) Or (poly)alkylene glycol monoalkyl ether acetate solvent such as propylene glycol ethyl ether acetate; other ether solvent such as diglyme, diethylene glycol methyl ether, diethylene glycol diethyl ether or tetrahydrofuran a ketone solvent such as methyl ethyl ketone, cyclohexanone, 2-heptanone or 3-heptanone; methyl 2-hydroxypropionate or ethyl 2-hydroxypropionate Ethyl lactate solvent; methyl 2-hydroxy-2-methylpropanoate, ethyl 2-hydroxy-2-methylpropanoate, methyl 3-methoxypropionate, 3-methoxypropane Ethyl acetate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate (EEP), ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-3- Methyl methyl butyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, acetic acid Propyl ester, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyrate Other ester solvents such as ester, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate or ethyl 2-methoxybutanoate; toluene or xylene An aromatic hydrocarbon solvent such as N-methylpyrrolidone, N,N-dimethylformamide or a guanamine solvent such as N,N-dimethylacetamide.

該有機溶劑(E)較佳可為丙二醇甲醚酯酸酯或3-乙氧基丙酸乙酯。 The organic solvent (E) is preferably propylene glycol methyl ether ester or ethyl 3-ethoxypropionate.

基於前述鹼可溶性樹脂(B)之總使用量為100重量份，該有機溶劑(E)之使用量為500重量份至5000重量份，較佳為800重量份至4,500重量份；更佳為1,000重量份至4,000重量份。 The organic solvent (E) is used in an amount of 500 parts by weight to 5000 parts by weight, preferably 800 parts by weight to 4,500 parts by weight, based on 100 parts by weight of the total amount of the alkali-soluble resin (B); more preferably 1,000 parts by weight. Parts by weight to 4,000 parts by weight.

染料(F)Dye (F)

本發明之彩色濾光片用感光性樹脂組成物可選擇性地包含染料(F)，且該染料(F)具有如下式(IV)所示之結構的紅色染料： The photosensitive resin composition for a color filter of the present invention may optionally contain a dye (F), and the dye (F) has a red dye having a structure represented by the following formula (IV):

於式(IV)中，Z1至Z4各自獨立地代表氫原子、-Z6、碳數為6至10之芳香羥基或經鹵素原子、-Z6、-OH、-OZ6、-SO3 -、-SO3H、-SO3M、-COOH、-COOZ6、-SO3Z6、-SO2NHZ8或-SO2NZ8Z9所取代碳數為6至10之芳香羥基；Z5代表-SO3 -、-SO3H、-SO3M、-COOH、-COOZ6、-SO3Z6、-SO2NHZ8或-SO2NZ8Z9；A代表鹵素原子；a代表0或1且b代表0至5之整數。當b代表2至5時，複數個Z5為相同或不相同。前述之Z6、Z8、Z9與M分別如下所述。 In the formula (IV), Z 1 to Z 4 each independently represent a hydrogen atom, -Z 6 , an aromatic hydroxy group having a carbon number of 6 to 10 or a halogen atom, -Z 6 , -OH, -OZ 6 , -SO 3 - , -SO 3 H, -SO 3 M, -COOH, -COOZ 6 , -SO 3 Z 6 , -SO 2 NHZ 8 or -SO 2 NZ 8 Z 9 is substituted with an aromatic hydroxy group having 6 to 10 carbon atoms ; Z 5 represents -SO 3 - , -SO 3 H, -SO 3 M, -COOH, -COOZ 6 , -SO 3 Z 6 , -SO 2 NHZ 8 or -SO 2 NZ 8 Z 9 ; A represents a halogen atom ; a represents 0 or 1 and b represents an integer of 0 to 5. When b represents 2 to 5, a plurality of Z 5 are the same or different. The aforementioned Z 6 , Z 8 , Z 9 and M are as follows, respectively.

前述之Z6代表碳數為1至10之烷基或經鹵素原子所取代碳數為1至10之烷基，其中該碳數為1至10之烷基或該經鹵素原子所取代碳數為1至10之烷基中的-CH2-係未被取代或可被-O-、羰基或-NZ7-所取代。該Z7代表碳數為1至10之烷基或經鹵素原子取代碳數為1至10之烷基。 The aforementioned Z 6 represents an alkyl group having 1 to 10 carbon atoms or an alkyl group having 1 to 10 carbon atoms substituted by a halogen atom, wherein the carbon number is 1 to 10 or the number of carbon atoms substituted by the halogen atom The -CH 2 - in the alkyl group of 1 to 10 is unsubstituted or may be substituted by -O-, carbonyl or -NZ 7 -. The Z 7 represents an alkyl group having 1 to 10 carbon atoms or an alkyl group having 1 to 10 carbon atoms substituted by a halogen atom.

前述之Z8及Z9各自獨立地代表碳數為1至10之直鏈烷基、支鏈烷基或環烷基，或者-Q。該Q代表碳數為6至10之芳香羥基、碳數為5至10之雜芳香基。再者，Q亦可代表經鹵素原子、-Z6、-OH、-OZ6、-NO2、-CH=CH2或-CH=CH-Z6所取代之碳數為6至10之芳香羥基，或者經鹵素原子、-Z6、-OH、-OZ6、-NO2、-CH=CH2或-CH=CH-Z6 所取代之碳數為5至10之雜芳香基，其中Z6之定義如前所述，在此不另贅述。 The aforementioned Z 8 and Z 9 each independently represent a linear alkyl group, a branched alkyl group or a cycloalkyl group having a carbon number of 1 to 10, or -Q. The Q represents an aromatic hydroxy group having 6 to 10 carbon atoms and a heteroaryl group having 5 to 10 carbon atoms. Further, Q may also represent an aromatic having a carbon number of 6 to 10 substituted by a halogen atom, -Z 6 , -OH, -OZ 6 , -NO 2 , -CH=CH 2 or -CH=CH-Z 6 . a hydroxy group, or a heteroaryl group having a carbon number of 5 to 10, which is substituted by a halogen atom, -Z 6 , -OH, -OZ 6 , -NO 2 , -CH=CH 2 or -CH=CH-Z 6 , wherein The definition of Z 6 is as described above, and will not be further described herein.

添加劑(G)Additive (G)

為滿足彩色濾光片片段之物性及化性需求，本發明之感光性樹脂組成物可選擇性地包含添加劑(G)，例如：填充劑、前述鹼可溶性樹脂(B)以外之高分子化合物、密著促進劑、抗氧化劑、紫外線吸收劑或防凝集劑等。 In order to satisfy the physical properties and chemical properties of the color filter segment, the photosensitive resin composition of the present invention may optionally contain an additive (G) such as a filler, a polymer compound other than the alkali-soluble resin (B), Adhesion promoter, antioxidant, ultraviolet absorber or anti-agglomerating agent.

