TWI408499B - Radiation sensitive composition for forming a colored layer, color filter and color liquid crystal display device - Google Patents
Radiation sensitive composition for forming a colored layer, color filter and color liquid crystal display device Download PDFInfo
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- TWI408499B TWI408499B TW096111102A TW96111102A TWI408499B TW I408499 B TWI408499 B TW I408499B TW 096111102 A TW096111102 A TW 096111102A TW 96111102 A TW96111102 A TW 96111102A TW I408499 B TWI408499 B TW I408499B
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
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- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Materials For Photolithography (AREA)
- Optical Filters (AREA)
Abstract
Description
本發明關於一種用於形成著色層之輻射敏感性組成物、一種濾光片及一種彩色液晶顯示器。尤其是，本發明關於一種用於形成常用於透射式或反射式彩色液晶顯示器或彩色影像感應裝置之濾光片中的著色層之輻射敏感性組成物、一種具有由上述輻射敏感性組成物形成之著色層的濾光片及一種具有前述濾光片的彩色液晶顯示器。The present invention relates to a radiation-sensitive composition for forming a colored layer, a filter, and a color liquid crystal display. More particularly, the present invention relates to a radiation-sensitive composition for forming a coloring layer commonly used in a filter for a transmissive or reflective color liquid crystal display or a color image sensing device, and a composition having the above-described radiation-sensitive composition a color filter and a color liquid crystal display having the foregoing filter.
在從已著色的輻射敏感性組成物製造濾光片方面，於習知方法中係將著色輻射敏感性組成物施加至基材或預塗覆具有預定圖案之遮罩層的基材上，乾燥施加的組成物，並藉由以輻射照射(以下稱“曝光”)預定圖案來顯影乾燥的塗層，而獲得各顏色的像素(參見JP 2－144502A及JP 3－53201A)。In the manufacture of a filter from a pigmented radiation-sensitive composition, in a conventional method, a colored radiation-sensitive composition is applied to a substrate or a substrate precoated with a mask layer having a predetermined pattern, dried. The composition is applied, and the dried coating is developed by irradiating (hereinafter referred to as "exposure") a predetermined pattern to obtain pixels of respective colors (see JP 2-144502A and JP 3-53201A).
近年來，濾光片技術發展之主流為降低曝光劑量並減少製程時間。然而，當曝光劑量減低時，習知的著色輻射敏感性組成物將導致顯影後膜剩餘比降低、圖案中產生缺損或是過切或圖案自基材分離。因此，當減少製程時間時，難以獲得具有優異圖案的像素或是黑矩陣。另外，就像素及黑矩陣而言，即便曝光劑量降低，仍要求著色層之溶劑抗性和對基材的黏著力優異。然而，對此，習知的著色輻射敏感性組成物並未完全符合要求。In recent years, the mainstream of filter technology development has been to reduce exposure dose and reduce process time. However, when the exposure dose is reduced, the conventional colored radiation-sensitive composition will result in a decrease in the film remaining ratio after development, a defect in the pattern, or an overcut or pattern separation from the substrate. Therefore, when the process time is reduced, it is difficult to obtain a pixel or a black matrix having an excellent pattern. Further, in the case of the pixel and the black matrix, even if the exposure dose is lowered, the solvent resistance of the colored layer and the adhesion to the substrate are required to be excellent. However, in this regard, conventional colored radiation-sensitive compositions are not fully satisfactory.
本發明之一目的在於提供一種用於形成著色層之新穎的輻射敏感性組成物，其係高度敏感且以低劑量曝光時之圖案形成與膜剩餘比優異，且其使像素和黑矩陣對各種溶劑之溶劑抗性及對基材之黏著力優異。It is an object of the present invention to provide a novel radiation-sensitive composition for forming a colored layer which is highly sensitive and which is excellent in pattern formation and film remnant ratio when exposed at low doses, and which allows for various pixel and black matrix pairs The solvent resistance of the solvent and the adhesion to the substrate are excellent.
本發明之另一目的在於提供一種濾光片及一種液晶顯示器，該濾光片具有由上述輻射敏感性組成物所形成的著色層，而該液晶顯示器具有該濾光片。Another object of the present invention is to provide a filter and a liquid crystal display having a coloring layer formed of the above-described radiation-sensitive composition, and the liquid crystal display has the filter.
由以下的描述，本發明之其他目的和優點將為顯而易見者。Other objects and advantages of the invention will be apparent from the description.
根據本發明，藉由一種用於形成著色層之輻射敏感性組成物而達成上述之本發明的目的及優點，該輻射敏感性組成物包含(A)著色劑、(B)鹼溶性樹脂、(C)多官能性單體以及(D)光聚合作用起始劑，該(B)鹼溶性樹脂係由共聚物所形成，而該共聚物係由(b1)選自不飽和羧酸、不飽和羧酸酐及不飽及苯酚化合物中之至少一者、(b2)N取代之順丁烯二醯亞胺、(b3)具有四氫呋喃結構之不飽和化合物以及(b4)異於(b1)、(b2)和(b3)之不飽和化合物所形成。According to the present invention, the objects and advantages of the present invention described above are achieved by a radiation-sensitive composition comprising a coloring agent comprising (A) a colorant, (B) an alkali-soluble resin, ( C) a polyfunctional monomer and (D) a photopolymerization initiator, the (B) alkali-soluble resin being formed from a copolymer, wherein the copolymer is selected from (b1) an unsaturated carboxylic acid, unsaturated At least one of a carboxylic anhydride and an unsaturated phenol compound, (b2) N-substituted maleimide, (b3) an unsaturated compound having a tetrahydrofuran structure, and (b4) different from (b1), (b2) And (b3) are formed by unsaturated compounds.
於本發明中，“著色層”意指“像素及/或黑短陣”。In the present invention, "colored layer" means "pixel and/or black short array".
其次，藉一種濾光片達成上述之本發明的目的及優點，該濾光片具有由上述用於形成著色層之輻射敏感性組成物所形成的著色層。Next, the above objects and advantages of the present invention are achieved by a filter having a coloring layer formed of the above-described radiation-sensitive composition for forming a coloring layer.
再者，藉一種彩色液晶顯示器而達成上述之本發明的目的及優點，該彩色液晶顯示器具有該濾光片。Furthermore, the above objects and advantages of the present invention are achieved by a color liquid crystal display having the filter.
以下將詳細說明本發明。The invention will be described in detail below.
針對色調而言，本發明之著色劑並無特殊限制，且本發明之著色劑視所欲獲得之濾光片用途之需要而決定。其可為顏料、染料及天然染料之任何一者。The coloring agent of the present invention is not particularly limited in terms of color tone, and the coloring agent of the present invention is determined depending on the needs of the filter to be obtained. It can be any of pigments, dyes and natural dyes.
因濾光片需具有高解析度色彩顯影及抗熱性，較佳以具有高色彩顯影及具有高抗熱性之著色劑，尤其是對熱分解具有高抗性之著色劑，作為本發明之著色劑。較佳為使用有機顏料或無機顏料，尤佳為使用有機顏料或碳黑。Since the filter needs to have high-resolution color development and heat resistance, it is preferably a coloring agent having high color development and high heat resistance, especially a coloring agent having high resistance to thermal decomposition, as a coloring agent of the present invention. . It is preferred to use an organic pigment or an inorganic pigment, and it is particularly preferred to use an organic pigment or carbon black.
上述有機顏料之實例包括於比色指數(Color Index)(C.I.：由英國染整暨色彩師協會所公佈)中經分類為顏料之化合物，特別是被指定為下示比色指數(C.I.)號之化合物。Examples of the above organic pigments include compounds classified as pigments in the Color Index (CI: published by the British Society of Dyeing and Finishing and Colorists), in particular, designated as the colorimetric index (CI) number shown below. Compound.
C.I.顏料黃1、C.I.顏料黃3、C.I.顏料黃12、C.I.顏料黃13、C.I.顏料黃14、C.I.顏料黃15、C.I.顏料黃16、C.I.顏料黃17、C.I.顏料黃20、C.I.顏料黃24、C.I.顏料黃31、C.I.顏料黃55、C.I.顏料黃60、C.I.顏料黃61、C.I.顏料黃65、C.I.顏料黃71、C.I.顏料黃73、C.I.顏料黃74、C.I.顏料黃81、C.I.顏料黃83、C.I.顏料黃93、C.I.顏料黃95、C.I.顏料黃97、C.I.顏料黃98、C.I.顏料黃100、C.I.顏料黃101、C.I.顏料黃104、C.I.顏料黃106、C.I.顏料黃108、C.I.顏料黃109、C.I.顏料黃110、C.I.顏料黃113、C.I.顏料黃114、C.I.顏料黃116、C.I.顏料黃117、C.I.顏料黃119、C.I.顏料黃120、C.I.顏料黃126、C.I.顏料黃127、C.I.顏料黃128、C.I.顏料黃129、C.I.顏料黃138、C.I.顏料黃139、C.I.顏料黃150、C.I.顏料黃151、C.I.顏料黃152、C.I.顏料黃153、C.I.顏料黃154、C.I.顏料黃155、C.I.顏料黃156、C.I.顏料黃166、C.I.顏料黃168、C.I.顏料黃175、C.I.顏料黃180、C.I.顏料黃185；C.I.顏料橙1、C.I.顏料橙5、C.I.顏料橙13、C.I.顏料橙14、C.I.顏料橙16、C.I.顏料橙17、C.I.顏料橙24、C.I.顏料橙34、C.I.顏料橙36、C.I.顏料橙38、C.I.顏料橙40、C.I.顏料橙43、C.I.顏料橙46、C.I.顏料橙49、C.I.顏料橙51、C.I.顏料橙61、C.I.顏料橙63、C.I.顏料橙64、C.I.顏料橙71、C.I.顏料橙73；C.I.顏料紫1、C.I.顏料紫19、C.I.顏料紫23、C.I.顏料紫29、C.I.顏料紫32、C.I.顏料紫36、C.I.顏料紫38；C.I.顏料紅1、C.I.顏料紅2、C.I.顏料紅3、C.I.顏料紅4、C.I.顏料紅5、C.I.顏料紅6、C.I.顏料紅7、C.I.顏料紅8、C.I.顏料紅9、C.I.顏料紅10、C.I.顏料紅11、C.I.顏料紅12、C.I.顏料紅14、C.I.顏料紅15、C.I.顏料紅16、C.I.顏料紅17、C.I.顏料紅18、C.I.顏料紅19、C.I.顏料紅21、C.I.顏料紅22、C.I.顏料紅23、C.I.顏料紅30、C.I.顏料紅31、C.I.顏料紅32、C.I.顏料紅37、C.I.顏料紅38、C.I.顏料紅40、C.I.顏料紅41、C.I.顏料紅42、C.I.顏料紅48：1、C.I.顏料紅48：2、C.I.顏料紅48：3、C.I.顏料紅48：4、C.I.顏料紅49：1、C.I.顏料紅49：2、C.I.顏料紅50：1、C.I.顏料紅52：1、C.I.顏料紅53：1、C.I.顏料紅57、C.I.顏料紅57：1、C.I.顏料紅57：2、C.I.顏料紅58：2、C.I.顏料紅58：4、C.I.顏料紅60：1、C.I.顏料紅63：1、C.I.顏料紅63：2、C.I.顏料紅64：1、C.I.顏料紅81：1、C.I.顏料紅83、C.I.顏料紅88、C.I.顏料紅90：1、C.I.顏料紅97、C.I.顏料紅101、C.I.顏料紅102、C.I.顏料紅104、C.I.顏料紅105、C.I.顏料紅106、C.I.顏料紅108、C.I.顏料紅112、C.I.顏料紅113、C.I.顏料紅114、C.I.顏料紅122、C.I.顏料紅123、C.I.顏料紅144、C.I.顏料紅146、C.I.顏料紅149、C.I.顏料紅150、C.I顏料紅151、C.I.顏料紅166、C.I.顏料紅168、C.I顏料紅170、C.I.顏料紅171、C.I.顏料紅172、C.I.顏料紅174、C.I.顏料紅175、C.I.顏料紅176、C.I.顏料紅177、C.I.顏料紅178、C.I.顏料紅179、C.I.顏料紅18o、C.I.顏料紅185、C.I.顏料紅187、C.I.顏料紅188、C.I.顏料紅190、C.I.顏料紅193、C.I.顏料紅194、C.I.顏料紅202、C.I.顏料紅206、C.I.顏料紅207、C.I.顏料紅208、C.I.顏料紅209、C.I.顏料紅215、C.I.顏料紅216、C.I.顏料紅220、C.I.顏料紅224、C.I.顏料紅226、C.I.顏料紅242、C.I.顏料紅243、C.I.顏料紅245、C.I.顏料紅254、C.I.顏料紅255、C.I.顏料紅264、C.I.顏料紅265；C.I.顏料藍15、C.I.顏料藍15：3、C.I.顏料藍15：4、C.I.顏料藍15：6、C.I.顏料藍60，C.I.顏料綠7、C.I.顏料綠36；C.I.顏料棕23、C.I.顏料棕25；C.I.顏料黑1、C.I.顏料黑7。CI Pigment Yellow 1, CI Pigment Yellow 3, CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 15, CI Pigment Yellow 16, CI Pigment Yellow 17, CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 55, CI Pigment Yellow 60, CI Pigment Yellow 61, CI Pigment Yellow 65, CI Pigment Yellow 71, CI Pigment Yellow 73, CI Pigment Yellow 74, CI Pigment Yellow 81, CI Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 95, CI Pigment Yellow 97, CI Pigment Yellow 98, CI Pigment Yellow 100, CI Pigment Yellow 101, CI Pigment Yellow 104, CI Pigment Yellow 106, CI Pigment Yellow 108, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 113, CI Pigment Yellow 114, CI Pigment Yellow 116, CI Pigment Yellow 117, CI Pigment Yellow 119, CI Pigment Yellow 120, CI Pigment Yellow 126, CI Pigment Yellow 127, CI Pigment Yellow 128, CI Pigment Yellow 129, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 152, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 156, CI Pigment Yellow 166, CI Pigment Yellow 168, CI Pigment Yellow 175, CI Pigment Yellow 180, CI Pigment Yellow 185; CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 16, CI Pigment Orange 17, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI Pigment Orange 51, CI Pigment Orange 61, CI Pigment Orange 63, CI Pigment Orange 64, CI Pigment Orange 71, CI pigment orange 73; CI pigment violet 1, CI pigment violet 19, CI pigment violet 23, CI pigment violet 29, CI pigment violet 32, CI pigment violet 36, CI pigment violet 38; CI pigment red 1, CI pigment red 2 CI Pigment Red 3, CI Pigment Red 4, CI Pigment Red 5, CI Pigment Red 6, CI Pigment Red 7, CI Pigment Red 8, CI Pigment Red 9, CI Pigment Red 10, CI Pigment Red 11, CI Pigment Red 12, CI Pigment Red 14, CI Pigment Red 15, CI Pigment Red 16, CI Pigment Red 17, CI Pigment Red 18, CI Pigment Red 19, CI Pigment Red 21, CI Pigment Red 22, CI Pigment Red 23, CI Pigment Red 30, CI Pigment Red 31, CI Pigment Red 32, CI Pigment Red 37, CI Pigment Red 38, CI Pigment Red 40, CI Pigment Red 41, CI Pigment Red 42, CI Pigment Red 48:1, CI Pigment Red 48:2, CI Pigment Red 48:3, CI Pigment Red 48:4, CI Pigment Red 49:1, CI Pigment Red 49:2, CI Pigment Red 50:1, CI Pigment Red 52:1, CI Pigment Red 53:1, CI Pigment Red 57, CI Pigment Red 57:1, CI Pigment Red 57:2, CI Pigment Red 58:2, CI Pigment Red 58:4 , CI Pigment Red 60:1, CI Pigment Red 63:1, CI Pigment Red 63:2, CI Pigment Red 64:1, CI Pigment Red 81:1, CI Pigment Red 83, CI Pigment Red 88, CI Pigment Red 90 : 1, CI Pigment Red 97, CI Pigment Red 101, CI Pigment Red 102, CI Pigment Red 104, CI Pigment Red 105, CI Pigment Red 106, CI Pigment Red 108, CI Pigment Red 112, CI Pigment Red 113, CI Pigment Red 114, CI Pigment Red 122, CI Pigment Red 123, CI Pigment Red 144, CI Pigment Red 146, CI Pigment Red 149, CI Pigment Red 150, CI Pigment Red 151, CI Pigment Red 166, CI Pigment Red 168, CI Pigment Red 170, CI Pigment Red 171, CI Pigment Red 172, CI Pigment Red 174, CI Pigment Red 175, CI Pigment Red 176, CI Pigment Red 177, CI Pigment Red 178, CI Pigment Red 179, CI Pigment Red 18o, CI Pigment Red 185, CI Pigment Red 187, CI Pigment Red 188, CI Pigment Red 190, CI Pigment Red 193, CI Pigment Red 194, CI Pigment Red 202, CI Pigment Red 206, CI Pigment Red 207, CI Pigment Red 208, CI Pigment Red 209, CI Pigment Red 215, CI Pigment Red 216, CI Pigment Red 220, CI Pigment Red 224, CI Pigment Red 226, CI Pigment Red 242, CI Pigment Red 243, CI Pigment Red 245, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 264, CI Pigment Red 265; CI Pigment Blue 15, CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI Pigment Blue 15:6 , CI Pigment Blue 60, CI Pigment Green 7, CI Pigment Green 36; CI Pigment Brown 23, CI Pigment Brown 25; CI Pigment Black 1, CI Pigment Black 7.
於藉由硫酸再結晶法、溶劑沖洗法或彼等的結合進行純化之後，可使用此等有機顏料。These organic pigments can be used after purification by sulfuric acid recrystallization, solvent washing or a combination thereof.
另外，無機顏料包括氧化鈦、硫酸鋇、碳酸鈣、氧化鋅、硫酸鉛、鉻黃、鉻酸鋅、鐵丹(紅鐵氧化物(III))、鎘紅、群青、普魯士藍、氧化鉻綠、鈷綠、琥珀、鈦黑、合成鐵黑、碳黑及類似者。In addition, inorganic pigments include titanium oxide, barium sulfate, calcium carbonate, zinc oxide, lead sulfate, chrome yellow, zinc chromate, iron oxide (red iron oxide (III)), cadmium red, ultramarine blue, Prussian blue, chrome oxide green , cobalt green, amber, titanium black, synthetic iron black, carbon black and the like.
於本發明中，可單獨地使用上述有機顏料及無機顏料，或可結合使用其二或多者。此外，可結合使用有機顏料及無機顏料。為形成像素，較佳係使用一或多種有機顏料。為形成黑矩陣，較佳係使用二或多種有機顏料及/或碳黑。In the present invention, the above organic pigments and inorganic pigments may be used singly or in combination of two or more thereof. Further, organic pigments and inorganic pigments may be used in combination. To form a pixel, it is preferred to use one or more organic pigments. To form a black matrix, it is preferred to use two or more organic pigments and/or carbon black.
於本發明中，於使用上述顏料之前，視需要可以聚合物將呈顆粒狀之上述顏料予以表面改質。用於顏料顆粒之表面改質的聚合物係選自，舉例而言JP 8－259876A等中所描述的聚合物，或用於分散顏料之市售的聚合物或寡聚物。In the present invention, the above-mentioned pigment in the form of particles may be surface-modified by a polymer before the use of the above pigment. The polymer used for surface modification of the pigment particles is selected from, for example, the polymers described in JP 8-259876A or the like, or commercially available polymers or oligomers for dispersing pigments.
另外，於本發明中，著色劑可與分散劑一起使用。Further, in the present invention, a coloring agent can be used together with a dispersing agent.
上述分散劑之實例包括陽離子性、陰離子性、非離子性、兩性、含有矽及含有氟的界面活性劑。Examples of the above dispersing agent include cationic, anionic, nonionic, amphoteric, cerium-containing and fluorine-containing surfactants.
上述界面活性劑之實例包括聚氧乙烯烷基醚類，例如聚氧乙烯月桂醚、聚氧乙烯硬脂醚、聚氧乙烯油醚等；聚氧乙烯烷基苯基醚類，例如聚氧乙烯正辛基苯基醚、聚氧乙烯正壬基苯基醚等；聚乙二醇－二酯類，例如聚乙二醇－二月桂酯、聚乙二醇－二硬酯酸酯等；去水山梨醇脂肪酸酯類；脂肪酸改質的聚酯類；三級胺改質的聚胺甲酸酯；聚乙烯亞胺；以及具有下示商品名之產品，例如KP(信越化學工業股份有限公司提供)、POLYFLOW(共榮化學股份有限公司提供)、“F－Top”(Tochem Products公司提供)、MEGAFAC(大日本油墨化學工業提供)、FLUORAD(住友3M股份有限公司提供)、Asahi Guard及Surflon(均由旭硝子股份有限公司提供)、BYK及Disperbyk(均由BIGCHEMIE JAPAN提供)以及Solsperse(利康公司提供)。Examples of the above surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene ether ether, etc.; polyoxyethylene alkylphenyl ethers such as polyoxyethylene N-octyl phenyl ether, polyoxyethylene n-decyl phenyl ether, etc.; polyethylene glycol-diester, such as polyethylene glycol-dilauryl ester, polyethylene glycol-distearate, etc.; Water sorbitol fatty acid esters; fatty acid modified polyesters; tertiary amine modified polyurethanes; polyethyleneimine; and products having the following trade names, such as KP (Shin-Etsu Chemical Co., Ltd.) Provided), POLYFLOW (provided by Kyoei Chemical Co., Ltd.), "F-Top" (provided by Tochem Products), MEGAFAC (provided by Dainippon Ink Chemical Industry), FLUORAD (provided by Sumitomo 3M Co., Ltd.), Asahi Guard and Surflon (both supplied by Asahi Glass Co., Ltd.), BYK and Disperbyk (both supplied by BIGCHEMIE JAPAN) and Solsperse (provided by Likang).
可單獨地使用此等界面活性劑，或可結合使用其二或多者。These surfactants may be used singly or in combination of two or more thereof.
每100重量份著色劑之界面活性劑含量較佳係50重量份或更低，更佳係0至30重量份。The surfactant content per 100 parts by weight of the colorant is preferably 50 parts by weight or less, more preferably 0 to 30 parts by weight.