該添加劑(G)可包含但不限於玻璃或鋁等之填充劑；聚乙烯醇、聚乙二醇單烷基醚或聚氟丙烯酸烷酯等鹼可溶性樹脂(B)以外之高分子化合物；乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基三(2-甲氧乙氧基)矽烷、N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-環氧丙醇丙基三甲氧基矽烷、3-環氧丙醇丙基甲基二甲氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-氯丙基甲基二甲氧基矽烷、3-氯丙基三甲氧基矽烷、3-甲基丙烯氧基丙基三甲氧基矽烷或3-硫醇基丙基三甲氧基矽烷等之密著促進劑；2,2-硫代雙(4-甲基-6-第三丁基苯酚)或2,6-二-第三丁基苯酚等抗氧化劑；2-(3-第三丁基-5-甲基-2-羥基苯基)-5-氯苯基疊氮或烷氧基苯酮等之紫外線吸收劑；聚丙烯酸鈉等之防凝集劑。 The additive (G) may include, but is not limited to, a filler such as glass or aluminum; a polymer compound other than the alkali-soluble resin (B) such as polyvinyl alcohol, polyethylene glycol monoalkyl ether or polyfluoroalkyl acrylate; Trimethoxy decane, vinyl triethoxy decane, vinyl tris(2-methoxyethoxy) decane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxy Baseline, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidylpropyltrimethoxydecane, 3-glycidylpropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3- a adhesion promoter such as chloropropyltrimethoxydecane, 3-methacryloxypropyltrimethoxydecane or 3-thiolpropyltrimethoxydecane; 2,2-thiobis(4- Antioxidant such as methyl-6-tert-butylphenol or 2,6-di-tert-butylphenol; 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5 An ultraviolet absorber such as a chlorophenyl azide or an alkoxybenzophenone; an anti-agglomerating agent such as sodium polyacrylate.

感光性樹脂組成物之製備Preparation of photosensitive resin composition

本發明之彩色濾光片用感光性樹脂組成物的製備 方法係將上述之顏料(A)、鹼可溶性樹脂(B)、具有乙烯性不飽和基之化合物(C)、光起始劑(D)及有機溶劑(E)放置於攪拌器中攪拌，使其均勻混合成溶液狀態，必要時亦可選擇性地添加染料(F)，或者填充劑、鹼可溶性樹脂(B)以外之高分子化合物、密著促進劑、抗氧化劑、紫外線吸收劑或防凝集劑等之添加劑(G)。 Preparation of photosensitive resin composition for color filter of the present invention The method comprises placing the above-mentioned pigment (A), an alkali-soluble resin (B), a compound (C) having an ethylenically unsaturated group, a photoinitiator (D), and an organic solvent (E) in a stirrer to be stirred. It is uniformly mixed into a solution state, and if necessary, a dye (F) or a filler, a polymer compound other than the alkali-soluble resin (B), a adhesion promoter, an antioxidant, an ultraviolet absorber, or an anti-agglomeration may be selectively added. Additives such as agents (G).

基於鹼可溶性樹脂(B)之總使用量為100重量份，顏料(A)之使用量為30重量份至300重量份，具有乙烯性不飽和基之化合物(C)之使用量為60重量份至600重量份，光起始劑(D)之使用量為10重量份至100重量份，且有機溶劑(E)之使用量為500重量份至5000重量份。 The total amount of the alkali-soluble resin (B) used is 100 parts by weight, the pigment (A) is used in an amount of 30 parts by weight to 300 parts by weight, and the compound (C) having an ethylenically unsaturated group is used in an amount of 60 parts by weight. The photoinitiator (D) is used in an amount of 10 parts by weight to 100 parts by weight to 600 parts by weight, and the organic solvent (E) is used in an amount of 500 parts by weight to 5000 parts by weight.

彩色濾光片之製備Preparation of color filters

本發明之彩色濾光片的製備係利用前述彩色濾光片用感光性樹脂組成物形成畫素層，並利用此方法製得彩色濾光片。 The color filter of the present invention is prepared by forming a pixel layer using the photosensitive resin composition for a color filter described above, and a color filter is produced by this method.

本發明之彩色濾光片之製備主要係藉由迴轉塗佈、流延塗佈、噴墨塗佈(ink-jet)或輥式塗佈等塗佈方式，將混合成溶液狀態之前述彩色濾光片用感光性樹脂組成物塗佈在基板上。於塗佈後，先以減壓乾燥之方式，去除大部分之溶劑，並以預烤(pre-bake)之方式去除溶劑而形成一預烤塗膜。其中，減壓乾燥及預烤之條件，依各成份之種類，配方比率而不同。減壓乾燥一般是在0至200mmHg之壓力下進行1秒鐘至60秒鐘，而預烤一般是在70℃至110℃ 溫度下進行1分鐘至15分鐘。然後，將該預烤塗膜放置於指定之光罩(mask)下曝光，其中曝光所使用之光線，以g線、b線、i線等之紫外線為佳，而紫外線裝置可為(超)高壓水銀燈或金屬鹵素燈。接著，於23±2℃溫度下將曝光後之預烤塗膜浸漬於顯影液15秒至5分鐘進行顯影，以去除不要之部分而形成圖案，而形成具有光硬化塗膜層的基板。 The color filter of the present invention is mainly prepared by a coating method such as rotary coating, cast coating, ink-jet coating or roll coating, and the color filter mixed in a solution state. The light sheet is coated on the substrate with a photosensitive resin composition. After coating, most of the solvent is removed by drying under reduced pressure, and the solvent is removed by pre-bake to form a pre-baked coating film. Among them, the conditions of drying under reduced pressure and pre-baking vary depending on the type of each component and the formulation ratio. Drying under reduced pressure is generally carried out at a pressure of 0 to 200 mmHg for 1 second to 60 seconds, while prebaking is generally carried out at 70 ° C to 110 ° C. The temperature is carried out for 1 minute to 15 minutes. Then, the pre-baked coating film is exposed to a designated mask, wherein the light used for the exposure is preferably ultraviolet rays such as g-line, b-line, i-line, etc., and the ultraviolet device can be (super) High pressure mercury lamp or metal halide lamp. Next, the exposed pre-baked coating film is immersed in a developing solution at a temperature of 23±2° C. for 15 seconds to 5 minutes to perform development, and a pattern is formed by removing unnecessary portions to form a substrate having a photo-curable coating layer.

前述基板之具體例，如：用於液晶顯示裝置等之無鹼玻璃、鈉鈣玻璃、硬質玻璃(派勒斯玻璃)、石英玻璃、於此些玻璃上附著透明導電膜者，或者用於固體攝影裝置等之光電變換裝置基板(如：矽基板)等等。此等基板一般係先形成隔離各畫素著色層之黑色矩陣(black matrix)。 Specific examples of the substrate include an alkali-free glass, a soda lime glass, a hard glass (Pyrus glass), a quartz glass, a transparent conductive film attached to such a glass, or a solid for a liquid crystal display device. A photoelectric conversion device substrate (such as a germanium substrate) of a photographing device or the like. These substrates generally form a black matrix that separates the colored layers of each pixel.