於本發明中，輻射敏感性樹脂組成物可藉適當方法製備。當使用顏料作為著色劑時，顏料較佳經研磨，例如經由玻珠磨機或軋輥磨機，且於同時經混合並於分散劑存在的情況下經分散於溶劑中，以獲得顏料分散物，以及將該顏料分散物與下文將提及之(B)組份、(C)組份及(D)組份混合，並可隨意與下文將提及之額外的溶劑和其他添加物混合，藉此可製備輻射敏感性樹脂組成物。In the present invention, the radiation-sensitive resin composition can be produced by a suitable method. When a pigment is used as the colorant, the pigment is preferably ground, for example, via a bead mill or a roll mill, and simultaneously mixed and dispersed in a solvent in the presence of a dispersant to obtain a pigment dispersion, And mixing the pigment dispersion with the components (B), (C) and (D) which will be mentioned later, and optionally mixed with the additional solvent and other additives mentioned below. This makes it possible to prepare a radiation-sensitive resin composition.
用於顏料分散物之製備的分散劑量，以每100重量份顏料計，較佳為100重量份或更低，更佳為0.5至100重量份，又更佳為1至70重量份，尤佳為10至50重量份。當分散劑含量超過100重量份時，樹脂組成物之可顯影性可能受損。The dispersing amount for the preparation of the pigment dispersion is preferably 100 parts by weight or less, more preferably 0.5 to 100 parts by weight, still more preferably 1 to 70 parts by weight, per 100 parts by weight of the pigment, particularly preferably It is 10 to 50 parts by weight. When the dispersant content exceeds 100 parts by weight, the developability of the resin composition may be impaired.
關於下文將描述之呈液體組成物形式的輻射敏感性樹脂組成物，用於其顏料分散物之製備的溶劑係可選自下文將描述作為實例者。Regarding the radiation-sensitive resin composition in the form of a liquid composition which will be described later, the solvent used for the preparation of the pigment dispersion thereof may be selected from those exemplified below.
用於顏料分散物之製備的溶劑量，以每100重量份顏料計，較佳為200至1000重量份，更佳為300至800重量份。The amount of the solvent used for the preparation of the pigment dispersion is preferably from 200 to 1,000 parts by weight, more preferably from 300 to 800 parts by weight per 100 parts by weight of the pigment.
當顏料分散物係以玻珠磨機製備時，舉例而言，係使用直徑為約0.5至10 mm之玻璃珠和鈦珠，且將含有顏料、溶劑及分散劑的顏料混合物混合並分散，且較佳以冷卻水或類似者予以冷卻。When the pigment dispersion is prepared by a bead mill, for example, glass beads and titanium beads having a diameter of about 0.5 to 10 mm are used, and a pigment mixture containing a pigment, a solvent, and a dispersant is mixed and dispersed, and It is preferably cooled by cooling water or the like.
於此情況中，以磨機容量計，玻珠的填充因子較佳係50至80%，且以磨機容量計，顏料混合物的裝料量較佳係約20至50%。此外，處理的時間較佳係2至50小時，更佳係2至25小時。In this case, the fill factor of the glass bead is preferably from 50 to 80% in terms of the mill capacity, and the charge amount of the pigment mixture is preferably from about 20 to 50% in terms of the mill capacity. Further, the treatment time is preferably from 2 to 50 hours, more preferably from 2 to 25 hours.
當顏料分散物係以軋輥磨機製備時，舉例而言，係使用三輥磨機或二輥磨機，且顏料混合物可較佳以冷卻水予以冷卻。When the pigment dispersion is prepared by a roll mill, for example, a three-roll mill or a two-roll mill is used, and the pigment mixture is preferably cooled by cooling water.
於此情況中，輥間距離較佳係10 μm或更小，且剪力較佳係約108 dyn/秒。用於處理的時間較佳係2至50小時，更佳係2至25小時。In this case, the distance between the rolls is preferably 10 μm or less, and the shear force is preferably about 10 8 dyn/sec. The time for the treatment is preferably from 2 to 50 hours, more preferably from 2 to 25 hours.
本發明之鹼溶性樹脂係以共聚物(以下稱“共聚物(BI)”)形成，該共聚物係由(b1)選自不飽和羧酸、不飽和羧酸酐及不飽及苯酚化合物中之至少－者(以下此等化合物總稱為“不飽和化合物(b1)”)、(b2)N取代之順丁烯二醯亞胺、(b3)具有四氫呋喃結構之不飽和化合物(以下稱“不飽和化合物(b3)”)以及(b4)異於該(b1)、(b2)及(b3)之不飽和化合物(以下稱“不飽和化合物(b4)”)所形成。共聚物(BI)係為在(A)著色劑之上作為黏著劑的組份，且其在顯影步驟中用於形成著色層的鹼性顯影溶液中具有溶解性。The alkali-soluble resin of the present invention is formed by a copolymer (hereinafter referred to as "copolymer (BI)") which is selected from (b1) an unsaturated carboxylic acid, an unsaturated carboxylic anhydride, and an unsaturated phenol compound. At least - (hereinafter referred to as "unsaturated compound (b1)"), (b2) N-substituted maleimide, (b3) unsaturated compound having a tetrahydrofuran structure (hereinafter referred to as "unsaturated" The compounds (b3)") and (b4) are formed differently from the unsaturated compounds of the above (b1), (b2) and (b3) (hereinafter referred to as "unsaturated compound (b4)"). The copolymer (BI) is a component as an adhesive on the (A) coloring agent, and it has solubility in an alkali developing solution for forming a coloring layer in a developing step.
於上述不飽和化合物(b1)中，上述不飽和羧酸及不飽和羧酸酐之實例包括：不飽和單羧酸類，例如(甲基)丙烯酸、巴豆酸、α－氯丙烯酸、桂皮酸等；不飽和二羧酸或其酐，例如順丁烯二酸、順丁烯二酐、反丁烯二酸、衣康酸、衣康酐、檸康酸、檸康酐、中康酸等；三價或以上之不飽和多價羧酸或其酐類；二價或以上之多價羧酸之單[(甲基)丙烯醯氧基烷基]酯類，例如單[2－(甲基)丙烯醯氧基乙基]琥珀酸酯、單[2－(甲基)丙烯醯氧基乙基]酞酸酯等；以及於兩終端各具有羧基和羥基之聚合物的單(甲基)丙烯酸酯類，例如單(甲基)丙烯酸ω－羧聚己內酯。In the above unsaturated compound (b1), examples of the above unsaturated carboxylic acid and unsaturated carboxylic acid anhydride include: unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, etc.; a saturated dicarboxylic acid or an anhydride thereof, such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid, etc.; Or an unsaturated polyvalent carboxylic acid or anhydride thereof; a mono[(meth)acryloxyalkyl]ester of a divalent or higher polyvalent carboxylic acid, such as mono [2-(methyl) propylene a methoxyethyl]succinate, a mono[2-(methyl)propenyloxyethyl]decanoate, and the like; and a mono(meth)acrylate having a polymer having a carboxyl group and a hydroxyl group at both terminals For example, ω-carboxypolycaprolactone mono(meth)acrylate.
在這些不飽和羧酸及不飽和羧酸酐中，單(2－丙烯醯氧基乙基)琥珀酸酯和單(2－丙烯醯氧基乙基)酞酸酯，係可得自市售之商品名為LIGHT－ESTER HOA－MS和LIGHT－ESTER HOA－MPA者(均由共榮化學股份有限公司提供)。Among these unsaturated carboxylic acids and unsaturated carboxylic anhydrides, mono(2-propenyloxyethyl) succinate and mono(2-propenyloxyethyl) phthalate are commercially available. The trade names are LIGHT-ESTER HOA-MS and LIGHT-ESTER HOA-MPA (both provided by Gongrong Chemical Co., Ltd.).
另外，上述不飽和苯酚化合物之實例包括：不飽和苯酚類，例如鄰乙烯苯酚、間乙烯苯酚、對乙烯苯酚、2－甲基－4－乙烯苯酚、3－甲基－4－乙烯苯酚、鄰異丙烯苯酚、間異丙烯苯酚、對異丙烯苯酚等；以及不飽和萘酚類，例如2－乙烯基－1－萘酚、3－乙烯基－1－萘酚、1－乙烯基－2－萘酚、3－乙烯基－2－萘酚、2-異丙烯基-1-萘酚、3-異丙烯基-1-萘酚等。Further, examples of the above unsaturated phenol compound include: unsaturated phenols such as o-vinylphenol, m-vinylphenol, p-vinylphenol, 2-methyl-4-ethenephenol, 3-methyl-4-ethenephenol, ortho Isopropene phenol, meta-isopropen phenol, p-isopropene phenol, etc.; and unsaturated naphthols such as 2-vinyl-1-naphthol, 3-vinyl-1-naphthol, 1-vinyl-2- Naphthol, 3-vinyl-2-naphthol, 2-isopropenyl-1-naphthol, 3-isopropenyl-1-naphthol, and the like.
較佳以(甲基)丙烯酸、對乙烯苯酚等且尤佳以(甲基)丙烯酸作為本發明之不飽和化合物(b1)。Preferred is (meth)acrylic acid, p-vinylphenol or the like, and (meth)acrylic acid is preferred as the unsaturated compound (b1) of the present invention.
此外，N取代之順丁烯二醯亞胺之實例包括，N-甲基順丁烯二醯亞胺、N-乙基順丁烯二醯亞胺、N-正丙基順丁烯二醯亞胺、N-異丙基順丁烯二醯亞胺、N-正丁基順丁烯二醯亞胺、N-第三丁基順丁烯二醯亞胺、N-正己基順丁烯二醯亞胺、N-環戊基順丁烯二醯亞胺、N-環己基順丁烯二醯亞胺、N-苯基順丁烯二醯亞胺及N-1-萘基順丁烯二醯亞胺。Further, examples of the N-substituted maleimide include N-methyl maleimide, N-ethyl maleimide, N-n-propylbutylene Imine, N-isopropyl maleimide, N-n-butyl maleimide, N-tert-butyl maleimide, N-n-hexyl maleimide , N-cyclopentyl maleimide, N-cyclohexyl maleimide, N-phenyl maleimide, and N-1-naphthyl-n-butylene amine.
較佳以N-環己基順丁烯二醯亞胺、N-苯基順丁烯二醯亞胺等且尤佳以N-苯基順丁烯二醯亞胺作為本發明之N取代之順丁烯二醯亞胺。Preferably, N-cyclohexylmethyleneimine, N-phenylmaleimide, and the like, and preferably N-phenylbutyleneimine, are used as the N-substituted sulfonate of the present invention. Butylene diimine.
可單獨使用上述N-取代之順丁烯二醯亞胺或可結合使用其中二或多者。The above N-substituted maleimide may be used singly or two or more of them may be used in combination.
另外，不飽和化合物(b3)的實例包括：(甲基)丙烯酸之四氫呋喃酯類，例如(甲基)丙烯酸四氫呋喃-2-基酯、(甲基)丙烯酸四氫呋喃-3-基酯等；(甲基)丙烯酸酯之含有四氫呋喃甲基團的酯類，例如(甲基)丙烯酸四氫呋喃甲酯、(甲基)丙烯酸2-(四氫呋喃甲基氧基)乙酯、(甲基)丙烯酸2-(3-四氫呋喃甲基氧基)乙酯等；二羧酸之含有丙烯醯基團的四氫呋喃酯類，例如[2-(甲基)丙烯醯氧基乙基](四氫呋喃－2－基)酞酸酯、[2－(甲基)丙烯醯氧基乙基](四氫呋喃－3－基)酞酸酯、[2－(甲基)丙烯醯氧基乙基](四氫呋喃－2－基)琥珀酸酯、[2－(甲基)丙烯醯氧基乙基](四氫呋喃－3－基)琥珀酸酯等；二羧酸之含有(甲基)丙烯醯基團的四氫呋喃酯類，例如[2－(甲基)丙烯醯氧基乙基](四氫呋喃基)酞酸酯、[2－(甲基)丙烯醯氧基乙基](四氫呋喃基)琥珀酸酯等；2－(甲基)丙烯醯氧基丙酸酯之四氫呋喃酯類，例如2－(甲基)丙烯醯氧基丙酸四氫呋喃－2－基酯、2－(甲基)丙烯醯氧基丙酸四氫呋喃－3－基酯等；2－(甲基)丙烯醯氧基丙酸酯之含有四氫呋喃甲基團的酯類，例如2－(甲基)丙烯醯氧基丙酸四氫呋喃甲酯、2－(甲基)丙烯醯氧基丙酸3－四氫呋喃甲酯、2－(甲基)丙烯醯氧基丙酸2－(四氫呋喃甲基氧基)乙酯、2－(甲基)丙烯醯氧基丙酸2－(3－四氫呋喃甲基氧基)乙酯等；苯乙烯衍生物，例如(四氫呋喃－2－基)氧基對苯乙烯、四氫呋喃甲基氧基對苯乙烯、2－(四氫呋喃甲基氧基)乙氧基對苯乙烯等；以及乙烯基醚類，例如(四氫呋喃－2－基)乙烯基醚、(四氫呋喃甲基)乙烯基醚、[2－(四氫呋喃甲基氧基)乙基]乙烯基醚等。Further, examples of the unsaturated compound (b3) include: tetrahydrofuran esters of (meth)acrylic acid, such as tetrahydrofuran-2-yl (meth)acrylate, tetrahydrofuran-3-yl (meth)acrylate, and the like; Ethyl esters containing tetrahydrofuran methyl group, such as tetrahydrofuran methyl (meth)acrylate, 2-(tetrahydrofuranmethyloxy)ethyl (meth)acrylate, 2-(3) (meth)acrylate -tetrahydrofuranmethyloxy)ethyl ester; etc.; tetrahydrofuran esters of a dicarboxylic acid containing an acrylonitrile group, such as [2-(methyl)propenyloxyethyl](tetrahydrofuran-2-yl)decanoate , [2-(Methyl)propenyloxyethyl](tetrahydrofuran-3-yl)decanoate, [2-(methyl)propenyloxyethyl](tetrahydrofuran-2-yl)succinate , [2-(methyl) propylene oxiranylethyl] (tetrahydrofuran-3-yl) succinate, etc.; dicarboxylic acid containing tetrahydrofuran esters of (meth) acrylonitrile groups, such as [2-( Methyl)propenyloxyethyl](tetrahydrofuranyl)decanoate, [2-(methyl)propenyloxyethyl](tetrahydrofuranyl)succinate, etc.; 2-(methyl)propene oxide Propionate Hydrofuryl esters such as 2-(methyl)propenyloxypropionic acid tetrahydrofuran-2-yl ester, 2-(methyl)propenyloxypropionic acid tetrahydrofuran-3-yl ester, etc.; 2-(methyl a THF containing a tetrahydrofuranmethyl group, such as 2-(methyl)propenyloxypropionic acid tetrahydrofuran methyl ester, 2-(methyl)propoxy methoxypropionic acid 3-tetrahydrofuran Methyl ester, 2-(tetrahydrofuranmethyloxy)ethyl 2-(methyl)propenyloxypropionate, 2-(3-tetrahydrofuranmethyloxy) 2-(methyl)propenyloxypropionic acid Ethyl ester or the like; a styrene derivative such as (tetrahydrofuran-2-yl)oxy-p-styrene, tetrahydrofuranmethyloxy-p-styrene, 2-(tetrahydrofuranmethyloxy)ethoxy-p-styrene, and the like; Vinyl ethers, for example, (tetrahydrofuran-2-yl)vinyl ether, (tetrahydrofuranmethyl)vinyl ether, [2-(tetrahydrofuranmethyloxy)ethyl]vinyl ether, and the like.
較佳以(甲基)丙烯酸四氫呋喃甲酯、[2－(甲基)丙烯醯氧基乙基](四氫呋喃甲基)琥珀酸酯等作為本發明之不飽和化合物(b3)。As the unsaturated compound (b3) of the present invention, tetrahydrofuran methyl (meth)acrylate, [2-(meth)acryloxyethyl) (tetrahydrofuranmethyl) succinate or the like is preferred.
可單獨使用上述不飽和化合物(b3)或可結合使用其中二或多者。The above unsaturated compound (b3) may be used singly or two or more of them may be used in combination.
不飽和化合物(b4)的實例包括：芳族乙烯基化合物類，例如苯乙烯、α－甲苯乙烯、鄰乙烯甲苯、間乙烯甲苯、對乙烯甲苯、對氯苯乙烯、鄰甲氧苯乙烯、間甲氧苯乙烯、對甲氧苯乙烯、鄰乙烯苯甲基甲基醚、間乙烯苯甲基甲基醚、對乙烯苯甲基甲基醚、鄰乙烯苯甲基環氧丙基醚、間乙烯苯甲基環氧丙基醚、對乙烯苯甲基環氧丙基醚等；茚類，例如茚、1－甲茚等；不飽和羧酸酯類，例如(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸2－乙基己酯、(甲基)丙烯酸2羥基乙酯、(甲基)丙烯酸2－羥基丙酯、(甲基)丙烯酸3－羥基丙酯、(甲基)丙烯酸2－羥基丁酯、(甲基)丙烯酸3－羥基丁酯、(甲基)丙烯酸4－羥基丁酯、(甲基)丙烯酸烯丙酯、(甲基)丙烯酸苯甲酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸2－甲氧乙酯、(甲基)丙烯酸2－苯氧乙酯、(甲基)丙烯酸甲氧二乙二醇酯、(甲基)丙烯酸甲氧三乙二醇酯、(甲基)丙烯酸甲氧丙二醇酯、(甲基)丙烯酸甲氧二丙二醇酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸二環戊二乙酯、(甲基)丙烯酸2－羥基－3－苯氧丙酯、單(甲基)丙烯酸甘油酯等；不飽和羧酸胺基烷酯類，例如(甲基)丙烯酸2－胺基乙酯、(甲基)丙烯酸2－二甲基胺基乙酯、(甲基)丙烯酸2－胺基丙酯、(甲基)丙烯酸2－二甲基胺基丙酯、(甲基)丙烯酸3胺基丙酯、(甲基)丙烯酸3二甲基胺基丙酯等；不飽和羧酸環氧丙酯類，例如(甲基)丙烯酸環氧丙酯等；乙烯氰化合物類，例如(甲基)丙烯腈、α－氯丙烯腈、二氰亞乙烯等；不飽和醯胺類，例如(甲基)丙烯醯胺、α－氯丙烯醯胺、N－2－羥基乙基(甲基)丙烯醯胺等；羧酸乙烯酯類，例如乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、苯甲酸乙烯酯等；不飽和醚類，例如乙烯基甲基醚、乙烯基乙基醚、烯丙基環氧丙基醚等；脂族共軛二烯類，例如1,3－丁二烯、異戊二烯、氯丁二烯；以及於聚合物分子鏈末端具有單(甲基)丙烯醯基團之巨單體類，例如聚苯乙烯、聚(甲基)丙烯酸甲酯、聚(甲基)丙烯酸正丁酯、聚矽氧烷等；可單獨使用上述不飽和化合物(b4)或可結合使用其中二或多者。Examples of the unsaturated compound (b4) include: aromatic vinyl compounds such as styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, and Methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyloxypropyl ether, Vinylbenzyl epoxypropyl ether, p-vinylbenzyloxypropyl ether, etc.; terpenoids such as hydrazine, 1-carbamidine, etc.; unsaturated carboxylic acid esters such as methyl (meth) acrylate, Ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, (meth)acrylic acid Dibutyl ester, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (methyl) ) 3-hydroxypropyl acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (methyl) Allyl acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-(meth) acrylate Phenoxyethyl ester, methoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxypropyl (meth)acrylate, methoxydipropylene glycol (meth)acrylate Ester, isodecyl (meth)acrylate, dicyclopentaethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, glycerol mono(meth)acrylate, etc.; Alkyl alcohol esters of saturated carboxylic acids, such as 2-aminoethyl (meth)acrylate, 2-dimethylaminoethyl (meth)acrylate, 2-aminopropyl (meth)acrylate, ( 2-dimethylaminopropyl methacrylate, 3-aminopropyl (meth) acrylate, 3 dimethylaminopropyl (meth) acrylate, etc.; unsaturated carboxylic acid glycidyl ester, For example, glycidyl (meth)acrylate, etc.; vinyl cyanide compounds such as (meth)acrylonitrile, α-chloroacrylonitrile, dicyanethylene, etc.; unsaturated amides such as (meth) propylene hydride Amine, α-chloropropene oxime Amine, N-2-hydroxyethyl (meth) acrylamide, etc.; vinyl carboxylates such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, etc.; unsaturated ethers, For example, vinyl methyl ether, vinyl ethyl ether, allyl epoxy propyl ether, etc.; aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chloroprene; And macromonomers having a mono(meth)acryloyl group at the end of the polymer molecular chain, such as polystyrene, poly(methyl) methacrylate, poly(methyl) methacrylate, polyoxyl Alkane or the like; the above unsaturated compound (b4) may be used singly or two or more of them may be used in combination.
於本發明中，共聚物(BI)較佳係得自(甲基)丙烯酸或其與至少一種其他的不飽和化合物(b1)、至少一種N取代的順丁烯二醯亞胺(b2)、至少一種不飽和化合物(b3)以及至少一種不飽和化合物(b4)之組合的共聚物(以下稱為“共聚物(BII)”)，其中，(b2)選自N－環己基順丁烯二醯亞胺或N－苯基順丁烯二醯亞胺；(b3)選自(甲基)丙烯酸四氫呋喃甲酯或[2－(甲基)丙烯醯氧基乙基](四氫呋喃甲基)琥珀酸酯；(b4)選自苯乙烯、(甲基)丙烯酸甲酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸2－乙基己酯、(甲基)丙烯酸2－羥基乙酯、(甲基)丙烯酸烯丙酯、(甲基)丙烯酸苯甲酯、單(甲基)丙烯酸甘油酯、聚苯乙烯巨單體或聚甲基丙烯酸甲酯巨單體。In the present invention, the copolymer (BI) is preferably derived from (meth)acrylic acid or its at least one other unsaturated compound (b1), at least one N-substituted maleimide (b2), a copolymer of at least one combination of an unsaturated compound (b3) and at least one unsaturated compound (b4) (hereinafter referred to as "copolymer (BII)"), wherein (b2) is selected from N-cyclohexyl-butenylene醯imino or N-phenyl maleimide; (b3) selected from methyl (meth) acrylate or [2-(methyl) propylene methoxyethyl] (tetrahydrofuran methyl) amber Acid ester; (b4) is selected from the group consisting of styrene, methyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate , allyl (meth) acrylate, benzyl (meth) acrylate, glycerol mono (meth) acrylate, polystyrene macromonomer or polymethyl methacrylate macromonomer.