再者，顯影液之具體例，如：氫氧化鈉、氫氧化鉀、碳酸鈉、碳酸氫鈉、碳酸鉀、碳酸氫鉀、矽酸鈉、甲基矽酸鈉、氨水、乙胺、二乙胺、二甲基乙醇胺、氫氧化四甲銨、氫氧化四乙銨、膽鹼、吡咯、呱啶或1,8-二氮雜二環-(5,4,0)-7-十一烯等鹼性化合物所構成之鹼性水溶液，其濃度一般為0.001重量百分比至10重量百分比，較佳為0.005重量百分比至5重量百分比，更佳為0.01重量百分比至1重量百分比。 Further, specific examples of the developer, such as: sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, potassium hydrogencarbonate, sodium citrate, sodium methyl citrate, ammonia, ethylamine, diethyl Amine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, acridine or 1,8-diazabicyclo-(5,4,0)-7-undecene The alkaline aqueous solution of the basic compound is generally present in a concentration of from 0.001% by weight to 10% by weight, preferably from 0.005% by weight to 5% by weight, more preferably from 0.01% by weight to 1% by weight.

於使用前述鹼性水溶液所構成之顯影液時，一般係於顯影後以水洗淨，並以壓縮空氣或壓縮氮氣風乾圖案。 When the developer composed of the above alkaline aqueous solution is used, it is usually washed with water after development, and air-dried with compressed air or compressed nitrogen.

於風乾具有光硬化塗膜層的基板後，利用熱板或烘箱等加熱裝置，在溫度100至280℃下加熱該基板1至15分鐘，以去除塗膜中的揮發性成分，並使塗膜中未反應的 乙烯性不飽和雙鍵進行熱硬化反應。使用各色(主要包括紅、綠、藍三色)之感光性樹脂組成物在預定的畫素上以同樣的步驟重複操作三次，即可得到紅、綠、藍三色之光硬化畫素著色層。 After drying the substrate having the photo-curable coating layer, the substrate is heated at a temperature of 100 to 280 ° C for 1 to 15 minutes by a heating means such as a hot plate or an oven to remove volatile components in the coating film and to coat the coating film. Unreacted The ethylenically unsaturated double bond undergoes a thermosetting reaction. The photosensitive resin composition of each color (mainly including red, green, and blue colors) is repeatedly operated in the same step three times on a predetermined pixel to obtain a light-hardened pixel coloring layer of red, green, and blue colors. .

其次，在前述之畫素著色層上，以220℃至250℃之溫度於真空下形成ITO(氧化銦錫)蒸鍍膜。必要時，對ITO蒸鍍膜進行蝕刻暨佈線，並塗佈液晶配向膜用聚醯亞胺，進而燒成之，即可製得液晶顯示器用之彩色濾光片。 Next, an ITO (Indium Tin Oxide) deposited film was formed under vacuum at a temperature of 220 ° C to 250 ° C on the above-mentioned pixel coloring layer. If necessary, the ITO vapor-deposited film is etched and wired, and the polyimine for the liquid crystal alignment film is applied and fired to obtain a color filter for a liquid crystal display.

液晶顯示裝置之製備Preparation of liquid crystal display device

本發明之液晶顯示裝置包含前述之彩色濾光片。 The liquid crystal display device of the present invention comprises the aforementioned color filter.

本發明之液晶顯示裝置主要係由前述方法所製得之彩色濾光片基板及設置有薄膜電晶體(Thin Film Transistor；TFT)之驅動基板所構成，其中在上述2片基板間介入間隙(晶胞間隔；cell gap)作對向配置，且用封止劑貼合2片基板的周圍部位。然後，在2片基板之表面及封止劑所區分出的間隙內充填注入液晶，並封住注入孔，以形成液晶晶胞(cell)。接著，在液晶晶胞的外表面，亦即構成液晶晶胞的各個基板的其他側面上，貼合偏光板，以製得液晶顯示裝置。 The liquid crystal display device of the present invention is mainly composed of a color filter substrate prepared by the above method and a driving substrate provided with a thin film transistor (TFT), wherein a gap is interposed between the two substrates (crystal The cell gap is arranged in the opposite direction, and the surrounding portion of the two substrates is bonded with a sealing agent. Then, the liquid crystal is filled in the gap between the surface of the two substrates and the sealant, and the injection hole is sealed to form a liquid crystal cell. Next, a polarizing plate is bonded to the outer surface of the liquid crystal cell, that is, the other side surface of each of the substrates constituting the liquid crystal cell, to obtain a liquid crystal display device.

以下利用數個實施方式以說明本發明之應用，然其並非用以限定本發明，本發明技術領域中具有通常知識者，在不脫離本發明之精神和範圍內，當可作各種之更動與潤飾。 The following embodiments are used to illustrate the application of the present invention, and are not intended to limit the present invention. Those skilled in the art can make various changes without departing from the spirit and scope of the present invention. Retouching.

製備第一鹼可溶性樹脂(B-1)Preparation of first alkali soluble resin (B-1)

以下係根據第1表製備合成例B-1-1至B-1-8之第一鹼可溶性樹脂。 The first alkali-soluble resin of Synthesis Examples B-1-1 to B-1-8 was prepared according to Table 1 below.

合成例B-1-1Synthesis Example B-1-1

將3重量份之1,2,2,6,6-五甲基-哌啶基丙烯酸甲酯(以下簡稱為FA-711MM)、45重量份之2-甲基丙烯醯乙氧基丁二酸酯(以下簡稱為HOMS)、12重量份之雙環戊烯基丙烯酸酯(以下簡稱為FA-511A)、20重量份之苯乙烯(以下簡稱為SM)、5重量份之苯甲基甲基丙烯酸酯(以下簡稱為BzMA)、15重量份之甲基丙烯酸甲酯(以下簡稱為MMA)、4重量份之2,2’-偶氮雙-2-甲基丁腈(以下簡稱為AMBN)及200重量份之3-乙氧基丙酸乙酯(以下簡稱為EEP)連續添加至500mL的四口燒瓶中，且入料速度控制在25重量份/分鐘，將溫度維持在100℃。反應6小時後，即可獲得第一鹼可溶性樹脂(B-1-1)。 3 parts by weight of methyl 1,2,2,6,6-pentamethyl-piperidinyl acrylate (hereinafter abbreviated as FA-711MM), 45 parts by weight of 2-methylpropenyl ethoxy succinic acid Ester (hereinafter abbreviated as HOMS), 12 parts by weight of dicyclopentenyl acrylate (hereinafter abbreviated as FA-511A), 20 parts by weight of styrene (hereinafter abbreviated as SM), and 5 parts by weight of benzyl methacrylic acid Ester (hereinafter abbreviated as BzMA), 15 parts by weight of methyl methacrylate (hereinafter abbreviated as MMA), 4 parts by weight of 2,2'-azobis-2-methylbutyronitrile (hereinafter abbreviated as AMBN) and 200 parts by weight of ethyl 3-ethoxypropionate (hereinafter abbreviated as EEP) was continuously added to a 500 mL four-necked flask, and the feed rate was controlled at 25 parts by weight/minute, and the temperature was maintained at 100 °C. After reacting for 6 hours, the first alkali-soluble resin (B-1-1) was obtained.

合成例B-1-2至B-1-8Synthesis Examples B-1-2 to B-1-8

合成例B-1-2至B-1-8係使用與合成例B-1-1之第一鹼可溶性樹脂之製作方法相同的製備方法，不同之處在於合成例B-1-2至B-1-8係改變第一鹼可溶性樹脂中原料的種類與使用量及聚合條件，且其配方及聚合條件如第1表所示，在此不另贅述。 Synthesis Examples B-1-2 to B-1-8 The same preparation methods as those of the first alkali-soluble resin of Synthesis Example B-1-1 were used, except that Synthesis Examples B-1-2 to B were used. -1-8 is a modification of the kind, usage amount, and polymerization conditions of the raw material in the first alkali-soluble resin, and the formulation and polymerization conditions are as shown in Table 1, and will not be further described herein.

製備第二鹼可溶性樹脂(B-2)Preparation of a second alkali soluble resin (B-2)

合成例B-2-1Synthesis Example B-2-1

首先，將100重量份的茀環氧化合物(新日鐵化學公司製造，型號為ESF-300之商品，且其環氧當量為231)、30重量份的丙烯酸、0.3重量份的氯化苄基三乙基銨、0.1重量份的2,6-二第三丁基對甲酚及130重量份的丙二醇單甲醚醋酸酯以連續式添加方式加入至500毫升的四頸燒瓶中。入料速度控制在25重量份/分鐘，並且反應過程的溫度維持在100℃至110℃。反應15小時後，即可獲得固成分濃度為50重量百分比的淡黃色透明混合液。 First, 100 parts by weight of a ruthenium epoxy compound (manufactured by Nippon Steel Chemical Co., Ltd., model ESF-300, and having an epoxy equivalent of 231), 30 parts by weight of acrylic acid, and 0.3 parts by weight of benzyl chloride Triethylammonium, 0.1 part by weight of 2,6-di-t-butyl-p-cresol and 130 parts by weight of propylene glycol monomethyl ether acetate were added in a continuous manner to a 500 ml four-necked flask. The feed rate was controlled at 25 parts by weight/minute, and the temperature of the reaction process was maintained at 100 ° C to 110 ° C. After 15 hours of reaction, a pale yellow transparent mixture having a solid concentration of 50% by weight was obtained.

接著，將100重量份的上述混合液添加至25重量份的乙二醇***醋酸酯中，同時添加6重量份的四氫鄰苯二甲酸酐及13重量份的二苯甲酮四甲酸二酐，並加熱至110℃至115℃。反應2小時後，即可製得第二鹼可溶性樹脂(B-2-1)，其酸價為98mgKOH/g，且重量平均分子量為2205。 Next, 100 parts by weight of the above mixture was added to 25 parts by weight of ethylene glycol ethyl ether acetate, while 6 parts by weight of tetrahydrophthalic anhydride and 13 parts by weight of benzophenone tetracarboxylic dianhydride were added. And heated to 110 ° C to 115 ° C. After reacting for 2 hours, a second alkali-soluble resin (B-2-1) having an acid value of 98 mgKOH/g and a weight average molecular weight of 2,205 was obtained.

合成例B-2-2Synthesis Example B-2-2

將100重量份的茀環氧化合物(新日鐵化學公司製造，型號為ESF-300之商品，且其環氧當量為231)、30重量份的丙烯酸、0.3重量份的氯化苄基三乙基銨、0.1重量份的2,6-二第三丁基對甲酚及130重量份的丙二醇單甲醚醋酸酯連續添加至500毫升的四頸燒瓶中。入料速度控制在25重量份/分鐘，且反應過程的溫度維持在100℃至110℃。反應15小時後，即可獲得固體成分濃度為50重量百分比之淡黃色透明混合液。 100 parts by weight of a ruthenium epoxy compound (manufactured by Nippon Steel Chemical Co., Ltd., model ESF-300, and having an epoxy equivalent of 231), 30 parts by weight of acrylic acid, and 0.3 parts by weight of benzyltriethyl chloride The ammonium complex, 0.1 part by weight of 2,6-di-t-butyl-p-cresol and 130 parts by weight of propylene glycol monomethyl ether acetate were continuously added to a 500-ml four-necked flask. The feed rate was controlled at 25 parts by weight/minute, and the temperature of the reaction process was maintained at 100 ° C to 110 ° C. After reacting for 15 hours, a pale yellow transparent mixture having a solid concentration of 50% by weight was obtained.

接著，將100重量份之上述混合液溶加至25重量份的乙二醇***醋酸酯中，同時添加13重量份的二苯甲酮四甲酸二酐，並加熱至90℃至95℃。反應2小時後，加入6重量份的四氫鄰苯二甲酸酐，且於90℃至95℃下反應4小時，即可製得第二鹼可溶性樹脂(B-2-2)，其酸價為99.0mgKOH/g，且重量平均分子量為2630。 Next, 100 parts by weight of the above mixed solution was added to 25 parts by weight of ethylene glycol ethyl ether acetate while 13 parts by weight of benzophenonetetracarboxylic dianhydride was added, and heated to 90 ° C to 95 ° C. After reacting for 2 hours, 6 parts by weight of tetrahydrophthalic anhydride is added, and the reaction is carried out at 90 ° C to 95 ° C for 4 hours to obtain a second alkali-soluble resin (B-2-2) having an acid value. It was 99.0 mgKOH/g, and the weight average molecular weight was 2630.

合成例B-2-3Synthesis Example B-2-3

將400重量份的環氧化合物(日本化藥公司製造，型號為NC-3000之商品，且其環氧當量為288)、102重量份的丙烯酸、0.3重量份的甲氧基酚(methoxyphenol)、5重量份的三苯基膦及264重量份的丙二醇單甲醚醋酸酯加至反應瓶中，並將溫度維持在95℃。反應9小時後，即可獲得中間產物，其酸價為2.2mgKOH/g。接著，加入151重量份的四氫鄰苯二甲酸酐(tetrahydrophthalic anhydride)，並在95℃下反應4小時，即可製得第二鹼可溶性樹脂(B-2-3)，其酸價為102mgKOH/g，且重量平均分子量為3200。 400 parts by weight of an epoxy compound (manufactured by Nippon Kayaku Co., Ltd., model number NC-3000, and having an epoxy equivalent of 288), 102 parts by weight of acrylic acid, 0.3 parts by weight of methoxyphenol, 5 parts by weight of triphenylphosphine and 264 parts by weight of propylene glycol monomethyl ether acetate were added to the reaction flask, and the temperature was maintained at 95 °C. After 9 hours of reaction, an intermediate product having an acid value of 2.2 mgKOH/g was obtained. Next, 151 parts by weight of tetrahydrophthalic anhydride was added and reacted at 95 ° C for 4 hours to obtain a second alkali-soluble resin (B-2-3) having an acid value of 102 mgKOH. /g, and the weight average molecular weight is 3,200.

製備第三鹼可溶性樹脂(B-3)Preparation of a third alkali soluble resin (B-3)

以下係根據第2表製備合成例B-3-1至B-3-4之第三鹼可溶性樹脂。 The third alkali-soluble resin of Synthesis Examples B-3-1 to B-3-4 was prepared according to Table 2 below.