共聚物(BII)的具體實例包括：(甲基)丙烯酸/N－苯基順丁烯二醯亞胺/(甲基)丙烯酸四氫呋喃甲酯/苯乙烯共聚物，(甲基)丙烯酸/N－苯基順丁烯二醯亞胺/(甲基)丙烯酸四氫呋喃甲酯/(甲基)丙烯酸甲酯共聚物，(甲基)丙烯酸/N－苯基順丁烯二醯亞胺/(甲基)丙烯酸四氫呋喃甲酯/(甲基)丙烯酸苯甲酯共聚物，(甲基)丙烯酸/N－苯基順丁烯二醯亞胺/(甲基)丙烯酸四氫呋喃甲酯/(甲基)丙烯酸2－羥基乙酯共聚物，(甲基)丙烯酸/N－苯基順丁烯二醯亞胺/(甲基)丙烯酸四氫呋喃甲酯/苯乙烯/(甲基)丙烯酸正丁酯共聚物，(甲基)丙烯酸/N－苯基順丁烯二醯亞胺/(甲基)丙烯酸四氫呋喃甲酯/(甲基)丙烯酸甲酯/(甲基)丙烯酸正丁酯共聚物，(甲基)丙烯酸/N－苯基順丁烯二醯亞胺/(甲基)丙烯酸四氫呋喃甲酯/(甲基)丙烯酸正丁酯/(甲基)丙烯酸苯甲酯共聚物，(甲基)丙烯酸/N－苯基順丁烯二醯亞胺/(甲基)丙烯酸四氫呋喃甲酯/(甲基)丙烯酸正丁酯/(甲基)丙烯酸2－羥基乙酯共聚物，(甲基)丙烯酸/N－苯基順丁烯二醯亞胺/(甲基)丙烯酸四氫呋喃甲酯/苯乙烯/(甲基)丙烯酸2－羥基乙酯共聚物，(甲基)丙烯酸/N－苯基順丁烯二醯亞胺/(甲基)丙烯酸四氫呋喃甲酯/(甲基)丙烯酸2－羥基乙酯/(甲基)丙烯酸苯甲酯共聚物，(甲基)丙烯酸/N－苯基順丁烯二醯亞胺/(甲基)丙烯酸四氫呋喃甲酯/(甲基)丙烯酸2－羥基乙酯/(甲基)丙烯酸苯酯共聚物，(甲基)丙烯酸/N－苯基順丁烯二醯亞胺/(甲基)丙烯酸四氫呋喃甲酯/(甲基)丙烯酸苯甲酯/單(甲基)丙烯酸甘油酯共聚物，(甲基)丙烯酸/N－苯基順丁烯二醯亞胺/(甲基)丙烯酸四氫呋喃甲酯/(甲基)丙烯酸甲酯/聚苯乙烯巨單體共聚物，(甲基)丙烯酸/N－苯基順丁烯二醯亞胺/(甲基)丙烯酸四氫呋喃甲酯/(甲基)丙烯酸甲酯/聚甲基丙烯酸甲酯巨單體共聚物，(甲基)丙烯酸/N－苯基順丁烯二醯亞胺/(甲基)丙烯酸四氫呋喃甲酯/(甲基)丙烯酸苯甲酯/聚苯乙烯巨單體共聚物，(甲基)丙烯酸/N－苯基順丁烯二醯亞胺/(甲基)丙烯酸四氫呋喃甲酯/(甲基)丙烯酸苯甲酯/聚(甲基)丙烯酸甲酯巨單體共聚物，(甲基)丙烯酸/N－苯基順丁烯二醯亞胺/(甲基)丙烯酸四氫呋喃甲酯/苯乙烯/(甲基)丙烯酸正丁酯/(甲基)丙烯酸2－羥基乙酯共聚物，(甲基)丙烯酸/N－苯基順丁烯二醯亞胺/(甲基)丙烯酸四氫呋喃甲酯/苯乙烯/(甲基)丙烯酸正丁酯/(甲基)丙烯酸苯甲酯共聚物，(甲基)丙烯酸/N－苯基順丁烯二醯亞胺/(甲基)丙烯酸四氫呋喃甲酯/苯乙烯/(甲基)丙烯酸苯甲酯/單(甲基)丙烯酸甘油酯共聚物，(甲基)丙烯酸/N－苯基順丁烯二醯亞胺/(甲基)丙烯酸四氫呋喃甲酯/(甲基)丙烯酸正丁酯/(甲基)丙烯酸2－羥基乙酯/(甲基)丙烯酸苯甲酯共聚物，(甲基)丙烯酸/N－苯基順丁烯二醯亞胺/(甲基)丙烯酸四氫呋喃甲酯/(甲基)丙烯酸正丁酯/(甲基)丙烯酸2－羥基乙酯/(甲基)丙烯酸苯酯共聚物，(甲基)丙烯酸/N－苯基順丁烯二醯亞胺/(甲基)丙烯酸四氫呋喃甲酯/(甲基)丙烯酸正丁酯/(甲基)丙烯酸苯甲酯/單(甲基)丙烯酸甘油酯共聚物，(甲基)丙烯酸/N－苯基順丁烯二醯亞胺/(甲基)丙烯酸四氫呋喃甲酯/(甲基)丙烯酸甲酯/(甲基)丙烯酸正丁酯/聚苯乙烯巨單體共聚物，(甲基)丙烯酸/N－苯基順丁烯二醯亞胺/(甲基)丙烯酸四氫呋喃甲酯/(甲基)丙烯酸甲酯/(甲基)丙烯酸正丁酯/聚甲基丙烯酸甲酯巨單體共聚物，(甲基)丙烯酸/N－苯基順丁烯二醯亞胺/(甲基)丙烯酸四氫呋喃甲酯/(甲基)丙烯酸正丁酯/(甲基)丙烯酸苯甲酯/聚苯乙烯巨單體共聚物，(甲基)丙烯酸/N－苯基順丁烯二醯亞胺/(甲基)丙烯酸四氫呋喃甲酯/(甲基)丙烯酸正丁酯/(甲基)丙烯酸苯甲酯/聚甲基丙烯酸甲酯巨單體共聚物，(甲基)丙烯酸/N－苯基順丁烯二醯亞胺/(甲基)丙烯酸四氫呋喃甲酯/(甲基)丙烯酸2－羥基乙酯/(甲基)丙烯酸苯甲酯/聚苯乙烯巨單體共聚物，(甲基)丙烯酸/N－苯基順丁烯二醯亞胺/(甲基)丙烯酸四氫呋喃甲酯/(甲基)丙烯酸2－羥基乙酯/(甲基)丙烯酸苯甲酯/聚(甲基)丙烯酸甲酯巨單體共聚物，(甲基)丙烯酸/N－苯基順丁烯二醯亞胺/(甲基)丙烯酸四氫呋喃甲酯/苯乙烯/(甲基)丙烯酸正丁酯/(甲基)丙烯酸苯甲酯/單(甲基)丙烯酸甘油酯共聚物，(甲基)丙烯酸/N－苯基順丁烯二醯亞胺/(甲基)丙烯酸四氫呋喃甲酯/苯乙烯/(甲基)丙烯酸2－羥基乙酯/(甲基)丙烯酸苯酯/聚苯乙烯巨單體共聚物，(甲基)丙烯酸/N－苯基順丁烯二醯亞胺/(甲基)丙烯酸四氫呋喃甲酯/苯乙烯/(甲基)丙烯酸2－羥基乙酯/(甲基)丙烯酸苯酯/聚甲基丙烯酸甲酯巨單體共聚物，(甲基)丙烯酸/N－苯基順丁烯二醯亞胺/(甲基)丙烯酸四氫呋喃甲酯/(甲基)丙烯酸正丁酯/(甲基)丙烯酸2－羥基乙酯/(甲基)丙烯酸苯甲酯/聚苯乙烯巨單體共聚物，(甲基)丙烯酸/N－苯基順丁烯二醯亞胺/(甲基)丙烯酸四氫呋喃甲酯/(甲基)丙烯酸正丁酯/(甲基)丙烯酸2－羥基乙酯/(甲基)丙烯酸苯甲酯/聚(甲基)丙烯酸甲酯巨單體共聚物，(甲基)丙烯酸/N－苯基順丁烯二醯亞胺/(甲基)丙烯酸四氫呋喃甲酯/苯乙烯/(甲基)丙烯酸正丁酯/(甲基)丙烯酸2－羥基乙酯/(甲基)丙烯酸苯酯/聚苯乙烯巨單體共聚物，(甲基)丙烯酸/N－苯基順丁烯二醯亞胺/(甲基)丙烯酸四氫呋喃甲酯/苯乙烯/(甲基)丙烯酸正丁酯/(甲基)丙烯酸2－羥基乙酯/(甲基)丙烯酸苯酯/聚甲基丙烯酸甲酯巨單體共聚物，(甲基)丙烯酸/單[2－(甲基)丙烯醯氧基乙基]琥珀酸酯/N－環己基順丁烯二醯亞胺/(甲基)丙烯酸四氫呋喃甲酯/苯乙烯/(甲基)丙烯酸烯丙酯共聚物，(甲基)丙烯酸/單[2－(甲基)丙烯醯氧基乙基]琥珀酸酯/N－環己基順丁烯二醯亞胺/(甲基)丙烯酸四氫呋喃甲酯/苯乙烯/(甲基)丙烯酸苯甲酯共聚物，(甲基)丙烯酸/單[2－(甲基)丙烯醯氧基乙基]琥珀酸酯/N－環己基順丁烯二醯亞胺/(甲基)丙烯酸四氫呋喃甲酯/(甲基)丙烯酸苯甲酯/單(甲基)丙烯酸甘油酯共聚物，(甲基)丙烯酸/單[2－(甲基)丙烯醯氧基乙基]琥珀酸酯/N－苯基順丁烯二醯亞胺/(甲基)丙烯酸四氫呋喃甲酯/苯乙烯/(甲基)丙烯酸烯丙酯共聚物，(甲基)丙烯酸/單[2－(甲基)丙烯醯氧基乙基]琥珀酸酯/N－苯基順丁烯二醯亞胺/(甲基)丙烯酸四氫呋喃酯/苯乙烯/(甲基)丙烯酸苯甲酯共聚物，(甲基)丙烯酸/單[2－(甲基)丙烯醯氧基乙基]琥珀酸酯/N－苯基順丁烯二醯亞胺/(甲基)丙烯酸四氫呋喃甲酯/(甲基)丙烯酸苯甲酯/單(甲基)丙烯酸甘油酯共聚物，(甲基)丙烯酸/單[2－(甲基)丙烯醯氧基乙基]琥珀酸酯/N－環己基順丁烯二醯亞胺/(甲基)丙烯酸四氫呋喃甲酯/苯乙烯/(甲基)丙烯酸正丁酯/(甲基)丙烯酸烯丙酯共聚物，(甲基)丙烯酸/單[2－(甲基)丙烯醯氧基乙基]琥珀酸酯/N－環己基順丁烯二醯亞胺/(甲基)丙烯酸四氫呋喃甲酯/苯乙烯/(甲基)丙烯酸正丁酯/(甲基)丙烯酸苯甲酯共聚物，(甲基)丙烯酸/單[2－(甲基)丙烯醯氧基乙基]琥珀酸酯/N－苯基順丁烯二醯亞胺/(甲基)丙烯酸四氫呋喃甲酯/苯乙烯/(甲基)丙烯酸正丁酯/(甲基)丙烯酸烯丙酯共聚物，(甲基)丙烯酸/單[2－(甲基)丙烯醯氧基乙基]琥珀酸酯/N－苯基順丁烯二醯亞胺/(甲基)丙烯酸四氫呋喃甲酯/苯乙烯/(甲基)丙烯酸正丁酯/(甲基)丙烯酸苯甲酯共聚物，(甲基)丙烯酸/單[2－(甲基)丙烯醯氧基乙基]琥珀酸酯/N－苯基順丁烯二醯亞胺/(甲基)丙烯酸四氫呋喃甲酯/(甲基)丙烯酸正丁酯/(甲基)丙烯酸苯甲酯/單(甲基)丙烯酸甘油酯共聚物，(甲基)丙烯酸/(甲基)丙烯酸ω－羧聚己內單酯/N－環己基順丁烯二醯亞胺/(甲基)丙烯酸四氫呋喃甲酯/苯乙烯/(甲基)丙烯酸苯甲酯/單(甲基)丙烯酸甘油酯共聚物，(甲基)丙烯酸/(甲基)丙烯酸ω－羧聚己內單酯/N－苯基順丁烯二醯亞胺/(甲基)丙烯酸四氫呋喃甲酯/苯乙烯/(甲基)丙烯酸苯甲酯/單(甲基)丙烯酸甘油酯共聚物，(甲基)丙烯酸/(甲基)丙烯酸ω－羧聚己內單酯/N－苯基順丁烯二醯亞胺/(甲基)丙烯酸四氫呋喃甲酯/苯乙烯/(甲基)丙烯酸正丁酯/(甲基)丙烯酸苯甲酯/單(甲基)丙烯酸甘油酯共聚物，以及於每一此等共聚物中以[2－(甲基)丙烯醯氧基乙基](四氫呋喃甲基)琥珀酸酯替換(甲基)丙烯酸四氫呋喃甲酯所形成的共聚物。Specific examples of the copolymer (BII) include: (meth)acrylic acid/N-phenylmaleimide/(meth)acrylic acid tetrahydrofuranmethyl ester/styrene copolymer, (meth)acrylic acid/N- Phenyl maleimide / methyl tetrahydrofuran (meth) acrylate / methyl (meth) acrylate, (meth) acrylate / N-phenyl maleimide / (methyl ) tetrahydrofuran methyl acrylate / benzyl (meth) acrylate copolymer, (meth) acrylate / N-phenyl maleimide / (meth) acrylate tetrahydrofuran / (meth) acrylic acid 2 -hydroxyethyl ester copolymer, (meth)acrylic acid / N-phenyl maleimide / methyl (meth) acrylate / styrene / n-butyl (meth) acrylate copolymer, (A) Acrylic acid / N-phenyl maleimide / methyl (meth) acrylate / methyl (meth) acrylate / n-butyl (meth) acrylate, (meth) acrylate / N-phenyl maleimide / tetrahydrofuran methyl (meth) acrylate / n-butyl (meth) acrylate / benzyl (meth) acrylate, (meth) acrylate / N - benzene Butylated butylene Amine/tetrahydrofuran methyl (meth)acrylate/n-butyl (meth)acrylate/2-hydroxyethyl (meth)acrylate copolymer, (meth)acrylic acid/N-phenyl maleimide /(meth)acrylic acid tetrahydrofuran methyl ester / styrene / 2-hydroxyethyl (meth) acrylate copolymer, (meth) acrylic acid / N-phenyl maleimide / (meth) acrylate tetrahydrofuran Methyl ester / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer, (meth) acrylate / N-phenyl maleimide / (meth) acrylate tetrahydrofuran Ester / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate copolymer, (meth) acrylate / N-phenyl maleimide / tetramethyl hydroxy (meth) acrylate / Benzyl (meth)acrylate/glycerol mono(meth)acrylate, (meth)acrylic acid/N-phenylmaleimide/tetramethylammonium (meth)acrylate/(methyl) Methyl acrylate/polystyrene macromonomer copolymer, (meth)acrylic acid/N-phenyl maleimide/(meth)acrylic acid tetrahydrofuran methyl ester/(meth)acrylic acid methyl ester/poly Methyl methacrylate Monomer copolymer, (meth)acrylic acid / N-phenyl maleimide / (meth) acrylate tetrahydrofuran methyl ester / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth)acrylic acid/N-phenylbutyleneimine/tetrahydrofuran methyl (meth)acrylate/benzyl benzyl (meth)acrylate/poly(methyl) acrylate macromonomer copolymer, (Meth)acrylic acid / N-phenyl maleimide / Methyl tetrahydrofuran / styrene / n-butyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate copolymerization , (meth)acrylic acid / N-phenyl maleimide / (meth) acrylate tetrahydrofuran / styrene / n-butyl (meth) acrylate / benzyl (meth) acrylate copolymerization , (meth)acrylic acid / N-phenyl maleimide / methyl (meth) acrylate / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymerization , (meth)acrylic acid / N-phenyl maleimide / methyl (meth) acrylate / n-butyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / ( Methyl methacrylate copolymer (Meth)acrylic acid / N-phenyl maleimide / Methyl tetrahydrofuran (meth) acrylate / n-butyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / (methyl ) phenyl acrylate copolymer, (meth)acrylic acid / N-phenyl maleimide / (meth) acrylate tetrahydrofuran methyl / n-butyl (meth) acrylate / (meth) acrylate Ester/mono(meth)acrylate copolymer, (meth)acrylic acid/N-phenyl maleimide/(meth)acrylic acid tetrahydrofuran methyl ester/(meth)acrylic acid methyl ester/(A) (n-butyl acrylate/polystyrene macromonomer copolymer, (meth)acrylic acid / N-phenyl maleimide / methyl (meth) acrylate / methyl (meth) acrylate /(Meth)acrylic acid n-butyl ester / polymethyl methacrylate macromonomer copolymer, (meth)acrylic acid / N-phenyl maleimide / (meth)acrylic acid tetrahydrofuran methyl ester / ( n-Butyl methacrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylate / N-phenyl maleimide / (meth) acrylate tetrahydrofuran Methyl ester / n-butyl (meth)acrylate /(Methyl) methacrylate / polymethyl methacrylate macromonomer copolymer, (meth)acrylic acid / N-phenyl maleimide / (meth)acrylic acid tetrahydrofuran methyl ester / ( 2-hydroxyethyl methacrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylate / N-phenyl maleimide / (methyl) Tetrahydrofuran methyl acrylate / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / poly(methyl) acrylate macromonomer copolymer, (meth) acrylate / N-phenyl cis Butylene diimide / tetrahydrofuran methyl (meth) acrylate / n-butyl (meth) acrylate / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer, (a Acrylic acid / N-phenyl maleimide / Methyl tetrahydrofuran / styrene / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate / polystyrene Macromonomer copolymer, (meth)acrylic acid/N-phenylmaleimide/(meth)acrylic acid tetrahydrofuranmethyl ester/styrene/2-hydroxyethyl (meth)acrylate/(methyl) ) phenyl acrylate / polymethacrylic acid Ester macromonomer copolymer, (meth)acrylic acid/N-phenylbutyleneimine/(meth)acrylic acid tetrahydrofuranmethyl ester/(meth)acrylic acid n-butyl ester/(meth)acrylic acid 2- Hydroxyethyl ester / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylate / N-phenyl maleimide / (meth) acrylate tetrahydrofuran / ( n-Butyl methacrylate / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / poly(methyl) acrylate macromonomer copolymer, (meth) acrylate / N- Phenyl maleimide / tetrahydrofuran methyl (meth) acrylate / n-butyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate / Polystyrene macromonomer copolymer, (meth)acrylic acid/N-phenyl maleimide/(meth)acrylic acid tetrahydrofuranmethyl ester/styrene/n-butyl (meth)acrylate/(A) 2-hydroxyethyl acrylate / phenyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, (meth)acrylic acid / mono [2-(methyl) propylene oxiranyl ethyl] Succinate/N-cyclohexylmethyleneimine/( Ethyl tetrahydrofuran methyl acrylate / styrene / allyl (meth) acrylate copolymer, (meth) acrylic acid / mono [2- (meth) propylene methoxyethyl] succinate / N-cyclohexyl Maleimide/tetramethylammonium (meth)acrylate/styrene/benzyl (meth)acrylate copolymer, (meth)acrylic acid/mono[2-(methyl)acryloxypropoxy Succinate/N-cyclohexylmethyleneimineimide/tetrahydrofuranmethyl (meth)acrylate/benzyl benzyl (meth)acrylate/glycerol mono(meth)acrylate, (methyl) Acrylic acid/mono[2-(methyl)propenyloxyethyl]succinate/N-phenyl maleimide/(meth)acrylic acid tetrahydrofuran methyl ester/styrene/(methyl) Allyl acrylate copolymer, (meth)acrylic acid / mono [2-(methyl) propylene methoxyethyl] succinate / N-phenyl maleimide / tetrahydrofuran (meth) acrylate Ester/styrene/benzyl methacrylate copolymer, (meth)acrylic acid/mono[2-(methyl)propenyloxyethyl]succinate/N-phenylbutylene Imine / tetrahydrofuran methyl (meth) acrylate / (meth) acrylic acid Methyl ester / glycerol mono(meth)acrylate copolymer, (meth)acrylic acid / mono [2-(methyl) propylene oxyethyl] succinate / N-cyclohexyl maleimide /(Meth)acrylic acid tetrahydrofuran methyl ester / styrene / n-butyl (meth) acrylate / allyl (meth) acrylate copolymer, (meth) acrylic acid / single [2- (meth) propylene oxime Ethyl ethyl] succinate / N-cyclohexyl maleimide / methyl (meth) acrylate / styrene / n-butyl (meth) acrylate / benzyl (meth) acrylate copolymerization , (meth)acrylic acid / mono [2-(methyl) propylene methoxyethyl] succinate / N-phenyl maleimide / (meth) acrylate tetrahydrofuran / styrene /(Meth)acrylic acid n-butyl ester / (meth)acrylic acid allyl ester copolymer, (meth)acrylic acid / mono [2-(methyl) propylene methoxyethyl] succinate / N-phenyl Maleimide / tetrahydrofuran methyl (meth) acrylate / n-butyl (meth) acrylate / benzyl (meth) acrylate, (meth) acrylate / single [2- (methyl) propylene oxiranyl ethyl succinate / N-phenyl maleic acid Amine/tetrahydrofuran methyl (meth)acrylate/n-butyl (meth)acrylate/benzyl benzyl (meth)acrylate/glycerol mono(meth)acrylate, (meth)acrylic acid/(methyl) Ω-carboxypolycaprolactone/N-cyclohexylmethyleneimine/(meth)acrylic acid tetrahydrofuranmethyl ester/styrene/benzyl methacrylate/mono(meth)acrylate Ester copolymer, (meth)acrylic acid / (meth)acrylic acid ω-carboxypolyhexyl monoester / N-phenyl maleimide / (meth) acrylate tetrahydrofuran methyl ester / styrene / (A Methyl acrylate/mono(meth) acrylate copolymer, (meth) acrylate / (meth) acrylate ω-carboxy polycaprolactone / N-phenyl maleimide / Tetrahydrofuran methyl (meth)acrylate/styrene/n-butyl (meth)acrylate/benzyl benzyl (meth)acrylate/glycerol mono(meth)acrylate, and in each of these copolymers A copolymer formed by substituting [2-(meth)acryloxyethyl](tetrahydrofuranmethyl)succinate for tetramethylammonium (meth)acrylate.
於上述共聚物(BII)中，(甲基)丙烯酸/N－苯基順丁烯二醯亞胺/(甲基)丙烯酸四氫呋喃甲酯/苯乙烯/(甲基)丙烯酸正丁酯共聚物、(甲基)丙烯酸/N－苯基順丁烯二醯亞胺/(甲基)丙烯酸四氫呋喃甲酯/苯乙烯/(甲基)丙烯酸正丁酯/(甲基)丙烯酸2－羥基乙酯共聚物、(甲基)丙烯酸/N－苯基順丁烯二醯亞胺/單[2－(甲基)丙烯醯氧基乙基]四氫呋喃甲基琥珀酸酯/苯乙烯/(甲基)丙烯酸正丁酯共聚物、(甲基)丙烯酸/N－苯基順丁烯二醯亞胺/單[2－(甲基)丙烯醯氧基乙基]四氫呋喃甲基琥珀酸酯/苯乙烯/(甲基)丙烯酸正丁酯/(甲基)丙烯酸2－羥基乙酯共聚物等係較佳者。In the above copolymer (BII), (meth)acrylic acid / N-phenyl maleimide / (meth)acrylic acid tetrahydrofuran methyl ester / styrene / n-butyl (meth) acrylate copolymer, (Meth)acrylic acid / N-phenyl maleimide / Methyl tetrahydrofuran / styrene / n-butyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate copolymerization , (meth)acrylic acid / N-phenyl maleimide / mono [2-(methyl) propylene oxyethyl] tetrahydrofuran methyl succinate / styrene / (meth) acrylic acid N-butyl ester copolymer, (meth)acrylic acid / N-phenyl maleimide / mono [2-(methyl) propylene oxyethyl] tetrahydrofuran methyl succinate / styrene / ( A n-butyl methacrylate/2-hydroxyethyl (meth) acrylate copolymer or the like is preferred.
於共聚物(BI)中，不飽和化合物(b1)之共聚合量比較佳係1至40重量%，尤佳係5至30重量%，N取代之順丁烯二醯亞胺(b2)之共聚合量比較佳係1至50重量%，尤佳係5至40重量%，不飽和化合物(b3)之共聚合量比較佳係1至70重量%，尤佳係10至40重量%，且不飽和化合物(b4)之共聚合量比較佳係1至80重量%，尤佳係5至60重量%。In the copolymer (BI), the copolymerization amount of the unsaturated compound (b1) is preferably from 1 to 40% by weight, particularly preferably from 5 to 30% by weight, based on the N-substituted maleimide (b2). The copolymerization amount is preferably from 1 to 50% by weight, particularly preferably from 5 to 40% by weight, and the copolymerization amount of the unsaturated compound (b3) is preferably from 1 to 70% by weight, particularly preferably from 10 to 40% by weight, and The amount of the copolymerization of the unsaturated compound (b4) is preferably from 1 to 80% by weight, particularly preferably from 5 to 60% by weight.
於本發明中，於共聚物(BI)中的不飽和化合物之共聚合量比以上述範圍界定，藉此可獲得在敏感度、對基材之黏著力及對溶劑抗性上優異的輻射敏感性組成物。In the present invention, the copolymerization amount of the unsaturated compound in the copolymer (BI) is defined by the above range, whereby radiation sensitivity excellent in sensitivity, adhesion to a substrate, and resistance to a solvent can be obtained. Sexual composition.
於本發明中，共聚物(BI)可與其他鹼溶性樹脂組合使用。In the present invention, the copolymer (BI) can be used in combination with other alkali-soluble resins.
上述鹼溶性樹脂並無特殊限制，只要其於(A)著色劑之上作用為黏著劑且在用於形成著色層的顯影步驟所用的鹼性顯影溶液中具有溶解性即可。舉例而言，鹼溶性樹脂較佳具有羧基，且其實例為由選自關於共聚物(BI)所描述之實例的不飽和羧酸或不飽和羧酸酐中之至少一者以及選自關於共聚物(BI)所描述之實例的N取代之順丁烯二醯亞胺或不飽和化合物(b4)中之至少一者所形成的共聚物(共聚物(BII))。The above alkali-soluble resin is not particularly limited as long as it acts as an adhesive on the (A) colorant and has solubility in the alkaline developing solution used in the developing step for forming the coloring layer. For example, the alkali-soluble resin preferably has a carboxyl group, and examples thereof are at least one selected from the group consisting of unsaturated carboxylic acids or unsaturated carboxylic anhydrides described in relation to the copolymer (BI) and selected from copolymers. (BI) A copolymer (copolymer (BII)) formed by at least one of N-substituted maleimide or unsaturated compound (b4) of the examples described.
尤其是，以由(i)至少一種含有(甲基)丙烯酸作為必要組份之不飽和羧酸以及(ii)選自N－環己基順丁烯二醯亞胺、N－苯基順丁烯二醯亞胺、苯乙烯、(甲基)丙烯酸甲酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸2乙基己酯、(甲基)丙烯酸2－羥基乙酯、(甲基)丙烯酸烯丙酯、(甲基)丙烯酸苯甲酯、單(甲基)丙烯酸甘油酯、聚苯乙烯巨單體及聚甲基丙烯酸甲酯巨單體中之至少一者所形成的共聚物，作為較佳的“其他”鹼溶性樹脂。In particular, it comprises (i) at least one unsaturated carboxylic acid containing (meth)acrylic acid as an essential component and (ii) selected from N-cyclohexylmethyleneimine, N-phenylbutylene Diimine, styrene, methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (methyl) a copolymer of at least one of allyl acrylate, benzyl (meth) acrylate, glycerol mono(meth) acrylate, polystyrene macromonomer, and polymethyl methacrylate macromonomer As a preferred "other" alkali soluble resin.
於本發明中，當以凝膠滲透層析術(GPC，洗提溶劑：四氫呋喃)進行測量時，共聚物(BI)和“其他”鹼溶性樹脂分別具有2000至300000，較佳3000至100000，之如苯乙烯的重量平均分子量(以下稱為“Mw”)。In the present invention, when measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran), the copolymer (BI) and the "other" alkali-soluble resin have 2,000 to 300,000, preferably 3,000 to 100,000, respectively. For example, the weight average molecular weight of styrene (hereinafter referred to as "Mw").
另外，當以凝膠滲透層析術(GPC，洗提溶劑：四氫呋喃)進行測量時，共聚物(BI)和“其他”鹼溶性樹脂分別具有3000至60000，較佳5000至25000，之如苯乙烯的數量平均分子量(以下稱為“Mn”)。Further, when measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran), the copolymer (BI) and the "other" alkali-soluble resin have 3,000 to 60,000, preferably 5,000 to 25,000, respectively, such as benzene. The number average molecular weight of ethylene (hereinafter referred to as "Mn").
於本發明中，使用具有上述指明之Mw和Mn的共聚物(BI)，或組合使用此共聚物(BI)與具有上述指明之Mw和Mn的其他鹼溶性化合物，藉此可獲得顯影性優異之輻射敏感性組成物，而可形成具有清晰圖案邊緣的像素和黑矩陣，且於顯影期間，基材的非曝光部分和遮罩層上之殘餘物、背景污染、剩餘膜的發生係受到抑制。In the present invention, a copolymer (BI) having the above-mentioned Mw and Mn is used, or a copolymer (BI) and another alkali-soluble compound having the above-mentioned Mw and Mn are used in combination, whereby excellent developability can be obtained. The radiation-sensitive composition forms a pixel having a sharp pattern edge and a black matrix, and during development, the non-exposed portion of the substrate and the residue on the mask layer, background contamination, and residual film formation are suppressed .
各共聚物(BI)和“其他”鹼溶性樹脂之Mw和Mn比(Mw/Mn)較佳係1至5，更佳係1至4。The Mw and Mn ratio (Mw/Mn) of each of the copolymer (BI) and the "other" alkali-soluble resin is preferably from 1 to 5, more preferably from 1 to 4.
於本發明中，可單獨使用上述共聚物(BI)或可結合使用其中二或多者，此亦適用於“其他”鹼溶性樹脂。In the present invention, the above copolymer (BI) may be used singly or in combination of two or more thereof, which is also applicable to "other" alkali-soluble resins.
於本發明中，以每100重量份(A)著色劑計，鹼溶性樹脂的總量較佳係10至1000重量份，更佳係20至500重量份。舉例而言，當鹼溶性樹脂的總量小於10重量份時，鹼顯影性可能會降低且背景污染或剩餘膜可能發生於基材的非曝光部分和遮罩層上。當其超過1000重量份時，著色劑的濃度相對降低，因此可能難以達成所欲薄膜之色濃度。In the present invention, the total amount of the alkali-soluble resin is preferably from 10 to 1,000 parts by weight, more preferably from 20 to 500 parts by weight, per 100 parts by weight of the (A) coloring agent. For example, when the total amount of the alkali-soluble resin is less than 10 parts by weight, alkali developability may be lowered and background contamination or residual film may occur on the non-exposed portion of the substrate and the mask layer. When it exceeds 1000 parts by weight, the concentration of the colorant is relatively lowered, so that it may be difficult to achieve the desired color density of the film.
另外，於鹼溶性樹脂中的共聚物(BI)含量較佳係10至100重量%，尤佳係20至100重量%。當共聚物(BI)含量小於10重量%時，本發明之所欲功效會受損。Further, the copolymer (BI) content in the alkali-soluble resin is preferably from 10 to 100% by weight, particularly preferably from 20 to 100% by weight. When the copolymer (BI) content is less than 10% by weight, the desired effects of the present invention are impaired.
本發明之多官能性單體意指具有二或多個可聚合之不飽和鍵的單體。The polyfunctional monomer of the present invention means a monomer having two or more polymerizable unsaturated bonds.
多官能性單體之實例包括：烷二醇(例如乙二醇、丙二醇等)之二(甲基)丙烯酸酯類；聚烷二醇(例如聚乙二醇、聚丙二醇等)之二(甲基)丙烯酸酯類；三元或以上的多元醇(例如甘油、三羥甲丙烷、新戊四醇、二新戊四醇等)之聚(甲基)丙烯酸酯類，以及它們的經二羧酸改質的產物；聚酯、環氧樹脂、胺甲酸乙酯樹脂、酸醇樹脂、聚矽氧樹脂、螺烷樹脂等之寡(甲基)丙烯酸酯類；雙端羥基化聚合物(例如雙端羥基聚－1,3－丁二烯、雙端羥基聚己內酯等)之二(甲基)丙烯酸酯類；以及三[2－(甲基)丙烯醯氧基乙基]磷酸酯。Examples of the polyfunctional monomer include: a di(meth)acrylate of an alkanediol (e.g., ethylene glycol, propylene glycol, etc.); a polyalkylene glycol (e.g., polyethylene glycol, polypropylene glycol, etc.) Acrylates; poly(meth)acrylates of ternary or higher polyols (eg, glycerol, trimethylolpropane, pentaerythritol, dipentaerythritol, etc.), and their dicarboxylic acids Acid-modified products; oligo(meth)acrylates of polyesters, epoxies, urethane resins, acid alcohol resins, polyoxyxylene resins, spiro resins, etc.; double-ended hydroxylated polymers (eg Di(meth)acrylates of double-end hydroxy poly-1,3-butadiene, double-ended hydroxypolycaprolactone, etc.; and tris[2-(methyl)propenyloxyethyl]phosphate .
於此等多官能性單體中，以三元或以上之多元醇的聚(甲基)丙烯酸酯或它們的經二羧酸改質的產物為較佳者，且以三丙烯酸三羥甲丙烷酯、三甲基丙烯酸三羥甲丙烷酯、三丙烯酸新戊四醇酯、三甲基丙烯酸新戊四醇酯、四丙烯酸新戊四醇酯、四甲基丙烯酸新戊四醇酯、五丙烯酸二新戊四醇酯、五甲基丙烯酸二新戊四醇酯、六丙烯酸二新戊四醇酯、六甲基丙烯酸二新戊四醇酯、下示式(1)化合物、下示式(2)化合物以及類似者為特佳者
尤其是，以三丙烯酸三羥甲丙烷酯和六丙烯酸二新戊四醇酯為尤佳者，因為其中著色層具有高強度和優異表面平滑度，且基材之未曝光部分及遮罩層上的背景污染、剩餘膜等的發生係受到抑制。In particular, trimethylolpropane triacrylate and dineopentaerythritol hexaacrylate are preferred because the colored layer has high strength and excellent surface smoothness, and the unexposed portion of the substrate and the mask layer The occurrence of background contamination, residual film, and the like is suppressed.
可單獨使用上述多官能性單體或可組合使用其中二或多者。The above polyfunctional monomers may be used singly or two or more of them may be used in combination.
於本發明中，以每100重量份(B)鹼溶性樹脂計，多官能性單體較佳係5至500重量份，更佳係20至300重量份。當多官能性單體含量小於5重量份時，著色層的強度和表面平滑度易於降低。當其超過500重量份時，鹼性顯影性易於降低或是基材之未曝光部分及遮罩層上易發生背景污染、剩餘膜等。In the present invention, the polyfunctional monomer is preferably from 5 to 500 parts by weight, more preferably from 20 to 300 parts by weight, per 100 parts by weight of the (B) alkali-soluble resin. When the content of the polyfunctional monomer is less than 5 parts by weight, the strength and surface smoothness of the colored layer are apt to be lowered. When it exceeds 500 parts by weight, the alkali developability is liable to be lowered or background contamination, residual film, and the like are liable to occur on the unexposed portions of the substrate and the mask layer.
另外，於本發明中，可組合使用具有一個可聚合的不飽和鍵之單官能性單體與多官能性單體。Further, in the present invention, a monofunctional monomer having a polymerizable unsaturated bond and a polyfunctional monomer may be used in combination.
上述單官能性單體的實例包括關於(B)鹼溶性樹脂所描述作為(b1)不飽和化合物、N取代之順丁烯二醯亞胺及不飽和化合物(b4)之實例的化合物、N－(甲基)丙烯醯基嗎啉、N－乙烯基吡咯烷酮、N－乙烯基－ε－己內醯胺以及其他市售產品M－5600(商品名，東亞合成股份有限公司提供)。Examples of the above monofunctional monomer include a compound described as (b1) an unsaturated compound, an N-substituted maleimide and an unsaturated compound (b4) with respect to (B) an alkali-soluble resin, N- (Meth)propenylmorpholine, N-vinylpyrrolidone, N-vinyl-ε-caprolactam, and other commercially available products M-5600 (trade name, supplied by East Asia Synthetic Co., Ltd.).
可單獨使用此等單官能性單體或可組合使用其中二或多者。These monofunctional monomers may be used singly or in combination of two or more thereof.
以多官能性單體和單官能性單體之總量為基準計，單官能性單體含量較佳係90重量%或以下，更佳係50重量%或以下。當單官能性單體含量超過90重量%時，所獲得之著色層的強度或表面平滑度可能不足。The monofunctional monomer content is preferably 90% by weight or less, more preferably 50% by weight or less based on the total of the polyfunctional monomer and the monofunctional monomer. When the monofunctional monomer content exceeds 90% by weight, the strength or surface smoothness of the obtained coloring layer may be insufficient.
於本發明中，以100重量份之(B)鹼溶性樹脂計，多官能性單體和單官能性單體的總量較佳係5至500重量份，更佳係20至300重量份。當上述總量少於5重量份時，著色層的強度和表面平滑度易於降低。當其超過500重量份時，舉例而言，鹼性顯影性易於降低或是基材之未曝光部分及遮罩層上易發生背景污染、剩餘膜等。In the present invention, the total amount of the polyfunctional monomer and the monofunctional monomer is preferably from 5 to 500 parts by weight, more preferably from 20 to 300 parts by weight, based on 100 parts by weight of the (B) alkali-soluble resin. When the total amount is less than 5 parts by weight, the strength and surface smoothness of the colored layer are apt to be lowered. When it exceeds 500 parts by weight, for example, alkali developability is liable to be lowered or background contamination, residual film, and the like are liable to occur on the unexposed portions of the substrate and the mask layer.
於本發明中之光聚合作用起始劑意指，藉以諸如可見光、紫外光、遠紅外光、電子輻射、X射線或類似者之輻射曝光，而產生能夠起始上述(C)多官能性單體及隨意之單官能性單體的聚合作用之活性物種的化合物。The photopolymerization initiator in the present invention means that the above (C) polyfunctional single can be initiated by exposure to radiation such as visible light, ultraviolet light, far infrared light, electron radiation, X-ray or the like. Compounds of active species in the polymerization of bulk and random monofunctional monomers.
上述光聚合作用起始劑的實例包括，苯乙酮化合物、二咪唑化合物、三化合物、安息香化合物、二苯基酮化合物、α－乙二酮化合物、多核苯醌化合物、氧葱酮化合物、偶氮化合物、O－醯肟化合物、鎓鹽化合物以及亞胺磺酸鹽化合物。Examples of the above photopolymerization initiator include an acetophenone compound, a diimidazole compound, and three A compound, a benzoin compound, a diphenyl ketone compound, an α-ethanedione compound, a polynuclear benzoquinone compound, an oxonone compound, an azo compound, an O-antimony compound, an onium salt compound, and an imide sulfonate compound.
此等化合物為藉曝光而產生活性基團或活性酸，或產生活性基團及活性酸兩者之化合物。These compounds are compounds which, by exposure, produce reactive groups or active acids, or which produce both active groups and active acids.
於本發明中，可單獨使用上述光聚合作用起始劑或可組合使用其中二或多者。本發明之光聚合作用起始劑較佳係選自苯乙酮化合物、二咪唑化合物、三化合物和O－醯肟化合物中之至少－者。In the present invention, the above photopolymerization initiators may be used singly or two or more of them may be used in combination. The photopolymerization initiator of the present invention is preferably selected from the group consisting of an acetophenone compound, a diimidazole compound, and three At least one of the compound and the O-quinone compound.
於本發明中，以每100重量份(C)多官能性單體或其與單官能性單體總合計，光聚合作用起始劑之含量較佳係0.01至120重量份，更佳係1至100重量份。當光聚合作用起始劑含量小於0.01重量份時，藉曝光造成之固化不足，且可能難以獲得具有以預定陣列排列的著色層圖案之濾光片。當其超過120重量份時，於顯影期間，形成之著色層易於脫離基材。In the present invention, the content of the photopolymerization initiator is preferably 0.01 to 120 parts by weight, more preferably 1 part by weight per 100 parts by weight of the (C) polyfunctional monomer or its total amount with the monofunctional monomer. Up to 100 parts by weight. When the photopolymerization initiator content is less than 0.01 parts by weight, curing by exposure is insufficient, and it may be difficult to obtain a filter having a coloring layer pattern arranged in a predetermined array. When it exceeds 120 parts by weight, the coloring layer formed is easily detached from the substrate during development.
於本發明之較佳光聚合作用起始劑中，具體而言苯乙酮化合物包括，舉例而言，2－羥基－2－甲基－1－苯基丙－1－酮、2－甲基－1－[4－(甲硫)苯基]－2－嗎啉丙－1－酮、2－苯甲基－2－二甲基胺基－1－(4－嗎啉苯基)丁－1－酮、1－羥基環己基苯基酮、2,2－二甲氧基－1,2－二苯基乙－1－酮及1,2－辛二酮。Among the preferred photopolymerization initiators of the present invention, specifically acetophenone compounds include, for example, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl 1-[4-(methylthio)phenyl]-2-morpholinepropan-1-one, 2-benzyl-2-oxomethylamino-1-(4-morpholinylphenyl)- 1-ketone, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one and 1,2-octanedione.
於此等苯乙酮化合物中，以2－甲基－1－[4－(甲硫)苯基]－2－嗎啉丙－1－酮、2－苯甲基 2－二甲基胺基－1－(4－嗎啉苯基)丁－1－酮及1,2－辛二酮為尤佳者。Among these acetophenone compounds, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinpropan-1-one, 2-benzyl-2-dimethylamino 1-(4-morpholinylphenyl)butan-1-one and 1,2-octanedione are preferred.
可單獨使用此上述苯乙酮化合物或可組合使用其中二或多者。The above acetophenone compounds may be used singly or two or more of them may be used in combination.
當使用苯乙酮化合物作為本發明之光聚合作用起始劑時，以每100重量份(C)多官能性單體或其與單官能性單體總合計，苯乙酮化合物之量較佳係0.01至80重量份，更佳係1至60重量份，又更佳係1至30重量份。當苯乙酮化合物含量小於0.01重量份時，藉曝光造成之固化不足，且可能難以獲得具有以預定陣列排列的著色層圖案之濾光片。當其超過80重量份時，於顯影期間，形成之著色層易於脫離基材。When an acetophenone compound is used as the photopolymerization initiator of the present invention, the amount of the acetophenone compound is preferably used per 100 parts by weight of the (C) polyfunctional monomer or a total of the monofunctional monomer. It is 0.01 to 80 parts by weight, more preferably 1 to 60 parts by weight, still more preferably 1 to 30 parts by weight. When the content of the acetophenone compound is less than 0.01 parts by weight, curing by exposure is insufficient, and it may be difficult to obtain a filter having a coloring layer pattern arranged in a predetermined array. When it exceeds 80 parts by weight, the coloring layer formed is easily detached from the substrate during development.