合成例B-3-1Synthesis Example B-3-1

在一容積1000毫升之四頸錐瓶上設置氮氣入口、攪拌器、加熱器、冷凝管及溫度計，並導入氮氣。於氮氣之環境下，將45重量份之2-甲基丙烯醯乙氧基丁二酸酯(以下簡稱為HOMS)、15重量份之雙環戊烯基丙烯酸酯(以下 簡稱為FA-511A)、20重量份之苯乙烯(以下簡稱為SM)、5重量份之苯甲基甲基丙烯酸酯(以下簡稱為BzMA)、15重量份之甲基丙烯酸甲酯(以下簡稱為MMA)及200重量份之3-乙氧基丙酸乙酯(以下簡稱為EEP)連續添加至四頸錐瓶中，並混合均勻。然後，將油浴之溫度提升至100℃，並將4重量份的2,2’-偶氮雙-2-甲基丁腈(以下簡稱為AMBN)溶於3-乙氧基丙酸乙酯中，將其平分成五等份的重量，並於1小時內添加至四頸錐瓶中。聚合過程中之反應溫度係維持100℃，並反應6小時。接著，自四頸錐瓶中取出聚合產物，並去除溶劑，即得到第三鹼可溶性樹脂(B-3-1)。 A nitrogen inlet, a stirrer, a heater, a condenser, and a thermometer were placed on a four-necked flask of 1000 ml volume, and nitrogen gas was introduced. 45 parts by weight of 2-methylpropenyl ethoxy succinate (hereinafter abbreviated as HOMS) and 15 parts by weight of dicyclopentenyl acrylate (hereinafter referred to as nitrogen) Abbreviated as FA-511A), 20 parts by weight of styrene (hereinafter abbreviated as SM), 5 parts by weight of benzyl methacrylate (hereinafter abbreviated as BzMA), and 15 parts by weight of methyl methacrylate (hereinafter referred to as MMA) and 200 parts by weight of ethyl 3-ethoxypropionate (hereinafter referred to as EEP) were continuously added to a four-necked flask and uniformly mixed. Then, the temperature of the oil bath was raised to 100 ° C, and 4 parts by weight of 2,2'-azobis-2-methylbutyronitrile (hereinafter abbreviated as AMBN) was dissolved in ethyl 3-ethoxypropionate. In the middle, it was divided into five equal parts and added to a four-necked flask within one hour. The reaction temperature during the polymerization was maintained at 100 ° C and reacted for 6 hours. Next, the polymerization product was taken out from the four-necked flask and the solvent was removed to obtain a third alkali-soluble resin (B-3-1).

合成例B-3-2至B-3-4Synthesis Example B-3-2 to B-3-4

合成例B-3-2至B-3-4係使用與合成例B-3-1之第三鹼可溶性樹脂之製作方法相同的製備方法，不同之處在於合成例B-3-2至B-3-4係改變第三鹼可溶性樹脂中原料的種類與使用量及聚合條件，且其配方及聚合條件如第2表所示，在此不另贅述。 Synthesis Examples B-3-2 to B-3-4 were prepared in the same manner as in the production method of the third alkali-soluble resin of Synthesis Example B-3-1 except that Synthesis Example B-3-2 to B The -3-4 system changes the kind, the amount of use, and the polymerization conditions of the raw materials in the third alkali-soluble resin, and the formulation and polymerization conditions are as shown in Table 2, and are not described herein.

製備感光性樹脂組成物Preparation of photosensitive resin composition

以下係根據第3及4表製備實施例1至11及比較例1至6之感光性樹脂組成物。 The photosensitive resin compositions of Examples 1 to 11 and Comparative Examples 1 to 6 were prepared according to Tables 3 and 4 below.

實施例1Example 1

將30重量份之顏料(A-1，其中C.I.Pigment R254與C.I.Pigment Yellow139之比例為80/20)、10重量份前述合成例B-1-1所製得之第一鹼可溶性樹脂(以下簡稱為 B-1-1)、90重量份前述合成例B-2-1所製得之第二鹼可溶性樹脂(以下簡稱為B-2-1)、40重量份之二季戊四醇六丙烯酸酯(東亞合成公司製造，以下簡稱為C-1)、3重量份之2-甲基-1-(4-甲基硫代苯基)-2-嗎啉代-1-丙酮(以下簡稱為D-1)、3重量份之2,2’-雙(2,4-二氯苯箕)-4,4’,5,5’-四苯基二咪唑(以簡稱為D-2)及4重量份之4,4’-雙(二乙胺)二苯甲酮(以下簡稱為D-3)，加至500重量份之3-乙氧基丙酸乙酯(以下簡稱為E-1)中，以搖動式攪拌器溶解混合，即可製得實施例1之彩色濾光片用感光性樹脂組成物。所得之彩色濾光片用感光性樹脂組成物以下列之各評價方式進行評價，所得結果如第3表所示，其中耐顯影性及電壓保持率之檢測方法容後再述。 30 parts by weight of the pigment (A-1, wherein the ratio of CIPigment R254 to CIPigment Yellow 139 is 80/20), 10 parts by weight of the first alkali-soluble resin obtained in the above Synthesis Example B-1-1 (hereinafter referred to as for B-1-1), 90 parts by weight of the second alkali-soluble resin (hereinafter abbreviated as B-2-1) obtained in the above Synthesis Example B-2-1, and 40 parts by weight of dipentaerythritol hexaacrylate (East Asia Synthesis) Manufactured by the company, hereinafter referred to as C-1), 3 parts by weight of 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone (hereinafter referred to as D-1) 3 parts by weight of 2,2'-bis(2,4-dichlorophenylhydrazine)-4,4',5,5'-tetraphenyldiimidazole (abbreviated as D-2) and 4 parts by weight 4,4'-bis(diethylamine)benzophenone (hereinafter abbreviated as D-3), added to 500 parts by weight of ethyl 3-ethoxypropionate (hereinafter referred to as E-1) to The photosensitive resin composition for a color filter of Example 1 was obtained by dissolving and mixing the shaker. The photosensitive resin composition obtained by the color filter was evaluated by the following evaluation methods, and the obtained result is shown in the third table, and the detection method of the development resistance and the voltage retention rate will be described later.

實施例2至11及比較例1至6Examples 2 to 11 and Comparative Examples 1 to 6

實施例2至11及比較例1至6係使用與實施例1之感光性樹脂組成物的製作方法相同之製備方法，不同之處在於實施例2至11及比較例1至6係改變感光性樹脂組成物中原料的種類及使用量，且其配方及評價結果分別如第3與4表所示，在此不另贅述。 In Examples 2 to 11 and Comparative Examples 1 to 6, the same production method as that of the photosensitive resin composition of Example 1 was used, except that Examples 2 to 11 and Comparative Examples 1 to 6 changed the photosensitivity. The type and amount of the raw materials in the resin composition, and the formulations and evaluation results thereof are shown in Tables 3 and 4, respectively, and will not be further described herein.