另外，上述二咪唑化合物的具體實例包括2,2’－雙(2－氯苯基)－4,4’,5,5’－四(4－乙氧基羰基苯基)－1,2’－二咪唑、2,2’－雙(2－溴苯基)－4,4’,5,5’－四(4－乙氧基羰基苯基)－1,2’－二咪唑、2,2’－雙(2－氯苯基)－4,4’,5,5’－四苯基－1,2’－二咪唑、2,2’－雙(2,4－二氯苯基)－4,4’,5,5’－四苯基－1,2’－二咪唑、2,2’－雙(2,4,6－三氯苯基)－4,4’,5,5’－四苯基－1,2’－二咪唑、2,2’－雙(2－溴苯基)－4,4’,5,5’－四苯基－1,2’－二咪唑、2,2’－雙(2,4－二溴苯基)－4,4’,5,5’－四苯基－1,2’－二咪唑及2,2’－雙(2,4,6－三溴苯基)－4,4’,5,5’－四苯基－1,2’－二咪唑。Further, specific examples of the above diimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2' -diimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-diimidazole, 2, 2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole, 2,2'-bis(2,4-dichlorophenyl) -4,4',5,5'-tetraphenyl-1,2'-diimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5 '-Tetraphenyl-1,2'-diimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole, 2,2'-bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole and 2,2'-bis (2,4, 6-Tribromophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole.
於此等二咪唑化合物中，以2,2’－雙(2－氯苯基)－4,4’,5,5’－四苯基－1,2’－二咪唑、2,2’－雙(2,4－二氯苯基)－4,4’,5,5’－四苯基－1,2’－二咪唑和2,2’－雙(2,4,6－三氯苯基)－4,4’,5,5’－四苯基－1,2’－二咪唑為較佳者，且以2,2’－雙(2,4－二氯苯基)－4,4’,5,5’－四苯基－1,2’－二咪唑為尤佳者。Among these diimidazole compounds, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole, 2,2'- Bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole and 2,2'-bis(2,4,6-trichlorobenzene 4,4',5,5'-tetraphenyl-1,2'-diimidazole is preferred, and 2,2'-bis(2,4-dichlorophenyl)-4, 4',5,5'-tetraphenyl-1,2'-diimidazole is especially preferred.
此等二咪唑化合物於溶劑中具有優異溶解度且不會產生諸如不溶解物質或沉澱物等異物，且其具有高敏感度並使得於低能帶時於曝光下之固化反應完全進行。另外，其不會於未曝光之部分造成固化反應。因此，於曝光後之塗覆膜中，不溶於顯影溶液中的已固化部分與於顯影溶液中具有高敏感度未固化部分係明顯地區分，藉此可形成高明晰度濾光片，其中無過切之著色層圖案係根據預定陣列而安排。These diimidazole compounds have excellent solubility in a solvent and do not generate foreign matter such as insoluble matter or precipitate, and they have high sensitivity and allow the curing reaction under exposure at a low energy band to proceed completely. In addition, it does not cause a curing reaction in the unexposed portion. Therefore, in the coated film after exposure, the cured portion which is insoluble in the developing solution is clearly distinguished from the uncured portion having high sensitivity in the developing solution, whereby a high-definition filter can be formed, wherein none The overcut pattern is arranged according to a predetermined array.
可單獨使用此上述二咪唑化合物或可組合使用其中二或多者。The above-mentioned diimidazole compound may be used singly or two or more of them may be used in combination.
當使用二咪唑化合物作為本發明之光聚合作用起始劑時，以(C)多官能性單體或其與單官能性單體總合計，二咪唑化合物之量較佳係0.01至40重量份，更佳係1至30重量份，又更佳係1至20重量份。當二咪唑化合物之量小於0.01重量份時，藉曝光造成之固化不足，且可能難以獲得具有以預定陣列排列的著色層圖案之濾光片。當其超過40重量份時，於顯影期間，形成之著色層易於脫離基材或是著色層表面易於變得粗糙。When a diimidazole compound is used as the photopolymerization initiator of the present invention, the amount of the diimidazole compound is preferably 0.01 to 40 parts by weight based on the total of the (C) polyfunctional monomer or its monofunctional monomer. More preferably, it is 1 to 30 parts by weight, and more preferably 1 to 20 parts by weight. When the amount of the diimidazole compound is less than 0.01 parts by weight, curing by exposure is insufficient, and it may be difficult to obtain a filter having a coloring layer pattern arranged in a predetermined array. When it exceeds 40 parts by weight, the coloring layer formed is liable to be detached from the substrate during development or the surface of the coloring layer is liable to become rough.
於本發明中，當使用二咪唑化合物作為光聚合作用起始劑時，較佳使用下示氫予體，因可使敏感度進一步改進。In the present invention, when a diimidazole compound is used as a photopolymerization initiator, it is preferred to use a hydrogen donor as shown below because the sensitivity can be further improved.
於此使用之氫予體意指可提供氫原子給曝光下由二咪唑化合物所產生之基團的化合物。The hydrogen donor as used herein means a compound which provides a hydrogen atom to give a group derived from a diimidazole compound upon exposure.
於本發明中，氫予體較佳係硫醇化合物或胺化合物，其將於下文中定義。In the present invention, the hydrogen donor is preferably a thiol compound or an amine compound, which will be defined hereinafter.
上述硫醇化合物意指，含有苯環或雜環作為基環且具有至少一個，較佳1至3個，更佳1至2個巰基直接接合至母核之化合物(以下稱“硫醇基氫予體”)。The above thiol compound means a compound having a benzene ring or a heterocyclic ring as a base ring and having at least one, preferably 1 to 3, more preferably 1 to 2 fluorenyl groups bonded directly to the mother nucleus (hereinafter referred to as "thiol hydrogen" Subject").
上述胺化合物意指，含有苯環或雜環作為基環且具有至少一個，較佳1至3個，更佳1至2個胺基直接接合至基環之化合物(以下稱“胺基氫予體”)。The above amine compound means a compound having a benzene ring or a heterocyclic ring as a base ring and having at least one, preferably 1 to 3, more preferably 1 to 2, amine groups directly bonded to the base ring (hereinafter referred to as "amine hydrogen" body").
此等氫予體可同時具有巰基與胺基。These hydrogen donors may have both a mercapto group and an amine group.
以下將更具體地解釋氫予體。The hydrogen donor will be explained more specifically below.
硫醇基氫予體可具有一或多個苯環或雜環，且可同時具有苯環和雜環兩者。當其具有二或多個此等環時，此等環可形成稠合環。The thiol-based hydrogen donor may have one or more benzene rings or heterocycles, and may have both a benzene ring and a heterocyclic ring. When it has two or more such rings, the rings may form a fused ring.
另外，當硫醇基氫予體具有二或多個巰基，且於其具有至少一個剩餘的自由巰基時，該剩餘的一或多個巰基可由烷基、芳烷基或芳基所取代。另外，只要至少剩餘一個自由巰基時，其具有於其中兩個硫原子透過諸如伸烷基或類似者之二價有機基團彼此接合的結構單元，或是於其中兩個硫原子彼此接合成二硫化物形式的結構單元。Additionally, when the thiol-based hydrogen donor has two or more thiol groups and has at least one remaining free sulfhydryl group, the remaining one or more thiol groups may be substituted with an alkyl group, an aralkyl group or an aryl group. Further, as long as at least one free fluorenyl group remains, it has a structural unit in which two sulfur atoms are bonded to each other through a divalent organic group such as an alkyl group or the like, or two of the sulfur atoms are bonded to each other. A structural unit in the form of a sulfide.
此外，硫醇基氫予體之不同於巰基之位置可被羧基、烷氧羰基、經取代的烷氧羰基、苯氧羰基、經取代的苯氧羰基、硝基或類似者取代。Further, the position of the thiol-based hydrogen donor different from the thiol group may be substituted by a carboxyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, a phenoxycarbonyl group, a substituted phenoxycarbonyl group, a nitro group or the like.
上述硫醇基氫予體之具體實例包括2－巰基苯并噻唑、2－巰基苯并噁唑、2－巰基苯并咪唑、2,5－二巰基－1,3,4－噻二唑及2－巰基－2,5－二甲基胺基吡啶。Specific examples of the above thiol-based hydrogen donor include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2,5-dimercapto-1,3,4-thiadiazole, and 2-mercapto-2,5-dimethylaminopyridine.
於此等硫醇基氫予體中，以2－巰基苯并噻唑及2－巰基苯并噁唑為較佳者，且以2－巰基苯并噻唑為尤佳者。Among these thiol-based hydrogen donors, 2-mercaptobenzothiazole and 2-mercaptobenzoxazole are preferred, and 2-mercaptobenzothiazole is preferred.
另外，胺基氫予體可具有一或多個苯環或雜環，且可同時具有苯環和雜環兩者。當其具有二或多個此等環時，此等環可形成稠合環。Further, the amino hydrogen donor may have one or more benzene rings or heterocyclic rings, and may have both a benzene ring and a heterocyclic ring. When it has two or more such rings, the rings may form a fused ring.
此外，於胺基氫予體中，一或多個胺基可被烷基或經取代的烷基所取代，且不同於胺基之位置可被羧基、烷氧羰基、經取代的烷氧羰基、苯氧羰基、經取代的苯氧羰基或腈基所取代。Further, in the amino hydrogen donor, one or more amine groups may be substituted by an alkyl group or a substituted alkyl group, and the position different from the amine group may be a carboxyl group, an alkoxycarbonyl group or a substituted alkoxycarbonyl group. Substituted by a phenoxycarbonyl group, a substituted phenoxycarbonyl group or a nitrile group.
上述胺基氫予體的具體實例包括4,4’－雙(二甲基胺基)二苯基酮、4,4’－雙(二乙基胺基)二苯基酮、4－二乙基胺基苯乙酮、4－二甲基胺基苯丙酮、乙基－4－二甲基胺基苯甲酸酯、4－二甲基胺基苯甲酸酯及4－二甲基胺基苯甲腈。Specific examples of the above amine hydrogen donor include 4,4'-bis(dimethylamino)diphenyl ketone, 4,4'-bis(diethylamino)diphenyl ketone, 4-diethyl Amino acetophenone, 4-dimethylaminopropiophenone, ethyl-4-dimethylaminobenzoate, 4-dimethylaminobenzoate and 4-dimethylamine Benzobenzonitrile.
於此等胺基氫予體中，以4,4’－雙(二甲基胺基)二苯基酮及4,4’－雙(二乙基胺基)二苯基酮為較佳者，且以4,4’－雙(二乙基胺基)二苯基酮為尤佳者。Among these amine hydrogen donors, 4,4'-bis(dimethylamino)diphenyl ketone and 4,4'-bis(diethylamino)diphenyl ketone are preferred. And 4,4'-bis(diethylamino)diphenyl ketone is particularly preferred.
胺基氫予體亦具有作為不同於二咪唑化合物的基團－產生劑之敏化劑的活性。The amine hydrogen donor also has activity as a sensitizer of a group-generating agent different from the diimidazole compound.
於本發明中，可單獨使用氫予體或可組合使用其中二或多者。較佳係組合使用至少一種硫醇基氫予體及至少一種胺基氫予體，因其確保於顯影期間，形成的著色層不易自基材剝落並因此獲得高著色層強度和高敏感度。In the present invention, hydrogen donors may be used singly or two or more of them may be used in combination. It is preferred to use at least one thiol hydrogen donor and at least one amine hydrogen donor in combination because it ensures that during formation, the formed coloring layer is less likely to flake off from the substrate and thus obtain high colored layer strength and high sensitivity.
硫醇基氫予體和胺基氫予體之組合的實例包括2－巰基苯并噻唑/4,4’－雙(二甲基胺基)二苯基酮、2－巰基苯并噻唑/4,4’－雙(二乙基胺基)二苯基酮、2－巰基苯并噁唑/4,4’－雙(二甲基胺基)二苯基酮、2－巰基苯并噁唑/4,4’－雙(二乙基胺基)二苯基酮及類似者。另外，以2－巰基苯并噻唑/4,4’－雙(二乙基胺基)二苯基酮及2－巰基苯并噁唑/4,4’－雙(二乙基胺基)二苯基酮之組合為較佳者，並以2－巰基苯并噻唑/4,4’－雙(二乙基胺基)二苯基酮之組合為尤佳者。Examples of the combination of a thiol group hydrogen donor and an amine hydrogen donor include 2-mercaptobenzothiazole/4,4'-bis(dimethylamino)diphenyl ketone, 2-mercaptobenzothiazole/4 , 4'-bis(diethylamino)diphenyl ketone, 2-mercaptobenzoxazole/4,4'-bis(dimethylamino)diphenyl ketone, 2-mercaptobenzoxazole /4,4'-bis(diethylamino)diphenyl ketone and the like. In addition, 2-mercaptobenzothiazole/4,4'-bis(diethylamino)diphenyl ketone and 2-mercaptobenzoxazole/4,4'-bis(diethylamino)di Combinations of phenyl ketones are preferred, and combinations of 2-mercaptobenzothiazole/4,4'-bis(diethylamino)diphenyl ketone are preferred.
於硫醇基氫予體和胺基氫予體之組合中，硫醇基氫予體：胺基氫予體之重量比較佳係1：1至1：4，更佳係1：1至1：3。In the combination of the thiol group hydrogen donor and the amine hydrogen donor, the weight of the thiol hydrogen donor: amine hydrogen donor is preferably from 1:1 to 1:4, more preferably from 1:1 to 1 :3.
當於本發明中組合使用氫予體與二咪唑化合物時，以每100重量份(C)多官能性單體或其與單官能性單體總合計，氫予體之量較佳係0.01至40重量份，更佳係1至30重量份，尤佳係1至20重量份。當氫予體含量低於0.01重量份時，敏感度改進的功效易於降低。當其超過40重量份時，於顯影期間，形成的著色層易於自基材剝落。When a hydrogen donor and a diimidazole compound are used in combination in the present invention, the amount of the hydrogen donor is preferably 0.01 to 100 parts by weight per 100 parts by weight of the (C) polyfunctional monomer or its total amount with the monofunctional monomer. 40 parts by weight, more preferably 1 to 30 parts by weight, particularly preferably 1 to 20 parts by weight. When the hydrogen donor content is less than 0.01 parts by weight, the effect of sensitivity improvement is apt to be lowered. When it exceeds 40 parts by weight, the formed coloring layer is liable to peel off from the substrate during development.
另外，上述三化合物的具體實例包括具有鹵甲基的三化合物，諸如2,4,6－三(三氯甲基)－s－三、2－甲基－4,6－雙(三氯甲基)－s－三、2－[2－(5甲基呋喃－2－基)乙烯基]－4,6－雙(三氯甲基)－s－三、2－[2－(呋喃－2－基)乙烯基]－4,6－雙(三氯甲基)－s－三、2－[2－(4－二基胺基－2－甲基苯基)乙烯基]－4,6雙(三氯甲基)－s三、2－[2－(3,4－二甲氧基苯基)乙烯基]－4,6－雙(三氯甲基)－s－三、2－(4－甲氧基苯基)－4,6－雙(三氯甲基)－s－三、2－(4－乙氧基苯乙烯基)－4,6－雙(三氯甲基)－s－三及2－(4－正丁氧基苯基)－4,6－雙(三氯甲基)－s－三。In addition, the above three Specific examples of the compound include three having a halomethyl group a compound such as 2,4,6-tris(trichloromethyl)-s-three 2-methyl-4,6-bis(trichloromethyl)-s-three ,2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-three ,2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-three 2-[2-(4-Diylamino-2-methylphenyl)vinyl]-4,6-bis(trichloromethyl)-s ,2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-s-three , 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-three , 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-three And 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-three .
於此等三化合物中，以2－[2－(3,4－二甲氧基苯基)乙烯基]－4,6－雙(三氯甲基)－s－三為尤佳者。Three of these Among the compounds, 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-three For the better.
可單獨使用此上述三化合物或可組合使用其中二或多者。This three can be used alone The compound may be used in combination of two or more of them.
當於本發明中使用三化合物作為光聚合作用起始劑時，以每100重量份(C)多官能性單體或是其與單官能性單體總合計，三化合物之量較佳係0.01至40重量份，更佳係1至30重量份，尤佳係1至20重量份。當三化合物之量低於0.01重量份時，藉曝光造成之固化不足，且可能難以獲得具有以預定陣列排列的著色層圖案之濾光片。當其超過40重量份時，於顯影期間，形成之著色層易於脫離基材。When using three in the present invention When the compound is used as a photopolymerization initiator, it is based on 100 parts by weight of (C) polyfunctional monomer or a total of monofunctional monomers thereof. The amount of the compound is preferably from 0.01 to 40 parts by weight, more preferably from 1 to 30 parts by weight, still more preferably from 1 to 20 parts by weight. When three When the amount of the compound is less than 0.01 parts by weight, curing by exposure is insufficient, and it may be difficult to obtain a filter having a coloring layer pattern arranged in a predetermined array. When it exceeds 40 parts by weight, the formed coloring layer is easily released from the substrate during development.
另外，上述O－醯肟化合物的具體實例包括1－[4－(苯基硫)苯基]－庚烷－1,2－二酮2－(O－苯甲醯肟)、1－[4－(苯基硫)苯基]－辛烷－1,2－二酮2－(O－苯甲醯肟)、1－[4－(苯甲醯基)苯基]－辛烷－1,2－二酮2－(O－苯甲醯肟)、1－[9－乙基－6－(2－甲基苯甲醯基)－9H－咔唑－3－基]－乙酮1－(O－醯肟)、1－[9－乙基－6－(3－甲基苯甲醯基)－9H－咔唑－3－基]－乙酮1－(O－醯肟)以及1－[9－乙基－6－苯甲醯基－9H－咔唑－3－基]－乙酮1－(O－醯肟)。Further, specific examples of the above O-ruthenium compound include 1-[4-(phenylthio)phenyl]-heptane-1,2-dione 2-(O-benzamide), 1-[4 -(phenylthio)phenyl]-octane-1,2-dione 2-(O-benzamide), 1-[4-(benzylidene)phenyl]-octane-1, 2-diketone 2-(O-benzamide), 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-ethanone 1- (O-醯肟), 1-[9-ethyl-6-(3-methylbenzhydryl)-9H-indazol-3-yl]-ethanone 1-(O-oxime) and 1 -[9-Ethyl-6-benzhydryl-9H-indazol-3-yl]-ethanone 1-(O-indole).
於此等O－醯肟化合物中，以1－[4－(苯基硫)苯基]一辛烷－1,2－二酮2－(O－苯甲醯肟)和1－[9－乙基－6－(2－甲基苯甲醯基)－9H－咔唑－3－基]－乙酮1－(O－醯肟)為尤佳者。Among such O-indole compounds, 1-[4-(phenylthio)phenyl]-octane-1,2-dione 2-(O-benzamide) and 1-[9- Ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-ethanone 1-(O-indole) is preferred.
可單獨使用此上述O－醯肟化合物或可組合使用其中二或多者。The above O-quinone compounds may be used singly or two or more of them may be used in combination.
當於本發明中使用O－醯肟化合物作為光聚合作用起始劑時，以每100重量份(C)多官能性單體或是其與單官能性單體總合計，O－醯肟化合物之量較佳係0.01至40重量份，更佳係1至30重量份，尤佳係1至20重量份。當O－醯肟化合物含量低於0.01重量份時，藉曝光造成之固化不足，且可能難以獲得具有以預定陣列排列的著色層圖案之濾光片。當其超過40重量份時，於顯影期間，形成之著色層易於脫離基材。When an O-antimony compound is used as a photopolymerization initiator in the present invention, an O-quinone compound is used per 100 parts by weight of the (C) polyfunctional monomer or a total of the monofunctional monomer. The amount is preferably from 0.01 to 40 parts by weight, more preferably from 1 to 30 parts by weight, still more preferably from 1 to 20 parts by weight. When the content of the O-tellurium compound is less than 0.01 parts by weight, curing by exposure is insufficient, and it may be difficult to obtain a filter having a coloring layer pattern arranged in a predetermined array. When it exceeds 40 parts by weight, the formed coloring layer is easily released from the substrate during development.
另外，上述鎓鹽化合物的實例包括二芳基碘鎓鹽、三芳基鋶鹽、二芳基鏻鹽及類似者。Further, examples of the above onium salt compound include a diaryliodonium salt, a triarylsulfonium salt, a diarylsulfonium salt, and the like.
上述二芳基碘鎓鹽的特別實例包括二苯基碘鎓四氟硼酸鹽、二苯基碘鎓六氟磷酸鹽、二苯基碘鎓六氟砷酸鹽、二苯基碘鎓三氟甲烷磺酸鹽、二苯基碘鎓三氟乙酸鹽、二苯基碘鎓對甲苯磺酸鹽、4－甲氧基苯基苯基碘鎓四氟硼酸鹽、4－甲氧基苯基苯基碘鎓六氟磷酸鹽、4－甲氧基苯基苯基碘鎓六氟砷酸鹽、4－甲氧基苯基苯基碘鎓三氟甲烷磺酸鹽、4－甲氧基苯基苯基碘鎓三氟乙酸鹽、4－甲氧基苯基苯基碘鎓對甲苯磺酸鹽、雙(4－第三丁基苯基)碘鎓四氟硼酸鹽、雙(4－第三丁基苯基)碘鎓六氟砷酸鹽、雙(4－第三丁基苯基)碘鎓三氟甲烷磺酸鹽、雙(4－第三丁基苯基)碘鎓三氟乙酸鹽以及雙(4－第三丁基苯基)碘鎓對甲苯磺酸鹽。Specific examples of the above diaryliodonium salt include diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethane Sulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium p-toluenesulfonate, 4-methoxyphenylphenyliodonium tetrafluoroborate, 4-methoxyphenylphenyl Iodine hexafluorophosphate, 4-methoxyphenylphenyliodonium hexafluoroarsenate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylbenzene Iodine iodine trifluoroacetate, 4-methoxyphenylphenyliodonium p-toluenesulfonate, bis(4-t-butylphenyl)iodonium tetrafluoroborate, bis(4-third Phenyl phenyl) iodonium hexafluoroarsenate, bis(4-t-butylphenyl)iodonium trifluoromethanesulfonate, bis(4-t-butylphenyl)iodonium trifluoroacetate and Bis(4-tert-butylphenyl)iodonium p-toluenesulfonate.
上述三芳基鋶鹽的特別實例包括三苯基鋶四氟硼酸鹽、三苯基鋶六氟磷酸鹽、三苯基鋶六氟砷酸鹽、三苯基鋶三氟甲烷磺酸鹽、三苯基鋶三氟乙酸鹽、三苯基鋶對甲苯磺酸鹽、4－甲氧基苯基二苯基鋶四氟硼酸鹽、4－甲氧基苯基二苯基鋶六氟磷酸鹽、4－甲氧基苯基二苯基鋶六氟砷酸鹽、4－甲氧基苯基二苯基鋶三氟甲烷磺酸鹽、4－甲氧基苯基二苯基鋶三氟乙酸鹽、4－甲氧基苯基二苯基鋶對甲苯磺酸鹽、4－苯基硫苯基二苯基四氟硼酸鹽、4－苯基硫苯基二苯基六氟磷酸鹽、4－苯基硫苯基二苯基六氟砷酸鹽、4－苯基硫苯基二苯基三氟甲烷磺酸鹽、4－苯基硫苯基二苯基三氟乙酸鹽以及4－苯基硫苯基二苯基對甲苯磺酸鹽。Specific examples of the above triarylsulfonium salt include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium trifluoromethanesulfonate, triphenylbenzene Base trifluoroacetate, triphenylsulfonium p-toluenesulfonate, 4-methoxyphenyldiphenylphosphonium tetrafluoroborate, 4-methoxyphenyldiphenylphosphonium hexafluorophosphate, 4 -Methoxyphenyldiphenylphosphonium hexafluoroarsenate, 4-methoxyphenyldiphenylphosphonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylphosphonium trifluoroacetate, 4-methoxyphenyldiphenylphosphonium p-toluenesulfonate, 4-phenylthiophenyldiphenyltetrafluoroborate, 4-phenylthiophenyldiphenylhexafluorophosphate, 4-benzene Thiophenyldiphenylhexafluoroarsenate, 4-phenylthiophenyldiphenyltrifluoromethanesulfonate, 4-phenylthiophenyldiphenyltrifluoroacetate, and 4-phenylsulfide Phenyldiphenyl p-toluenesulfonate.
上述二芳基鏻鹽的特別實例包括(1－6－η－異丙苯)(η－環戊二烯)六氟磷酸鐵及類似者。Specific examples of the above diarylsulfonium salt include (1-6-η-cumene) (η-cyclopentadienyl) iron hexafluorophosphate and the like.
於此等鎓鹽化合物中，以二苯基碘鎓六氟磷酸鹽、三苯基鋶三氟甲烷磺酸鹽等為尤佳者。Among these onium salt compounds, diphenyliodonium hexafluorophosphate, triphenylsulfonium trifluoromethanesulfonate and the like are particularly preferred.
可單獨使用此上述鎓鹽化合物或可組合使用其中二或多者。The above-mentioned onium salt compound may be used singly or two or more of them may be used in combination.
當於本發明中使用鎓鹽化合物作為光聚合作用起始劑時，以每100重量份(C)多官能性單體或是其與單官能性單體總合計，鎓鹽化合物之量較佳係0.01至40重量份，更佳係1至30重量份，尤佳係1至20重量份。當鎓鹽化合物之量低於0.01重量份時，藉曝光造成之固化不足，且可能難以獲得具有以預定陣列排列的著色層圖案之濾光片。當其超過40重量份時，於顯影期間，形成之著色層易於脫離基材。When the onium salt compound is used as the photopolymerization initiator in the present invention, the amount of the onium salt compound is preferably used per 100 parts by weight of the (C) polyfunctional monomer or the total of the monofunctional monomer. It is 0.01 to 40 parts by weight, more preferably 1 to 30 parts by weight, particularly preferably 1 to 20 parts by weight. When the amount of the onium salt compound is less than 0.01 parts by weight, curing by exposure is insufficient, and it may be difficult to obtain a filter having a coloring layer pattern arranged in a predetermined array. When it exceeds 40 parts by weight, the formed coloring layer is easily released from the substrate during development.
本發明之用於形成著色層之輻射敏感性組成物視需要可含有各種添加物。The radiation-sensitive composition for forming a coloring layer of the present invention may contain various additives as needed.
上述添加物的實例包括有機酸或有機胺化合物(除上述氫予體之外)、固化劑、固化輔劑及類似者。Examples of the above additives include organic acids or organic amine compounds (other than the above hydrogen donors), curing agents, curing adjuvants, and the like.
上述有機酸和有機胺化合物係為改進輻射敏感性組成份於鹼性顯影溶液中之溶解度的組份，且其更加抑制顯影後剩餘之未溶解物質。The above organic acid and organic amine compound are components which improve the solubility of the radiation-sensitive component in the alkaline developing solution, and further suppress the undissolved matter remaining after development.
上述有機酸較佳係脂族羧酸或是每分子具有至少一個羧基的含有苯基之羧酸。The above organic acid is preferably an aliphatic carboxylic acid or a phenyl group-containing carboxylic acid having at least one carboxyl group per molecule.
上述脂族羧酸的實例包括：單羧酸類，例如甲酸、乙酸、丙酸、丁酸、戊酸、三甲基乙酸、己酸、二乙基乙酸、庚酸、辛酸等；二羧酸類，例如乙二酸、丙二酸、丁二酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、十三烷二酸、甲基丙二酸、乙基丙二酸、二甲基丙二酸、甲基丁二酸、四甲基丁二酸、環己二羧酸、衣康酸、檸康酸、順丁烯二酸、反丁烯二酸、中康酸等；以及三羧酸類，例如丙三甲酸、烏頭酸、降莰三酸等；另外，上述含有苯基之羧酸的實例包括於其中羧基直接接合至苯基的化合物，以及於其中羧基透過碳鏈接合至苯基的羧酸。Examples of the above aliphatic carboxylic acid include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trimethylacetic acid, caproic acid, diethylacetic acid, heptanoic acid, octanoic acid and the like; dicarboxylic acids, For example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, tridecanedioic acid, methylmalonic acid, B Malonic acid, dimethylmalonic acid, methyl succinic acid, tetramethyl succinic acid, cyclohexanedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid And mesaconic acid; and tricarboxylic acids such as propylene tricarboxylic acid, aconitic acid, oxalic acid, etc.; in addition, examples of the above phenyl group-containing carboxylic acid include compounds in which a carboxyl group is directly bonded to a phenyl group, and A carboxylic acid in which a carboxyl group is bonded to a phenyl group through a carbon.
含有苯基之羧酸的實例包括：芳族單羧酸類，例如苯甲酸、甲苯甲酸、茴香酸、2,3－二甲苯甲酸、3,5－二甲苯甲酸等；芳族二羧酸類，例如酞酸、異酞酸、對酞酸等；三價或以上之芳族聚羧酸類，例如偏苯二甲酸、對稱苯二甲酸、1,2,3,5－苯四甲酸、1,2,4,5－苯四甲酸等；苯乙酸、氫阿托酸、氫桂皮酸、苦杏仁酸、苯琥珀酸、阿托酸、桂皮酸、桂皮二烯酸、香豆酸、繖形酸及類似者。Examples of the phenyl group-containing carboxylic acid include: aromatic monocarboxylic acids such as benzoic acid, toluic acid, anisic acid, 2,3-xylenecarboxylic acid, 3,5-xylenecarboxylic acid, etc.; aromatic dicarboxylic acids, for example Tannic acid, isophthalic acid, p-citric acid, etc.; trivalent or higher aromatic polycarboxylic acids such as phthalic acid, symmetrical phthalic acid, 1,2,3,5-benzenetetracarboxylic acid, 1,2, 4,5-benzenetetracarboxylic acid, etc.; phenylacetic acid, hydrogen atoic acid, hydrogen cinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, cinnamic acid, coumaric acid, umbrella acid and the like By.
於此等有機酸中，就鹼溶性、於溶劑中的溶解度(將於下文進行說明)，和預防背景污染及於基材之未曝光部分或遮罩層上之剩餘膜的觀點而言，脂族二羧酸係較佳者，而以丙二酸、己二酸、衣康酸、檸康酸、反丁烯二酸、中康酸等作為尤佳之脂族羧酸。且以芳族二羧酸作為較佳之含有苯基之羧酸，並以酞酸為尤佳者。Among these organic acids, in terms of alkali solubility, solubility in a solvent (to be described later), and prevention of background contamination and remaining film on the unexposed portion or the mask layer of the substrate, the grease is used. The dicarboxylic acid is preferred, and malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid or the like is preferred as the aliphatic carboxylic acid. Further, an aromatic dicarboxylic acid is preferred as the carboxylic acid having a phenyl group, and citric acid is preferred.
可單獨使用此上述有機酸或可組合使用其中二或多者。These organic acids may be used singly or in combination of two or more.
以全部輻射敏感性組成物為基準計，有機酸含量較佳係15重量%或更低，更佳係10重量%或更低。當有機酸含量超過15重量%時，形成之著色層對基材之黏著力易降低。The organic acid content is preferably 15% by weight or less, more preferably 10% by weight or less, based on the total of the radiation-sensitive composition. When the organic acid content exceeds 15% by weight, the adhesion of the formed coloring layer to the substrate is apt to reduce.
上述有機胺化合物較佳係脂族胺或每分子具有一或多個胺基之含有苯基的胺。The above organic amine compound is preferably an aliphatic amine or a phenyl group-containing amine having one or more amine groups per molecule.
上述脂族胺的實例包括：單(環)烷基胺類，例如正丙基胺、異丙基胺、正丁基胺、異丁基胺、第二丁基胺、第三丁基胺、正戊基胺、正己基胺、正庚基胺、正辛基胺、正壬基胺、正癸基胺、正十一烷基胺、正十二烷基胺、環己胺、2－甲基環己胺、3－甲基環己胺、4－甲基環己胺、2－乙基環己胺、3－乙基環己胺、4－乙基環己胺等；二(環)烷基胺類，例如甲基乙基胺、二乙基胺、甲基正丙基胺、乙基正丙基胺、二正丙基胺、二異丙基胺、二正丁基胺、二異丁基胺、二第二丁基胺、二第三丁基胺、二正戊基胺、二正己基胺、甲基環己胺、乙基環己胺、二環己胺等；三(環)烷基胺類，例如二甲基乙基胺、甲基二乙基胺、三乙基胺、二甲基正丙基胺、二乙基正丙基胺、甲基二正丙基胺、乙基二正丙基胺、三正丙基胺、三異丙基胺、三正丁基胺、三異丁基胺、三第二丁基胺、三第三丁基胺、三正戊基胺、三正己基胺、二甲基環己胺、二乙基環己胺、甲基二環己胺、乙基二環己胺、三環己胺等；單(環)烷醇胺類，例如2－胺基乙醇、3－胺基－1－丙醇、1－胺基－2－丙醇、4－胺基－1－丁醇、5－胺基－1－戊醇、6－胺基－1－己醇、4－胺基－1－環己醇等；二(環)烷醇胺類，例如二乙醇胺、二正丙醇胺、二異丙醇胺、二正丁醇胺、二異丁醇胺、二正己醇胺、二(4－環己醇)胺等；三(環)烷醇胺類，例如三乙醇胺、三正丙醇胺、三異丙醇胺、三正丁醇胺、三異丁醇胺、三正戊醇胺、三正己醇胺、三(4－環己醇)胺等；胺基(環)烷二醇類，例如3－胺基－1,2－丙二醇、2－胺基－1,3－丙二醇、4－胺基－1,2－丁二醇、4－胺基－1,3－丁二醇、4－胺基－1,2－環己二醇、4－胺基－1,3－環己二醇、3－二甲基胺基－1,2－丙二醇、3－二乙基胺基－1,2－丙二醇、2－二甲基胺基－1,3－丙二醇、2－二乙基胺基－1,3－丙二醇等；含有胺基之環烷甲醇類，例如1－胺基環戊甲醇、4－胺基環戊甲醇、1－胺基環己甲醇、4－胺基環己甲醇、4－二甲基胺基環戊甲醇、4－二乙基胺基環戊甲醇、4－二甲基胺基環己甲醇、4－二乙基胺基環己甲醇；以及胺基羧酸類，例如β－丙胺酸、2－胺基丁酸、3－胺基丁酸、4－胺基丁酸、2－胺基異丁酸、3－胺基異丁酸、2－胺基戊酸、5－胺基戊酸、6－胺基己酸、1－胺基環丙羧酸、1－胺基環己羧酸、4－胺基環己羧酸等。Examples of the above aliphatic amines include mono(cyclo)alkylamines such as n-propylamine, isopropylamine, n-butylamine, isobutylamine, second butylamine, tert-butylamine, N-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine, n-undecylamine, n-dodecylamine, cyclohexylamine, 2-methyl Cyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine, 2-ethylcyclohexylamine, 3-ethylcyclohexylamine, 4-ethylcyclohexylamine, etc.; Alkylamines such as methyl ethylamine, diethylamine, methyl n-propylamine, ethyl n-propylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, two Isobutylamine, di-tert-butylamine, di-t-butylamine, di-n-pentylamine, di-n-hexylamine, methylcyclohexylamine, ethylcyclohexylamine, dicyclohexylamine, etc.; Cycloalkylamines such as dimethylethylamine, methyldiethylamine, triethylamine, dimethyl-n-propylamine, diethyl-n-propylamine, methyldi-n-propylamine , ethyl di-n-propylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, Second butylamine, tri-tert-butylamine, tri-n-pentylamine, tri-n-hexylamine, dimethylcyclohexylamine, diethylcyclohexylamine, methyldicyclohexylamine, ethyldicyclohexyl Amine, tricyclohexylamine, etc.; mono(cyclo)alkanolamines, such as 2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1 -butanol, 5-amino-1-pentanol, 6-amino-1-hexanol, 4-amino-1-cyclohexanol, etc.; di(cyclo)alkanolamines, such as diethanolamine, two N-propanolamine, diisopropanolamine, di-n-butanolamine, diisobutanolamine, di-n-hexanolamine, bis(4-cyclohexanol)amine, etc.; tri(cyclo)alkanolamines, for example, three Ethanolamine, tri-n-propanolamine, triisopropanolamine, tri-n-butanolamine, triisobutanolamine, tri-n-pentanolamine, tri-n-hexanolamine, tris(4-cyclohexanol)amine, etc.; (cyclo)alkanediols, such as 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, 4-amino-1 , 3-butanediol, 4-amino-1,2-cyclohexanediol, 4-amino-1,3-cyclohexanediol, 3-dimethylamino-1,2-propanediol, 3 -two Ethylamino-1,2-propanediol, 2-dimethylamino-1,3-propanediol, 2-diethylamino-1,3-propanediol, etc.; amine-containing cycloalkane methanols, for example 1-aminocyclopentanol, 4-aminocyclopentanol, 1-aminocyclohexanemethanol, 4-aminocyclohexanemethanol, 4-dimethylaminocyclopentanol, 4-diethylamino Cyclopentanol, 4-dimethylaminocyclohexanemethanol, 4-diethylaminocyclohexanemethanol; and aminocarboxylic acids such as β-alanine, 2-aminobutyric acid, 3-aminobutyl Acid, 4-aminobutyric acid, 2-aminoisobutyric acid, 3-aminoisobutyric acid, 2-aminopentanoic acid, 5-aminopentanoic acid, 6-aminocaproic acid, 1-amino group Cyclopropanecarboxylic acid, 1-aminocyclohexanecarboxylic acid, 4-aminocyclohexanecarboxylic acid, and the like.
另外，上述含有苯基之胺的實例包括於其中胺基直接接合至苯基的化合物與其中胺基透過碳鏈接合至苯基的化合物。Further, examples of the above phenyl group-containing amine include a compound in which an amine group is directly bonded to a phenyl group and a compound in which an amine group is bonded to a phenyl group through a carbon.
含有苯基之胺的實例包括：芳族胺類，例如苯胺、2－甲基苯胺、3－甲基苯胺、4－甲基苯胺、4－乙基苯胺、4－正丙基苯胺、4－異丙基苯胺、4－正丁基苯胺、4－第三丁基苯胺、1－萘基胺、2萘基胺、N,N－二甲基苯胺、N,N－二乙基苯胺、4－甲基－N,N－二甲基苯胺等；胺基苯甲基醇類，例如2－胺基苯甲基醇、3－胺基苯甲基醇、4－胺基苯甲基醇、4－二甲基胺基苯甲基醇、4－二乙基胺基苯甲基醇等；以及胺基苯酚類，例如2－胺基苯酚、3－胺基苯酚、4－胺基苯酚、4－二甲基胺基苯酚、4－二乙基胺基苯酚等。Examples of the phenyl group-containing amine include: aromatic amines such as aniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-ethylaniline, 4-n-propylaniline, 4- Isopropylaniline, 4-n-butylaniline, 4-tert-butylaniline, 1-naphthylamine, 2naphthylamine, N,N-dimethylaniline, N,N-diethylaniline, 4 -methyl-N,N-dimethylaniline, etc.; aminobenzyl alcohols, such as 2-aminobenzyl alcohol, 3-aminobenzyl alcohol, 4-aminobenzyl alcohol, 4-dimethylaminobenzyl alcohol, 4-diethylaminobenzyl alcohol, etc.; and aminophenols such as 2-aminophenol, 3-aminophenol, 4-aminophenol, 4-dimethylaminophenol, 4-diethylaminophenol, and the like.
於此等有機胺化合物中，就於溶劑中的溶解度(將於下文進行說明)，和預防背景污染及於基材之未曝光部分或遮罩層上之剩餘膜的觀點而言，單(環)烷醇胺類、胺基(環)烷二醇類係較佳者，而以2－胺基乙醇、3胺基－1－丙醇、5－胺基－1－戊二醇、3－胺基－1,2－丙二醇、2－胺基－1,3－丙二醇、4－胺基－1,2－丁二醇等作為尤佳之脂族胺。且以胺基苯酚作為較佳之含有苯基之胺，並以2－胺基苯酚、3－胺基苯酚、4－胺基苯酚等為尤佳者。Among these organic amine compounds, the solubility in a solvent (which will be described later), and the prevention of background contamination and the remaining film on the unexposed portion of the substrate or the mask layer, Alkanolamines, amine (cyclo)alkanediols are preferred, but 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanediol, 3- Amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol and the like are particularly preferred aliphatic amines. Further, an aminophenol is preferred as the amine containing a phenyl group, and 2-aminophenol, 3-aminophenol, 4-aminophenol or the like is particularly preferred.
上述固化劑係一種與(B)鹼溶性樹脂之羧基及/或四氫呋喃環反應以固化(B)鹼溶性樹脂的組份。The curing agent is a component which reacts with (B) a carboxyl group and/or a tetrahydrofuran ring of an alkali-soluble resin to cure (B) an alkali-soluble resin.
上述固化劑的實例包括環氧化合物和氧環丁烷化合物。Examples of the above curing agent include an epoxy compound and an oxycyclobutane compound.
上述環氧化合物較佳係選自多官能性環氧化合物，其具體實例包括芳族環氧樹脂類，例如雙酚A環氧樹脂、氫化的雙酚A環氧樹脂、雙酚F環氧樹脂、氫化的雙酚F環氧樹脂、酚醛式環氧樹脂等；其他環氧樹脂類，例如脂族環氧樹脂、雜環環氧樹脂、環氧丙基醚樹脂、環氧丙基胺樹脂、環氧化的油等；此等環氧樹脂之溴化的衍生物、丁二烯的(共)聚合物之環氧化的產物、異戊二烯的(共)聚合物之環氧化的產物、含有環氧丙基的不飽和化合物之(共)聚合物、三聚異氰酸三環氧丙酯及類似者。The above epoxy compound is preferably selected from polyfunctional epoxy compounds, and specific examples thereof include aromatic epoxy resins such as bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, and bisphenol F epoxy resin. , hydrogenated bisphenol F epoxy resin, phenolic epoxy resin, etc.; other epoxy resins, such as aliphatic epoxy resin, heterocyclic epoxy resin, epoxy propyl ether resin, epoxypropylamine resin, Epoxidized oil, etc.; brominated derivatives of such epoxy resins, epoxidized products of (co)polymers of butadiene, epoxidized products of (co)polymers of isoprene, containing (co)polymer of epoxypropyl unsaturated compound, triglycidyl isocyanate and the like.
上述環氧化合物較佳係選自含有環氧基之不飽和化合物，其具體實例包括(甲基)丙烯酸環氧丙酯、(甲基)丙烯酸3,4－環氧丁酯、(甲基)丙烯酸6,7－環氧庚酯、鄰乙烯苯甲基環氧丙基醚、間乙烯苯甲基環氧丙基醚及對乙烯苯甲基環氧丙基醚。The above epoxy compound is preferably selected from the group consisting of epoxy group-containing unsaturated compounds, and specific examples thereof include glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, (methyl). 6,7-epoxyheptyl acrylate, o-vinylbenzyloxypropyl ether, m-vinylbenzyloxypropyl ether and p-vinylbenzyloxypropyl ether.
另外，上述氧環丁烷化合物較佳係選自多官能性氧環丁烷化合物，其具體實例包括低分子量化合物，例如雙碳酸環氧丁酯、雙己二環氧丁酯、雙對酞酸環氧丁酯、雙對苯二甲基二羧酸環氧丁酯、雙1,4－環己二羧酸環氧丁酯等，以及高聚合物化合物，例如酚醛樹脂之氧環丁烷之醚化的產物、含有氧環丁基之不飽和化合物的(共)聚合物等。Further, the above oxycyclobutane compound is preferably selected from the group consisting of polyfunctional oxycyclobutane compounds, and specific examples thereof include low molecular weight compounds such as butylene carbonate, butyl hexabutyl epoxide, and dipyruic acid. Butylene butyl carbonate, bisbutylene dicarboxylate butyl acrylate, bis 1,4-cyclohexanedicarboxylate butyl butyl ester, and the like, and high polymer compounds such as oxycyclobutane of phenolic resin An etherified product, a (co)polymer of an oxocyclobutyl group-containing unsaturated compound, and the like.
可單獨使用此此等固化劑或可組合使用其中二或多者。These curing agents may be used singly or in combination of two or more thereof.