評價方式Evaluation method 1. 耐顯影性Development resistance

將溶液態之彩色濾光片用感光性樹脂組成物以旋轉塗佈的方式塗佈在尺寸為100mm×100mm的玻璃基板上，並於約100mmHg的壓力下進行減壓乾燥約30秒鐘。 然後，於溫度80℃下預烤2分鐘，藉以形成膜厚2.5μm的預烤塗膜。接著，以色度計(大塚電子公司製造，型號為MCPD)測定其色度(L*，a*，b*)。 The color filter of the solution state was applied onto a glass substrate having a size of 100 mm × 100 mm by spin coating using a photosensitive resin composition, and dried under reduced pressure at a pressure of about 100 mmHg for about 30 seconds. Then, it was prebaked at a temperature of 80 ° C for 2 minutes to form a prebaked coating film having a film thickness of 2.5 μm. Next, the chromaticity (L*, a*, b*) was measured with a colorimeter (manufactured by Otsuka Electronics Co., Ltd., model: MCPD).

之後，以紫外光曝光機(Canon製造，型號為PLA-501F)照射上述之預烤塗膜，其中紫外光曝光機的光強度設定為100mJ/cm2。然後，將預烤塗膜浸漬於23℃的顯影液1分鐘。以純水洗淨後，再次測定其色度，利用下式(V)計算色度變化(△Eab*)，並根據下述基準進行評價，其中所得到的色度變化(△Eab*)越小，表示耐顯影性越好：△Eab*=[(△L)2+(△a)2+(△b)2]½ 式(V) Thereafter, the above prebaked coating film was irradiated with an ultraviolet light exposure machine (manufactured by Canon, model: PLA-501F), wherein the light intensity of the ultraviolet light exposure machine was set to 100 mJ/cm 2 . Then, the prebaked coating film was immersed in a developing solution at 23 ° C for 1 minute. After washing with pure water, the chromaticity was measured again, and the chromaticity change (ΔEab*) was calculated by the following formula (V), and evaluated according to the following criteria, wherein the obtained chromaticity change (ΔEab*) was more Small, indicating better development resistance: △Eab * =[(ΔL) 2 +(△a) 2 +(△b) 2 ] 1⁄2 (V)

◎：△Eab*<2。 ◎: ΔEab*<2.

○：2≦△Eab*<4。 ○: 2≦△Eab*<4.

△：4≦△Eab*<6。 △: 4 ≦ ΔEab* < 6.

×：6≦△Eab*。 ×: 6≦△Eab*.

2. 電壓保持率2. Voltage retention rate

形成用以防止鈉離子溶出之SiO2膜，並進一步於鈉鈣玻璃基板上蒸鍍預定圖案之銦錫氧化物(Inidium Tin Oxide；ITO)電極。將前述實施例1至11及比較例1至6所製得之感光性樹脂組成物以旋轉塗佈之方式塗佈於上述玻璃基板上。然後，以100℃之溫度進行預烤1分鐘，以形成膜厚為2.0μm之預烤塗膜。接著，不覆蓋光罩，並以700J/m2之光照射前述之預烤塗膜。將曝光後之塗膜浸置於溫度為23℃，且濃度為0.04重量百分比之氫氧化鉀所形成 之顯影液中。經過1分鐘後，用超純水洗滌並風乾。然後，以230℃之溫度對顯影後之塗膜後烤30分鐘，而形成硬化塗膜。 An SiO 2 film for preventing sodium ions from eluting is formed, and an indium tin oxide (ITO) electrode of a predetermined pattern is further deposited on the soda lime glass substrate. The photosensitive resin compositions obtained in the above Examples 1 to 11 and Comparative Examples 1 to 6 were applied onto the glass substrate by spin coating. Then, prebaking was performed at a temperature of 100 ° C for 1 minute to form a prebaked coating film having a film thickness of 2.0 μm. Next, the mask was not covered, and the aforementioned prebaked coating film was irradiated with light of 700 J/m 2 . The exposed coating film was immersed in a developing solution of potassium hydroxide having a temperature of 23 ° C and a concentration of 0.04% by weight. After 1 minute, it was washed with ultrapure water and air dried. Then, the film after development was baked at a temperature of 230 ° C for 30 minutes to form a hard coat film.

接著，利用封止劑黏結前述硬化塗膜所形成之畫素基板及已蒸鍍預定圖案之ITO電極，並將粒徑為1.8mm之玻璃珠放置於兩者之間。將液晶材料(默克公司製造，其型號為MLC6608之液晶材料)注入前述封止劑、畫素基板及ITO電極之間的間隙，以形成液晶晶胞。 Next, the pixel substrate formed of the cured coating film and the ITO electrode having a predetermined pattern were deposited by a sealing agent, and a glass bead having a particle diameter of 1.8 mm was placed between the two. A liquid crystal material (manufactured by Merck, a liquid crystal material of the type MLC6608) was injected into a gap between the sealing agent, the pixel substrate, and the ITO electrode to form a liquid crystal cell.

然後，將所製得之液晶晶胞放置於60℃之恆溫器中，並以液晶電壓保持率測定儀器(東洋株式會社製造，型號為VHR-1A型之儀器)量測所製得之液晶晶胞的電壓保持率。測量之電壓為5.5伏特之方波，且其量測頻率為60Hz。 Then, the obtained liquid crystal cell was placed in a thermostat at 60 ° C, and the liquid crystal crystal obtained by measuring the liquid crystal voltage holding ratio measuring instrument (manufactured by Toyo Co., Ltd., model VHR-1A type) was measured. Cell voltage retention. The measured voltage is a square wave of 5.5 volts and its measurement frequency is 60 Hz.

前述之電壓保持率係代表一數值，且此數值係代表(液晶晶胞經過16.7毫秒後之電位差/液晶晶胞於0毫秒所施加之電壓)。當液晶晶胞之電壓保持率不超過90%時，所製得之液晶晶胞於16.7毫秒內無法穩定保持電壓，而使得液晶晶胞中之液晶分子容易產生殘影之缺陷。前述實施例1至11及比較例1至6所測得之電壓保持率依據以下基準進行評價：◎：95%<電壓保持率≦100%。 The aforementioned voltage holding ratio represents a value, and this value represents (the potential difference after the liquid crystal cell passes after 16.7 milliseconds / the voltage applied by the liquid crystal cell at 0 milliseconds). When the voltage holding ratio of the liquid crystal cell is not more than 90%, the obtained liquid crystal cell cannot stably maintain the voltage within 16.7 milliseconds, and the liquid crystal molecules in the liquid crystal cell are liable to cause defects of image sticking. The voltage holding ratios measured in the above Examples 1 to 11 and Comparative Examples 1 to 6 were evaluated in accordance with the following criteria: ◎: 95% < voltage holding ratio ≦ 100%.

○：90%<電壓保持率≦95%。 ○: 90% < voltage holding ratio ≦ 95%.

△：80%<電壓保持率≦90%。 △: 80% < voltage holding ratio ≦ 90%.

×：電壓保持率≦80%。 ×: The voltage holding ratio is ≦80%.

由第3與4表之結果可知，當本發明之感光性樹脂組成物中之鹼可溶性樹脂(B)包含第一鹼可溶性樹脂(B-1)時，所製得之感光性樹脂組成物具有較佳之電壓保持率。其次，當鹼可溶性樹脂(B)包含第二鹼可溶性樹脂(B-2)時，所製得之感光性樹脂組成物具有較佳之耐顯影性。 As is apparent from the results of the third and fourth tables, when the alkali-soluble resin (B) in the photosensitive resin composition of the present invention contains the first alkali-soluble resin (B-1), the obtained photosensitive resin composition has The preferred voltage retention. Next, when the alkali-soluble resin (B) contains the second alkali-soluble resin (B-2), the obtained photosensitive resin composition has better developability.

再者，當鹼可溶性樹脂(B)中之第一鹼可溶性樹脂(B-1)與第二鹼可溶性樹脂(B-2)的重量比為10/90至90/10時，所製得之感光性樹脂組成物具有更佳之耐顯影性。 Further, when the weight ratio of the first alkali-soluble resin (B-1) to the second alkali-soluble resin (B-2) in the alkali-soluble resin (B) is from 10/90 to 90/10, The photosensitive resin composition has better developability.

需補充的是，本發明雖以特定的化合物、組成、反應條件、製程、分析方法或特定儀器作為例示，說明本發明之彩色濾光片用感光性樹脂組成物及其應用，惟本發明所屬技術領域中任何具有通常知識者可知，本發明並不限於此，在不脫離本發明之精神和範圍內，本發明之彩色濾光片用感光性樹脂組成物及其應用亦可使用其他的化合物、組成、反應條件、製程、分析方法或儀器進行。 It should be noted that the present invention describes a photosensitive resin composition for a color filter of the present invention and an application thereof by using specific compounds, compositions, reaction conditions, processes, analytical methods, or specific instruments as examples, but the present invention belongs to It is to be understood by those skilled in the art that the present invention is not limited thereto, and other compounds may be used for the photosensitive resin composition for color filters of the present invention and applications thereof without departing from the spirit and scope of the present invention. , composition, reaction conditions, process, analytical methods or instruments.

雖然本發明已以實施方式揭露如上，然其並非用以限定本發明，在本發明所屬技術領域中任何具有通常知識者，在不脫離本發明之精神和範圍內，當可作各種之更動與潤飾，因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。 The present invention has been disclosed in the above embodiments, and is not intended to limit the present invention. Any one of ordinary skill in the art to which the present invention pertains can make various changes without departing from the spirit and scope of the invention. The scope of protection of the present invention is therefore defined by the scope of the appended claims.

Claims (6)

一種彩色濾光片用感光性樹脂組成物，包含：一顏料(A)；一鹼可溶性樹脂(B)，包含：一第一鹼可溶性樹脂(B-1)，具有如下式(I)所示之受阻胺結構： 於該式(I)中，該X1代表氫原子、碳數為1至18之直鏈烷基、支鏈烷基或環烷基、碳數為6至20之芳香基、碳數為7至12之芳香烷基、醯基、氧自由基，或者-OX4；該X4代表氫原子、碳數為1至18之直鏈烷基、支鏈烷基或環烷基、碳數為6至20之芳香基，或者碳數為7至12之芳香烷基；該X2及該X3各自獨立地代表甲基、乙基、苯基或互相鍵結形成碳數為4至12之脂肪族環；該＊代表共價鍵，其中該第一鹼可溶性樹脂(B-1)由一混合物所共聚合形成，該混合物包含具有式(I)所示之受阻胺結構之乙烯性單體(b-1-1)、具有一個或一個以上羧酸基之乙烯性不飽和單體(b-1-2)以及其他可共聚合之乙烯性不飽和單體(b-1-3)，且基於該具有式(I)所示之受阻胺結構之 乙烯性單體(b-1-1)、該具有一個或一個以上羧酸基之乙烯性不飽和單體(b-1-2)與該其他可共聚合之乙烯性不飽和單體(b-1-3)的總使用量為100重量份，該具有式(I)所示之受阻胺結構之乙烯性單體(b-1-1)之使用量為20重量份至45重量份，但不包括20重量份；以及一第二鹼可溶性樹脂(B-2)，由一第一混合物反應而獲得，其中該第一混合物包含一具有至少兩個環氧基之環氧化合物(b-2-1)，以及一具有至少一個羧酸基與至少一個乙烯性不飽和基之化合物(b-2-2)，其中該第一鹼可溶性樹脂(B-1)與該第二鹼可溶性樹脂(B-2)之重量比為10/90至90/10；一具有乙烯性不飽和基之化合物(C)；一光起始劑(D)；以及一有機溶劑(E)。 A photosensitive resin composition for a color filter comprising: a pigment (A); an alkali-soluble resin (B) comprising: a first alkali-soluble resin (B-1) having the following formula (I) The hindered amine structure: In the formula (I), the X 1 represents a hydrogen atom, a linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group or a cycloalkyl group, an aromatic group having 6 to 20 carbon atoms, and a carbon number of 7 An aromatic alkyl group, a fluorenyl group, an oxygen radical, or -OX 4 to 12; the X 4 represents a hydrogen atom, a linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group or a cycloalkyl group, and the carbon number is An aromatic group of 6 to 20, or an aromatic alkyl group having 7 to 12 carbon atoms; the X 2 and the X 3 each independently represent a methyl group, an ethyl group, a phenyl group or a bond to each other to form a carbon number of 4 to 12 An aliphatic ring; the * represents a covalent bond, wherein the first alkali-soluble resin (B-1) is formed by copolymerization of a mixture comprising an ethylenic monomer having a hindered amine structure represented by the formula (I) (b-1-1), an ethylenically unsaturated monomer (b-1-2) having one or more carboxylic acid groups, and other copolymerizable ethylenically unsaturated monomers (b-1-3), And based on the ethylenic monomer (b-1-1) having a hindered amine structure represented by the formula (I), the ethylenically unsaturated monomer having one or more carboxylic acid groups (b-1-2) And the total copolymerizable ethylenically unsaturated monomer (b-1-3) The amount of the ethylenic monomer (b-1-1) having a hindered amine structure represented by the formula (I) is from 20 parts by weight to 45 parts by weight, but not including 20 parts by weight; a second alkali-soluble resin (B-2) obtained by reacting a first mixture, wherein the first mixture comprises an epoxy compound (b-2-1) having at least two epoxy groups, and one having a compound of at least one carboxylic acid group and at least one ethylenically unsaturated group (b-2-2), wherein the weight ratio of the first alkali-soluble resin (B-1) to the second alkali-soluble resin (B-2) It is 10/90 to 90/10; a compound (C) having an ethylenically unsaturated group; a photoinitiator (D); and an organic solvent (E). 如申請專利範圍第1項所述之彩色濾光片用感光性樹脂組成物，基於該鹼可溶性樹脂(B)之總使用量為100重量份，該顏料(A)之使用量為30重量份至300重量份，該具有乙烯性不飽和基之化合物(C)之使用量為40重量份至400重量份，該光起始劑(D)之使用量為10重量份至100重量份，且該有機溶劑(E)之使用量為500重量份至5000重量份。 The photosensitive resin composition for a color filter according to claim 1, wherein the total amount of the alkali-soluble resin (B) used is 100 parts by weight, and the amount of the pigment (A) used is 30 parts by weight. The compound (C) having an ethylenically unsaturated group is used in an amount of 40 parts by weight to 400 parts by weight, and the photoinitiator (D) is used in an amount of 10 parts by weight to 100 parts by weight to 300 parts by weight, and The organic solvent (E) is used in an amount of from 500 parts by weight to 5000 parts by weight. 如申請專利範圍第1項所述之彩色濾光片用感光性 樹脂組成物，其中該具有至少兩個環氧基之環氧化合物(b-2-1)包含如下式(II)所示之化合物、如下式(III)所示之化合物或上述兩者之一組合： 於該式(II)中，該Y1、Y2、Y3及Y4分別獨立地代表氫原子、鹵原子、碳數為1至5之烷基或烷氧基，或者碳數為6至12之芳香基或芳烷基；於該式(III)中，該R1至R14分別獨立地代表氫原子、鹵素原子、碳數為1至8之烷基或碳數為6至15之芳香基，且n代表0至10之整數。 The photosensitive resin composition for color filters according to claim 1, wherein the epoxy compound (b-2-1) having at least two epoxy groups is represented by the following formula (II) a compound, a compound represented by the following formula (III) or a combination of the two: In the formula (II), the Y 1 , Y 2 , Y 3 and Y 4 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms or an alkoxy group, or a carbon number of 6 to An aromatic group or an aralkyl group of 12; in the formula (III), the R 1 to R 14 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or a carbon number of 6 to 15 An aryl group, and n represents an integer from 0 to 10. 一種製造彩色濾光片之方法，其係利用如申請專利範圍第1至3項中之任一項所述之彩色濾光片用感光性樹脂組成物形成一畫素層。 A method of producing a color filter, which comprises forming a pixel layer using a photosensitive resin composition for a color filter according to any one of claims 1 to 3. 一種彩色濾光片，其係藉由如申請專利範圍第4項所述之方法製得。 A color filter produced by the method of claim 4 of the patent application. 一種液晶顯示裝置，包含如申請專利範圍第5項所述之彩色濾光片。 A liquid crystal display device comprising the color filter of claim 5 of the patent application.
TW103110906A 2014-03-24 2014-03-24 Photosensitive resin composition for color filter and application thereof TWI559085B (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
TW103110906A TWI559085B (en) 2014-03-24 2014-03-24 Photosensitive resin composition for color filter and application thereof
CN201510109906.1A CN104950571B (en) 2014-03-24 2015-03-13 Photosensitive resin composition for color filter and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
TW103110906A TWI559085B (en) 2014-03-24 2014-03-24 Photosensitive resin composition for color filter and application thereof