以輻射敏感性組成物之固體含量為基準計，固化劑含量較佳係30重量%或更低，更佳係20重量%或更低。當固化劑含量超過30重量%時，所獲得之輻射敏感性組成物的儲存安定性易降低。The curing agent content is preferably 30% by weight or less, more preferably 20% by weight or less, based on the solid content of the radiation-sensitive composition. When the content of the curing agent exceeds 30% by weight, the storage stability of the obtained radiation-sensitive composition is liable to be lowered.
上述固化輔劑係一種促進基於上述固化劑、藉執行上述固化劑之環氧基團及/或環氧丁環的開環作用而進行固化反應的組份。The curing auxiliary agent is a component which accelerates a curing reaction by the ring-opening action of the epoxy group and/or the butylene ring of the curing agent based on the curing agent.
上述固化輔劑的實例包括多價羧酸、多價甲酸酐、胺基化合物和熱產酸劑。Examples of the above curing adjuvant include a polyvalent carboxylic acid, a polyvalent formic anhydride, an amine compound, and a thermal acid generator.
上述多價羧酸的具體實例包括類似於上述有機酸並具有二或多個羧基者，而上述胺基化合物的具體實例包括上述有機胺化合物。Specific examples of the above polyvalent carboxylic acid include those similar to the above organic acid and having two or more carboxyl groups, and specific examples of the above amine compound include the above organic amine compound.
另外，上述多價甲酸酐的具體實例包括芳族多價甲酸酐類，例如酞酸酐、焦蜜石酸酐、苯偏三酸酐、3,3’,4,4’－二苯基酮四羧酸二酐等；脂族多價甲酸酐類，例如衣康酸酐、琥珀酸酐、檸康酸酐、十二號珀酸酐、1,2,3－異丙三甲酸酐、順丁烯二酸酐、1,2,3,4－丁四甲酸二酐等；脂環族多價甲酸酐類，例如六氫酞酸酐、3,4－二甲基四氫酞酸酐、1,2,4－環戊三甲酸酐、1,2,4－環己三甲酸酐、環戊四甲酸二酐、1,2,4,5－環己四甲酸二酐、HIMIC酐等；含有酯基團的甲酸酐類，例如乙二醇雙苯偏三酸酐、甘油苯偏三酸酐等，以及市售之商品名為ADEKA HARDENER EH－700(旭電化工業公司提供)、RIKACID HH(新日化股份有限公司提供)、MH－700(新日化股份有限公司提供)及類似者的其他環氧樹脂固化劑。Further, specific examples of the above polyvalent formic anhydride include aromatic polyvalent formic anhydrides such as phthalic anhydride, pyrogallic anhydride, trimellitic anhydride, 3,3',4,4'-diphenyl ketone tetracarboxylic acid A dianhydride or the like; an aliphatic polyvalent formic anhydride such as itaconic anhydride, succinic anhydride, citraconic anhydride, 12th chloric anhydride, 1,2,3-isopropyltricarboxylic anhydride, maleic anhydride, 1,2 , 3,4-butanetetracarboxylic dianhydride, etc.; alicyclic polyvalent anhydrides such as hexahydrophthalic anhydride, 3,4-dimethyltetrahydrophthalic anhydride, 1,2,4-cyclopentane anhydride, 1,2,4-cyclohexanetricarboxylic anhydride, cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, HIMIC anhydride, etc.; a formic anhydride containing an ester group, such as ethylene glycol Diphenyl trimellitic anhydride, glycerol trimellitic anhydride, etc., and commercially available under the trade name ADEKA HARDENER EH-700 (provided by Asahi Denki Kogyo Co., Ltd.), RIKACID HH (provided by Shin-Sun Chemical Co., Ltd.), MH-700 (new Other chemical curing agents available from Nippon Chemical Co., Ltd. and similar.
另外，上述熱產酸劑的實例包括鋶鹽(除關於上述(D)光聚合作用起始劑之三芳基鋶鹽以外)、苯并硫鎓鹽、銨鹽和鏻鹽。Further, examples of the above thermal acid generator include a phosphonium salt (except for the triarylsulfonium salt of the above (D) photopolymerization initiator), a benzothiazine salt, an ammonium salt, and a phosphonium salt.
上述鋶鹽的具體實例包括：烷基鋶鹽類，例如4－乙醯苯基二甲基鋶六氟銻酸鹽、4－乙醯氧苯基二甲基鋶六氟砷酸鹽、二甲基－4－(苯甲氧基羰氧基)苯基鋶六氟銻酸鹽、二甲基－4－(苯甲醯氧基)苯基鋶六氟銻酸鹽、二甲基－4－(苯甲醯氧基)苯基鋶六氟砷酸鹽、二甲基－3－氯－4－乙醯氧苯基鋶六氟銻酸鹽等；苯甲基鋶鹽類，例如苯甲基－4－羥基苯基甲基鋶六氟銻酸鹽、苯甲基－4－羥基苯基甲基鋶六氟磷酸鹽、4－乙醯氧基苯基苯甲基甲基鋶六氟銻酸鹽、苯甲基－4－甲氧基苯基甲基鋶六氟銻酸鹽、苯甲基－2－甲基－4－羥基苯基甲基鋶六氟銻酸鹽、苯甲基－3－氯－4－羥基苯基甲基鋶六氟砷酸鹽、4－甲氧基苯甲基－4－羥基苯基甲基鋶六氟磷酸鹽等；二苯甲基鋶鹽類，例如二苯甲基－4－羥基苯基鋶六氟銻酸鹽、二苯甲基－4－羥基苯基鋶六氟磷酸鹽、4－乙醯氧基苯基二苯甲基鋶六氟銻酸鹽、二苯甲基－4－甲氧基苯基鋶六氟銻酸鹽、二苯甲基－3－氯－4－羥基苯基鋶六氟砷酸鹽、二苯甲基－3－甲基－4－羥基－5－第三丁基苯基鋶六氟銻酸鹽、苯甲基－4－甲氧基苯基－4－羥基苯基鋶六氟磷酸鹽等；以及經取代的苯甲基鋶鹽類，例如對氯苯甲基－4－羥基苯基甲基鋶六氟銻酸鹽、對硝基苯甲基－4－羥基苯基甲基鋶六氟銻酸鹽、對氯苯甲基－4－羥基苯基甲基鋶六氟磷酸鹽、對硝基苯甲基－3－甲基－4－羥基苯基甲基鋶六氟銻酸鹽、3,5－二氯苯甲基－4－羥基苯基甲基鋶六氟銻酸鹽、鄰氯苯甲基－3－氯－4－羥基苯基甲基鋶六氟銻酸鹽等。Specific examples of the above sulfonium salt include alkyl sulfonium salts such as 4-ethyl phenyl phenyl hexafluoroantimonate, 4-ethyl fluorenyl phenyl dimethyl hexafluoro arsenate, and dimethyl 4-(benzyloxycarbonyloxy)phenylphosphonium hexafluoroantimonate, dimethyl-4-(benzylideneoxy)phenylphosphonium hexafluoroantimonate, dimethyl-4- (benzylideneoxy)phenylphosphonium hexafluoroarsenate, dimethyl-3-chloro-4-ethenyloxyphenylphosphonium hexafluoroantimonate, etc.; benzylhydrazine salts, such as benzyl 4-hydroxyphenylmethylphosphonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylphosphonium hexafluorophosphate, 4-ethenyloxyphenylbenzylmethylphosphonium hexafluoroantimonate Salt, benzyl-4-methoxyphenylmethyl hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethyl hexafluoroantimonate, benzyl-3- -Chloro-4-hydroxyphenylmethylphosphonium hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenylmethylphosphonium hexafluorophosphate, etc.; diphenylmethyl phosphonium salts, for example, two Benzyl-4-hydroxyphenylphosphonium hexafluoroantimonate, diphenylmethyl-4-hydroxyphenylphosphonium hexafluorophosphate, 4 Ethyloxyphenyl diphenylmethyl hexafluoroantimonate, benzhydryl-4-methoxyphenyl hexafluoroantimonate, diphenylmethyl-3-chloro-4-hydroxyphenyl Hexafluoroarsenate, benzhydryl-3-methyl-4-hydroxy-5-tert-butylphenylphosphonium hexafluoroantimonate, benzyl-4-methoxyphenyl-4- Hydroxyphenyl sulfonium hexafluorophosphate; and substituted benzyl sulfonium salts such as p-chlorobenzyl-4-hydroxyphenylmethyl hexafluoroantimonate, p-nitrobenzyl-4 -hydroxyphenylmethylhydrazine hexafluoroantimonate, p-chlorobenzyl-4-hydroxyphenylmethylphosphonium hexafluorophosphate, p-nitrobenzyl-3-methyl-4-hydroxyphenyl Hexafluoroantimonate, 3,5-dichlorobenzyl-4-hydroxyphenylmethylphosphonium hexafluoroantimonate, o-chlorobenzyl-3-chloro-4-hydroxyphenylmethylhydrazine Hexafluoroantimonate.
另外，上述苯并硫鎓鹽的具體實例包括苯甲基苯并硫鎓鹽類，例如3－苯甲基苯并硫鎓六氟銻酸鹽、3－苯甲基苯并硫鎓六氟磷酸鹽、3－苯甲基苯并硫鎓四氟硼酸鹽、3－(對甲氧基苯甲基)苯并硫鎓六氟銻酸鹽、3－苯甲基－2－甲基硫苯并硫鎓六氟銻酸鹽、3－苯甲基－5－氯苯并硫鎓六氟銻酸鹽等。Further, specific examples of the above benzothiazepine salt include benzyl benzothiazine salts, such as 3-benzylmethylbenzothiazepine hexafluoroantimonate, 3-benzylmethylbenzothiazepine hexafluorophosphate Salt, 3-benzylmethylbenzothiazepine tetrafluoroborate, 3-(p-methoxybenzyl)benzothiazepine hexafluoroantimonate, 3-benzyl-2-methylthiobenzoate Thiopurine hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazepine hexafluoroantimonate, and the like.
於此等熱產酸劑中，以4－乙醯氧基苯基二苯甲基鋶六氟砷酸鹽、苯甲基－4－羥基苯基甲基鋶六氟銻酸鹽、4－乙醯氧基苯基苯甲基甲基鋶六氟銻酸鹽、二苯甲基－4－甲氧基苯基鋶六氟銻酸鹽、4－乙醯氧基苯基苯甲基甲基鋶六氟銻酸鹽、3－苯甲基苯并硫鎓六氟銻酸鹽等為較佳者。Among these thermal acid generators, 4-ethyloxy phenyl diphenylmethyl hexafluoroarsenate, benzyl-4-hydroxyphenylmethyl hexafluoroantimonate, 4-B Nonyloxyphenylbenzylmethylhydrazine hexafluoroantimonate, benzhydryl-4-methoxyphenylphosphonium hexafluoroantimonate, 4-ethenyloxyphenylbenzylmethylhydrazine Hexafluoroantimonate, 3-benzylmethylbenzothiazepine hexafluoroantimonate or the like is preferred.
可單獨使用此此等固化輔劑或可組合使用其中二或多者。These curing adjuvants may be used singly or in combination of two or more thereof.
以輻射敏感性組成物全部固體含量為基準計，固化輔劑含量較佳係15重量%或更低，更佳係10重量%或更低。當固化輔劑含量超過15重量%時，所獲得之輻射敏感性組成物的儲存安定性易降低，或於顯影期間形成之著色層易於自基材剝落。The curing adjuvant content is preferably 15% by weight or less, more preferably 10% by weight or less, based on the total solid content of the radiation-sensitive composition. When the curing adjuvant content exceeds 15% by weight, the storage stability of the obtained radiation-sensitive composition is liable to be lowered, or the coloring layer formed during development is liable to peel off from the substrate.
不同於前述的添加物實例包括：分散輔劑類，例如銅酞青衍生物之藍色顏料衍生物、黃色顏料衍生物等；填料類，例如玻璃、氧化鋁等；聚合物化合物類，例如聚乙烯醇、聚乙二醇單烷基醚、聚(丙醯酸氟烷酯)等；界面活性劑類，例如非離子性、陽離子性和陰離子性界面活性劑等；黏著促進劑類，例如乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基三(2－甲氧基乙氧基)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－縮水甘油醚氧基丙基三甲氧基矽烷、3－縮水甘油醚氧基丙基甲基二甲氧基矽烷、2－(3,4－環氧基環己基)乙基三甲氧基矽烷、3－氯丙基甲基二甲氧基矽烷、3－氯丙基三甲氧基矽烷、3－甲基丙烯醯氧基丙基三甲氧基矽烷、3－巰基丙基三甲氧基矽烷等；抗氧化劑類，例如2,2’－硫雙(4－甲基－6－第三丁基苯酚)、2,6－二第三丁基苯酚等；紫外線吸收劑類，例如2－(3－第三丁基－5－甲基－2－羥基苯酚)－5－氯苯并***、烷氧基二苯基酮等；以及聚集抑制劑類，例如聚丙烯酸鈉，熱基團產生劑，例如1,1’－偶氮雙(環己－1－甲腈)、2－苯基偶氮－4－甲氧基－2,4－二甲基戊腈等。Examples of the additives different from the foregoing include: a dispersing auxiliary such as a blue pigment derivative of a copper indigo derivative, a yellow pigment derivative or the like; a filler such as glass, alumina, etc.; a polymer compound such as a poly Vinyl alcohol, polyethylene glycol monoalkyl ether, poly(fluoroalkanoate), etc.; surfactants such as nonionic, cationic and anionic surfactants; adhesion promoters such as ethylene Trimethoxy decane, vinyl triethoxy decane, vinyl tris(2-methoxyethoxy) decane, N-(2-aminoethyl)-3-aminopropylmethyl dimethyl Oxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxy Decane, 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxy Decane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, etc. Antioxidants such as 2,2'-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-t-butylphenol, etc.; ultraviolet absorbers such as 2-(3) -T-butyl-5-methyl-2-hydroxyphenol)-5-chlorobenzotriazole, alkoxydiphenyl ketone, etc.; and aggregation inhibitors such as sodium polyacrylate, thermal group generating agent For example, 1,1'-azobis(cyclohexyl-1-carbonitrile), 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, and the like.
本發明之用於形成著色層的輻射敏感性組成物含有上述(A)至(D)組份作為必要組份，且視需要含有上述添加組份。其較佳以加入溶劑的方式製備為液態組份形式。The radiation-sensitive composition for forming a coloring layer of the present invention contains the above components (A) to (D) as essential components, and optionally contains the above-mentioned additive components. It is preferably prepared in the form of a liquid component by adding a solvent.
上述溶劑可視需要選自，於使用前分散或溶解有(A)至(D)組份及用於構成輻射敏感性組成物之添加組份而不與此等組份進行反應且展現適當揮發性之溶劑。The above solvent may be selected from the group consisting of (A) to (D) components and the added components for constituting the radiation-sensitive composition before use, without reacting with the components and exhibiting appropriate volatility. Solvent.
上述溶劑的實例包括：(聚)烯烴二醇單烷基醚類，例如乙二醇甲基醚、乙二醇乙基醚、乙二醇正丙基醚、乙二醇正丁基醚、二乙二醇甲基醚、二乙二醇乙基醚、二乙二醇正丙基醚、二乙二醇正丁基醚、三乙二醇甲基醚、三乙二醇乙基醚、丙二醇甲基醚、丙二醇乙基醚、丙二醇正丙基醚、丙二醇正丁基醚、二丙二醇甲基醚、二丙二醇乙基醚、二丙二醇正丙基醚、二丙二醇正丁基醚、三丙二醇甲基醚、三丙二醇乙基醚等；(聚)烯烴二醇－單烷基醚乙酸酯類，例如乙二醇－甲基醚乙酸酯、乙二醇－乙基醚乙酸酯、二乙二醇－甲基醚乙酸酯、二乙二醇－乙基醚乙酸酯、丙二醇－甲基醚乙酸酯、丙二醇－乙基醚乙酸酯等；其他醚類，例如二乙二醇二甲基醚、二乙二醇甲基乙基醚、二乙二醇二乙基醚、四氫呋喃等；酮類，例如甲基乙基酮、環己酮、2－庚酮、3－庚酮等；乳酸烷酯類，例如乳酸甲酯、乳酸乙酯等；Examples of the above solvent include: (poly)olefin diol monoalkyl ethers such as ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol n-butyl ether, diethylene glycol Alcohol 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, propylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol n-propyl ether, dipropylene glycol n-butyl ether, tripropylene glycol methyl ether, three Propylene glycol ethyl ether; (poly) olefin diol - monoalkyl ether acetate, such as ethylene glycol - methyl ether acetate, ethylene glycol - ethyl ether acetate, diethylene glycol - A Ethyl ether acetate, diethylene glycol-ethyl ether acetate, propylene glycol-methyl ether acetate, propylene glycol-ethyl ether acetate, etc.; other ethers such as diethylene glycol dimethyl ether , diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, etc.; ketones, such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3- Ketone; lactic acid alkyl esters such as methyl lactate, ethyl lactate and the like;
其他酯類，例如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、乙氧基乙酸乙酯、羥基乙酸乙酯、2－羥基－3－甲基丁酸甲酯、乙酸3－甲基－3甲氧基丁酯、丙酸3－甲基－3甲氧基丁酯、乙酸乙酯、乙酸正丙酯、乙酸異丙酯、乙酸正丁酯、乙酸異丁酯、甲酸正戊酯、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、丙酮乙酸甲酯、丙酮乙酸乙酯、2－酮基丁酸乙酯等；芳族烴類，例如甲苯、二甲苯等；醯胺類或內醯胺類，例如N,N－二甲基甲醯胺、N,N－二甲基乙醯胺、N－甲基吡咯烷酮等。Other esters such as ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3- Ethyl ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, propionic acid 3- Methyl-3 methoxybutyl ester, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, Ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate, 2 - ketobutyrate or the like; aromatic hydrocarbons such as toluene, xylene, etc.; guanamines or linoleamides such as N,N-dimethylformamide, N,N-dimethyl B Indoleamine, N-methylpyrrolidone, and the like.
於此等溶劑中，就溶解度、顏料分散度、施用表現等觀點而言，以丙二醇甲基醚、乙二醇－甲基醚乙酸酯、丙二醇－甲基醚乙酸酯、丙二醇－乙基醚乙酸酯、二乙二醇二甲基醚、二乙二醇甲基乙基醚、環己酮、2－庚酮、3－庚酮、乳酸乙酯、3－甲氧基丙酸乙酯、3－乙氧基丙酸甲酯、3－乙氧基丙酸乙酯、丙酸3－甲基－3－甲氧基丁酯、乙酸正丁酯、乙酸異丁酯、甲酸正戊酯、乙酸異戊酯、丙酸正丁酯、丁酸乙酯、丁酸異丙酯、丁酸正丁酯、丙酮酸乙酯等為較佳者。Among such solvents, propylene glycol methyl ether, ethylene glycol-methyl ether acetate, propylene glycol-methyl ether acetate, propylene glycol-ethyl are used in terms of solubility, pigment dispersion, and application performance. Ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, ethyl lactate, 3-methoxypropionic acid Ester, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutyl propionate, n-butyl acetate, isobutyl acetate, n-pentyl formate Ester, isoamyl acetate, n-butyl propionate, ethyl butyrate, isopropyl butyrate, n-butyl butyrate, ethyl pyruvate and the like are preferred.
可單獨使用上述溶劑或可組合使用其中二或多者。The above solvents may be used singly or two or more of them may be used in combination.
於上述溶劑的組合中，可使用高沸點溶劑，例如苯甲基乙基醚、二正己基醚、丙酮基丙酮、異佛酮、己酸、辛酸、1－辛醇、1－壬醇、苯甲醇、乙酸苯甲酯、苯甲酸乙酯、草酸二乙酯、順丁烯二酸二乙酯、γ－丁內酯、碳酸伸乙酯、碳酸伸丙酯、乙二醇苯基醚等。In the combination of the above solvents, a high boiling solvent such as benzyl ethyl ether, di-n-hexyl ether, acetone acetone, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzene can be used. Methanol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethyl carbonate, propyl carbonate, ethylene glycol phenyl ether, and the like.
可單獨使用此等高沸點溶劑或可組合使用其中二或多者。These high boiling solvents may be used singly or in combination of two or more thereof.
雖無特殊限制，但就所獲得之輻射敏感性組成物的塗覆性與安定性的觀點而言，所欲的溶劑量係使得除溶劑以外之組成物的組份總濃度較佳係5至50重量%，更佳係10至40重量%。Although not particularly limited, the desired amount of the solvent is such that the total concentration of the components other than the solvent is preferably 5 to 5 in terms of the coatability and stability of the radiation-sensitive composition obtained. 50% by weight, more preferably 10 to 40% by weight.
本發明之濾光片具有由本發明之用於形成著色層之輻射敏感性組成物所形成的著色層。The filter of the present invention has a coloring layer formed by the radiation sensitive composition of the present invention for forming a colored layer.
下文將說明用於形成本發明濾光片中之著色層的方法。A method for forming the coloring layer in the filter of the present invention will be described below.
首先，視需要形成遮罩層於基材的表面上以分隔欲形成像素的部分，於基材上施加含有例如紅色顏料分散於其中的輻射敏感性組成物之液體組成物，施加的液體組成物係經預烘烤以揮發溶劑並形成塗覆膜。First, a mask layer is formed on a surface of a substrate as needed to partition a portion where a pixel is to be formed, and a liquid composition containing a radiation-sensitive composition in which, for example, a red pigment is dispersed, is applied to the substrate, and the applied liquid composition is applied. It is prebaked to volatilize the solvent and form a coating film.
接著使塗覆膜透過光罩而曝光，繼而藉由以鹼性顯影溶液進行之顯影以溶解並移除塗覆膜之未曝光的部分並進行後烘烤，藉此形成其中紅色像素圖案係以預定陣列排列的像素陣列。The coating film is then exposed through a reticle, followed by development with an alkaline developing solution to dissolve and remove the unexposed portions of the coating film and post-baking, thereby forming a red pixel pattern therein. A pixel array of predetermined arrays.