Publications (2)

Publication Number Publication Date
TW201537296A TW201537296A (en) 2015-10-01
TWI559085B true TWI559085B (en) 2016-11-21

Family

ID=54165334

Family Applications (1)

Application Number Title Priority Date Filing Date
TW103110906A TWI559085B (en) 2014-03-24 2014-03-24 Photosensitive resin composition for color filter and application thereof

Country Status (2)

Country Link
CN (1) CN104950571B (en)
TW (1) TWI559085B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102504338B1 (en) * 2015-12-03 2023-02-28 롬엔드하스전자재료코리아유한회사 Photosensitive resin composition and organic insulating film using same

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010054808A (en) * 2008-08-28 2010-03-11 Jsr Corp Radiation sensitive composition for coloring layer formation, color filter, and color liquid crystal display element
TW201339194A (en) * 2012-03-19 2013-10-01 Chi Mei Corp Photosensitive resin composition, color filter and liquid crystal display device
TW201344354A (en) * 2012-03-28 2013-11-01 Jsr Corp Color filter, organic EL display element and colored composition

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101082771B (en) * 2006-05-30 2010-06-16 奇美实业股份有限公司 Photosensitive resin composition for colorful color filter
JPWO2011046230A1 (en) * 2009-10-16 2013-03-07 シャープ株式会社 Radiation-sensitive resin composition and method for forming interlayer insulating film
JP5504824B2 (en) * 2009-10-28 2014-05-28 Ｊｓｒ株式会社 Positive radiation-sensitive resin composition, interlayer insulating film and method for forming the same
TWI459137B (en) * 2012-05-10 2014-11-01 Chi Mei Corp Photosensitive resin composition for color filters and uses thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010054808A (en) * 2008-08-28 2010-03-11 Jsr Corp Radiation sensitive composition for coloring layer formation, color filter, and color liquid crystal display element
TW201339194A (en) * 2012-03-19 2013-10-01 Chi Mei Corp Photosensitive resin composition, color filter and liquid crystal display device
TW201344354A (en) * 2012-03-28 2013-11-01 Jsr Corp Color filter, organic EL display element and colored composition

Also Published As

Publication number Publication date
TW201537296A (en) 2015-10-01
CN104950571A (en) 2015-09-30
CN104950571B (en) 2019-05-10

Similar Documents

Publication Publication Date Title
JP4821206B2 (en) Photosensitive coloring composition for color filter and color filter
TWI531860B (en) Photosensitive resin composition for color filter and its application
JP2007034119A5 (en)
JP6174663B2 (en) Alkali-soluble resin, photosensitive resin composition containing the same, and application thereof
TWI559084B (en) Blue photosensitive resin composition for color filter and application thereof
CN108415221B (en) Photosensitive resin composition and application thereof
TW201640224A (en) Photosensitive resin composition for color filter and application of the same
TWI506369B (en) Photosensitive resin composition, color filter and method for manufacturing the same, liquid crystal display apparatus
JP2016206661A (en) Photosensitive resin composition, pixel layer, protective film, spacer, thin film transistor, color filter, and liquid crystal display device
CN104698752B (en) Photosensitive resin composition, color filter and manufacturing method thereof, and liquid crystal display device
TWI489208B (en) Photosensitive resin composition, color filter and liquid crystal display device having the same
TWI536099B (en) Photosensitive resin composition for color filter and application thereof
TWI533083B (en) Photosensitive resin composition for color filter and its application
TWI559085B (en) Photosensitive resin composition for color filter and application thereof
TWI431423B (en) Photosensitive resin composition for color filter and color filter using the same
TWI666518B (en) Photosensitive resin composition and uses thereof
TWI483073B (en) Photosensitive resin composition, color filter and method for manufacturing the same, liquid crystal display apparatus
TWI412885B (en) Photosensitive resin composition, and black matrix, color filter and liquid crystal display element made by using the composition
TWI529490B (en) Photosensitive resin composition for color filter and application thereof
TW201635013A (en) Photosensitive resin composition for color filter and application thereof
TWI535742B (en) Photosensitive resin composition for color filter and its application
US20190049780A1 (en) Photosensitive resin composition and manufacturing method of the same, black matrix, pixel layer, protection film, color filter, and liquid crystal display apparatus
TWI537348B (en) Photosensitive resin composition for color filter and its application
TWI669573B (en) Photosensitive resin composition and uses thereof
TWI486709B (en) Photosensitive resin composition for color filter and application of the same

Legal Events

Date Code Title Description
MM4A Annulment or lapse of patent due to non-payment of fees