隨後，使用含有綠色或藍色顏料分散於其中的輻射敏感性組成物之液體組成物，以相同於上述之方式執行施加液體組成物、預烘焙、曝光、顯影及後烘焙，且綠色之陣列和藍色陣列係以相同於上述之方法連續地形成，藉此獲得具有在基材上配置之紅、綠和藍三原色像素陣列之濾光片。然而，於本發明中之各顏色像素形成之順序不應受限於前述順序。Subsequently, applying a liquid composition, prebaking, exposure, development, and post-baking, and an array of green colors, is performed in the same manner as described above using a liquid composition containing a radiation-sensitive composition in which a green or blue pigment is dispersed. The blue array is continuously formed in the same manner as described above, thereby obtaining a filter having a pixel array of three primary colors of red, green, and blue disposed on a substrate. However, the order in which the respective color pixels are formed in the present invention should not be limited to the foregoing order.
另外，可由含有例如黑色顏料分散於其中之輻射敏感性組成物的液體組成物，以相同於上述像素之形成的方式形成黑矩陣。Further, the black matrix may be formed in the same manner as the formation of the above-described pixels by a liquid composition containing, for example, a radiation-sensitive composition in which a black pigment is dispersed.
用於形成像素及/或黑矩陣的基材之實例包括，玻璃基材、矽基材、聚碳酸酯基材、聚酯基材、芳族聚醯胺基材、聚醯胺醯亞胺基材和聚醯亞胺基材。Examples of the substrate for forming a pixel and/or a black matrix include a glass substrate, a ruthenium substrate, a polycarbonate substrate, a polyester substrate, an aromatic polyamide substrate, and a polyamidimide group. Materials and polyimide substrates.
另外，視需要可對此等基材進行預處理，例如以矽烷偶合劑或類似者之化學處理、電漿處理、離子鍍覆、濺鍍、氣相反應法、真空氣相沉積或類似者。In addition, the substrates may be subjected to pretreatment as needed, for example, chemical treatment with a decane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction, vacuum vapor deposition or the like.
為施加輻射敏感性組成物之液體組成物至基材上，視需要可採用噴霧法、輥塗法、旋塗法、狹縫擠壓塗法、刮棒塗法、噴墨法或類似者，而其中以旋塗法和狹縫擠壓塗法為較佳者。In order to apply the liquid composition of the radiation-sensitive composition to the substrate, if necessary, a spray method, a roll coating method, a spin coating method, a slit extrusion coating method, a bar coating method, an inkjet method or the like may be employed. Among them, spin coating and slit extrusion coating are preferred.
作為乾燥塗覆膜厚度之塗覆膜厚度較佳係0.1至10 μm，更佳係0.2至8.0 μm，尤佳係0.2至6.0 μm。The thickness of the coating film as the thickness of the dried coating film is preferably from 0.1 to 10 μm, more preferably from 0.2 to 8.0 μm, still more preferably from 0.2 to 6.0 μm.
用於形成像素及/或黑矩陣的輻射可選自例如可見光、紫外光、遠紫外光、電子束、X射線或類似者。以具有190至450 nm範圍中之波長的輻射為較佳者。The radiation used to form the pixels and/or black matrix may be selected, for example, from visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like. Radiation having a wavelength in the range of 190 to 450 nm is preferred.
輻射的曝光劑量較佳係10至10000 J/m2 。The exposure dose of the radiation is preferably from 10 to 10,000 J/m 2 .
另外，上述鹼性顯影溶液較佳係選自例如碳酸鈉、氫氧化鈉、氫氧化鉀、氫氧化四甲銨、膽鹼、1,8－二氮雜雙環－[5.4.0]－7－十一烯、1,5－二氮雜雙環－[4.3.0]－5－壬烯及類似者的水性溶液。Further, the above alkaline developing solution is preferably selected from, for example, sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo-[5.4.0]-7- An aqueous solution of undecene, 1,5-diazabicyclo-[4.3.0]-5-decene and the like.
上述鹼性顯影溶液可含有適量的例如水溶性有機溶劑，如甲醇或乙醇或界面活性劑。此外，鹼性顯影後較佳為繼之以水進行沖洗。The above alkaline developing solution may contain an appropriate amount of, for example, a water-soluble organic solvent such as methanol or ethanol or a surfactant. Further, it is preferred to carry out rinsing with water after alkaline development.
可採用噴淋顯影法、噴灑顯影法、浸漬(浸潤)顯影法、攪拌(液體堆壓)法或類似者作為顯影的方法。顯影之相關條件以常溫及5至300秒為佳。A spray development method, a spray development method, a dipping (wetting) development method, a stirring (liquid stacking) method or the like can be employed as the development method. The conditions for development are preferably at room temperature and 5 to 300 seconds.
以上述方式所獲得之本發明濾光片極有用於透射式或反射式彩色液晶顯示器、彩色影像感測裝置、彩色感測器及類似者。The filter of the present invention obtained in the above manner is extremely useful for a transmissive or reflective color liquid crystal display, a color image sensing device, a color sensor, and the like.
本發明之彩色液晶顯示器具有本發明之濾光片。The color liquid crystal display of the present invention has the filter of the present invention.
根據本發明之彩色液晶顯示器的一面向，可藉由本發明用於形成著色層的輻射敏感性組成物以上述方式在薄膜電晶體基材陣列上形成像素及/或黑色矩陣，而製得具有特別優異性質的彩色液晶顯示器。According to one aspect of the color liquid crystal display of the present invention, a pixel and/or a black matrix can be formed on the thin film transistor substrate array by the radiation sensitive composition for forming a coloring layer of the present invention in the above manner, thereby producing a special Excellent color liquid crystal display.
本發明用於形成著色層的輻射敏感性組成物含有上述(A)至(D)組份作為必要組份，且尤其以下示組成物(a)至(d)為尤佳者。The radiation-sensitive composition for forming a coloring layer of the present invention contains the above components (A) to (D) as essential components, and particularly the following compositions (a) to (d) are particularly preferred.
(a)用於形成著色層之輻射敏感性組成物，其中(B)鹼溶性樹脂含有共聚物(BII)。(a) A radiation-sensitive composition for forming a coloring layer, wherein (B) the alkali-soluble resin contains a copolymer (BII).
(b)上述(a)之用於形成著色層的輻射敏感性組成物，其中(C)多官能性單體係選自三丙烯酸三羥甲丙烷酯、三丙烯酸新戊四醇酯及三丙烯酸二新戊四醇酯中之至少一者。(b) The radiation-sensitive composition for forming a coloring layer according to (a) above, wherein the (C) polyfunctional single system is selected from the group consisting of trimethylolpropane triacrylate, neopentyl glycol triacrylate, and triacrylic acid. At least one of dipentaerythritol ester.
(c)上述(a)或(b)之用於形成著色層的輻射敏感性組成物，其中光聚合作用起始劑係選自苯乙酮化合物、二咪唑化合物、三化合物和O－醯肟化合物中之至少一者。(c) The radiation-sensitive composition for forming a coloring layer according to (a) or (b) above, wherein the photopolymerization initiator is selected from the group consisting of an acetophenone compound, a diimidazole compound, and three At least one of a compound and an O-tellurium compound.
(d)上述(a)、(b)或(c)之用於形成著色層的輻射敏感性組成物，其中(A)著色劑係有機顏料或碳黑。(d) The radiation-sensitive composition for forming a coloring layer of (a), (b) or (c) above, wherein (A) the coloring agent is an organic pigment or carbon black.
另外，本發明之較佳濾光片(e)具有由上述用於形成著色層之輻射敏感性組成物(a)、(b)、(c)或(d)所形成之像素及/或黑矩陣。Further, the preferred filter (e) of the present invention has pixels and/or black formed by the above-described radiation-sensitive composition (a), (b), (c) or (d) for forming a colored layer. matrix.
另外，本發明之較佳彩色液晶顯示器(f)具有上述濾光片(e)，且本發明之更佳彩色液晶顯示器(g)具有在薄膜電晶體基材陣列上之上述濾光片(e)。Further, the preferred color liquid crystal display (f) of the present invention has the above filter (e), and the preferred color liquid crystal display (g) of the present invention has the above-described filter on the thin film transistor substrate array (e) ).
如前述，本發明之用於形成著色層之輻射敏感性組成物具有高敏感度，且即便於低曝光劑量下，其圖案形式和膜剩餘比優異，其並可形成對各種溶劑之溶劑抗性優異以及對基材之黏著力優異的像素及黑矩陣。As described above, the radiation-sensitive composition for forming a coloring layer of the present invention has high sensitivity, and is excellent in pattern form and film remaining ratio even at a low exposure dose, and can form solvent resistance to various solvents. Excellent pixel and black matrix with excellent adhesion to the substrate.
本發明之用於形成著色層之輻射敏感性組成物因此極適合用於製造各種濾光片，包括用於電子工業界中之彩色液晶顯示器的濾光片。The radiation-sensitive composition of the present invention for forming a colored layer is therefore highly suitable for use in the manufacture of various filters, including filters for color liquid crystal displays in the electronics industry.
現將參照以下實例更具體地說明本發明，但本發明不應受到此等實例之限制。The invention will now be more specifically described with reference to the following examples, but the invention should not be limited by these examples.
將3重量份的2,2’－偶氮雙異丁腈和200重量份丙二醇－甲基醚乙酸酯裝入具有冷卻管和攪拌器的燒瓶中，並接著裝入15重量份之甲基丙烯酸、15重量份的N－苯基順丁烯二醯亞胺、30重量份的甲基丙烯酸四氫呋喃甲酯、10重量份的苯乙烯、30重量份的甲基丙烯酸正丁酯以及作為分子量調整劑之3重量份的α－甲基苯乙烯二聚物，繼而進行氮取代。接著開始適度地攪拌，將反應混合物的溫度增加至80℃並維持此溫度持續5小時以執行聚合作用，藉此獲得共聚物(BI)之溶液。此共聚物(BI)將稱為“鹼溶性樹脂(B－1)”。3 parts by weight of 2,2'-azobisisobutyronitrile and 200 parts by weight of propylene glycol-methyl ether acetate were charged into a flask equipped with a cooling tube and a stirrer, and then charged with 15 parts by weight of methyl group. Acrylic acid, 15 parts by weight of N-phenyl maleimide, 30 parts by weight of tetrahydrofuran methyl methacrylate, 10 parts by weight of styrene, 30 parts by weight of n-butyl methacrylate, and adjusted as molecular weight 3 parts by weight of the α-methylstyrene dimer of the agent, followed by nitrogen substitution. Then, moderate stirring was started, the temperature of the reaction mixture was increased to 80 ° C and this temperature was maintained for 5 hours to carry out polymerization, whereby a solution of the copolymer (BI) was obtained. This copolymer (BI) will be referred to as "alkali-soluble resin (B-1)".
將3重量份的2,2’－偶氮雙異丁腈和200重量份丙二醇－甲基醚乙酸酯裝入具有冷卻管和攪拌器的燒瓶中，並接著裝入15重量份之甲基丙烯酸、15重量份的N－苯基順丁烯二醯亞胺、30重量份的(2－甲基丙烯醯氧基乙基)(四氫呋喃甲基)琥珀酸酯、10重量份的苯乙烯、30重量份的甲基丙烯酸正丁酯以及作為分子量調整劑之3重量份的α－甲基苯乙烯二聚物，繼而進行氮取代。接著開始適度地攪拌，將反應混合物的溫度增加至80℃並維持此溫度持續5小時以執行聚合作用，藉此獲得共聚物(BI)之溶液。此共聚物(BI)將稱為“鹼溶性樹脂(B－2)”。3 parts by weight of 2,2'-azobisisobutyronitrile and 200 parts by weight of propylene glycol-methyl ether acetate were charged into a flask equipped with a cooling tube and a stirrer, and then charged with 15 parts by weight of methyl group. Acrylic acid, 15 parts by weight of N-phenyl maleimide, 30 parts by weight of (2-methacryloxyethyl) (tetrahydrofuranmethyl) succinate, 10 parts by weight of styrene, 30 parts by weight of n-butyl methacrylate and 3 parts by weight of α-methylstyrene dimer as a molecular weight modifier, followed by nitrogen substitution. Then, moderate stirring was started, the temperature of the reaction mixture was increased to 80 ° C and this temperature was maintained for 5 hours to carry out polymerization, whereby a solution of the copolymer (BI) was obtained. This copolymer (BI) will be referred to as "alkali-soluble resin (B-2)".
將3重量份的2,2’－偶氮雙異丁腈和200重量份丙二醇－甲基醚乙酸酯裝入具有冷卻管和攪拌器的燒瓶中，並裝入15重量份之甲基丙烯酸、45重量份的甲基丙烯酸苯甲酯、10重量份的苯乙烯、30重量份的甲基丙烯酸正丁酯以及作為分子量調整劑之3重量份的α－甲基苯乙烯二聚物，繼而進行氮取代。接著開始適度地攪拌，將反應混合物的溫度增加至80℃並維持此溫度持續5小時以執行聚合作用，藉此獲得共聚物之溶液。此共聚物將稱為“鹼溶性樹脂(B－3)”。3 parts by weight of 2,2'-azobisisobutyronitrile and 200 parts by weight of propylene glycol-methyl ether acetate were placed in a flask equipped with a cooling tube and a stirrer, and 15 parts by weight of methacrylic acid was charged. 45 parts by weight of benzyl methacrylate, 10 parts by weight of styrene, 30 parts by weight of n-butyl methacrylate, and 3 parts by weight of α-methylstyrene dimer as a molecular weight regulator, and then Perform nitrogen substitution. Then, moderate stirring was started, the temperature of the reaction mixture was increased to 80 ° C and this temperature was maintained for 5 hours to carry out polymerization, whereby a solution of the copolymer was obtained. This copolymer will be referred to as "alkali-soluble resin (B-3)".
以玻珠研磨處理作為(A)著色劑之20重量份的重量比為80/20之C.I.顏料紅254/C.I.顏料紅177混合物、作為分散劑之5重量份(固體含量)的BYK－2001以及作為溶劑之75重量份的丙二醇－甲基醚乙酸酯，以製備顏料分散物(R1)。20 parts by weight of a mixture of CI Pigment Red 254/CI Pigment Red 177 in a weight ratio of 80/20, and 5 parts by weight (solid content) of BYK-2001 as a dispersing agent, as a coloring agent of (A) 75 parts by weight of propylene glycol-methyl ether acetate as a solvent to prepare a pigment dispersion (R1).
以相同於製備實例1之方式製備顏料分散物(R2)，除了以作為分散劑之5重量份(固體含量)的Solsperse 24000取代BYK－2001之外。The pigment dispersion (R2) was prepared in the same manner as in Preparation Example 1, except that 5 parts by weight (solid content) of Solsperse 24000 as a dispersing agent was substituted for BYK-2001.
以玻珠研磨處理作為(A)著色劑之20重量份的重量比為50/50之C.I.顏料綠36/C.I.顏料黃150混合物、作為分散劑之5重量份(固體含量)的BYK－2001以及作為溶劑之75重量份的丙二醇－甲基醚乙酸酯，以製備顏料分散物(G1)。20 parts by weight of a (A) colorant, a mixture of CI pigment green 36/CI pigment yellow 150 in a weight ratio of 50/50, and 5 parts by weight (solid content) of BYK-2001 as a dispersing agent. 75 parts by weight of propylene glycol-methyl ether acetate as a solvent to prepare a pigment dispersion (G1).
以相同於製備實例3之方式製備顏料分散物(G2)，除了以作為分散劑之5重量份(固體含量)的Solsperse 24000取代BYK－2001之外。The pigment dispersion (G2) was prepared in the same manner as in Preparation Example 3 except that 5 parts by weight (solid content) of Solsperse 24000 as a dispersing agent was substituted for BYK-2001.
以玻珠研磨處理作為(A)著色劑之20重量份的重量比為90/10之C.I.顏料藍15：6/C.I.顏料紫23混合物、作為分散劑之5重量份(固體含量)的BYK－2001以及作為溶劑之75重量份的丙二醇－甲基醚乙酸酯，以製備顏料分散物(B1)。20 parts by weight of a (A) coloring agent as a coloring agent of 90% by weight of a mixture of CI Pigment Blue 15:6/CI Pigment Violet 23, and 5 parts by weight (solid content) of BYK- as a dispersing agent. 2001 and 75 parts by weight of propylene glycol-methyl ether acetate as a solvent to prepare a pigment dispersion (B1).
以相同於製備實例5之方式製備顏料分散物(B2)，除了以作為分散劑之5重量份(固體含量)的Solsperse 24000取代BYK－2001之外。The pigment dispersion (B2) was prepared in the same manner as in Preparation Example 5 except that 5 parts by weight (solid content) of Solsperse 24000 as a dispersing agent was substituted for BYK-2001.
混合100重量份之顏料分散物(R1)、15重量份(固體含量)之鹼溶性樹脂(B－1)、作為(C)多官能性單體之20重量份的六丙烯酸二新戊四醇酯、作為(D)光聚合作用起始劑之5重量份的2－甲基－1[4－(甲基硫)苯基]－2－嗎啉丙－1－酮以及作為溶劑之丙二醇－甲基醚乙酸酯，以製備具有固體濃度25重量%之液體組成物(R1－1)。100 parts by weight of the pigment dispersion (R1), 15 parts by weight (solid content) of the alkali-soluble resin (B-1), and 20 parts by weight of the (C) polyfunctional monomer of dipentaerythritol hexaacrylate Ester, 5 parts by weight of 2-methyl-1[4-(methylthio)phenyl]-2-morpholinepropan-1-one as (D) photopolymerization initiator and propylene glycol as solvent Methyl ether acetate to prepare a liquid composition (R1-1) having a solid concentration of 25% by weight.
根據下示步驟，以液體組成物(R1－1)形成圖案並進行評估。表1顯示評估結果。According to the procedure shown below, the liquid composition (R1-1) was patterned and evaluated. Table 1 shows the results of the evaluation.
圖案形成以旋塗器將液體組成物(R1－1)施加至六個玻璃基材之每一者的表面，並接著於90℃預烘烤所施加的液體組成物持續4分鐘以形成1.3 μm厚的塗覆膜於各基材上。接著將六個基材冷卻至室溫，並透過光罩使各基材於高壓水銀燈下以300 J/m2 、400 J/m2 、500 J/m2 、750 J/m2 、1000 J/m2 或2000 J/m2 之曝光劑量進行曝光。於顯影壓力(噴嘴直徑為1 mm)為1 kgf/cm2 時，射出23℃之0.04重量%的氫氧化鉀水性溶液至基材上的塗覆膜上以執行噴淋顯影，並接續於220℃後烘烤塗覆膜持續30分鐘以形成200×200 μm點圖案。Patterning The liquid composition (R1-1) was applied to the surface of each of the six glass substrates by a spin coater, and then the applied liquid composition was prebaked at 90 ° C for 4 minutes to form 1.3 μm. A thick coating film is applied to each substrate. Then, the six substrates were cooled to room temperature, and each substrate was passed through a reticle under a high pressure mercury lamp at 300 J/m 2 , 400 J/m 2 , 500 J/m 2 , 750 J/m 2 , 1000 J. The exposure dose of /m 2 or 2000 J/m 2 was exposed. When the developing pressure (nozzle diameter is 1 mm) is 1 kgf/cm 2 , a 0.04% by weight aqueous solution of potassium hydroxide at 23 ° C is sprayed onto the coating film on the substrate to perform spray development, and is continued at 220. The coating film was baked at ° C for 30 minutes to form a 200 × 200 μm dot pattern.
敏感度之評估透過掃描式電子顯微鏡觀察各基材上的點圖案。當形成優異的圖案且膜剩餘比(以顯影前後膜厚度之膜厚度比進行計算＝顯影後膜厚度×100/顯影前膜厚度)為90%或更高時，此等情況之評估結果為○；當形成優異的圖案但膜剩餘比低於90%或觀察到圖案部分地消失時，此等情況之評估結果為△；而當沒有圖案形成時，此等情況之評估結果為×。Evaluation of Sensitivity A dot pattern on each substrate was observed by a scanning electron microscope. When an excellent pattern is formed and the film remaining ratio (calculated by the film thickness ratio of the film thickness before and after development = film thickness after development × 100 / film thickness before development) is 90% or more, the evaluation result of these cases is ○ When an excellent pattern is formed but the film remaining ratio is less than 90% or the pattern is partially disappeared, the evaluation result of these cases is Δ; and when no pattern is formed, the evaluation result of these cases is ×.
溶劑抗性之評估於25℃下將基材浸於N－甲基吡咯烷酮中持續30分鐘，並透過掃描式電子顯微鏡觀察各基材於浸潤前後之點圖案。當圖案未變化且浸潤前後膜厚度之膜厚度比(浸潤後膜厚度×100/浸潤前膜厚度)為95%或更高時，此等情況之評估結果為○；當膜厚度比低於95%或觀察到圖案部分地消失時，此等情況之評估結果為△；而當浸潤後全部圖案自基材剝離時，此等情況之評估結果為×。若因敏感度缺失而無法形成點圖案時，不進行評估(於表1中此等情況以“－”表示)。Evaluation of Solvent Resistance The substrate was immersed in N-methylpyrrolidone at 25 ° C for 30 minutes, and the dot pattern of each substrate before and after infiltration was observed by a scanning electron microscope. When the pattern is not changed and the film thickness ratio of the film thickness before and after wetting (film thickness after infiltration × 100 / film thickness before infiltration) is 95% or more, the evaluation result of these cases is ○; when the film thickness ratio is lower than 95 When the pattern is partially disappeared, the evaluation result of these cases is Δ; and when all the patterns are peeled off from the substrate after the infiltration, the evaluation result of these cases is ×. If a dot pattern cannot be formed due to lack of sensitivity, no evaluation is made (in Table 1, these cases are indicated by "-").
黏著力的評估以旋塗器將液體組成物(R1－1)施加至玻璃基材表面上，施加的組成物於90℃進行預烘烤持續4分鐘以形成1.3 μm的塗覆膜。接著將基材冷卻至室溫，並使塗覆膜於高壓水銀燈下以2000 J/m2 之曝光劑量進行曝光。於顯影壓力(噴嘴直徑為1 mm)為1 kgf/cm2 時，射出23℃之0.04重量%的氫氧化鉀水性溶液至塗覆膜上以執行噴淋顯影，並接續於220℃後烘塗覆膜持續30分鐘。接著根據JIS K5400標準以100方格形式橫切塗覆膜並進行黏著力評估。當沒有方格剝離時，此等情況之評估結果為○；當1至10個方格剝離時，此等情況之評估結果為△，而當超過10個方格剝離時，此等情況之評估結果為×。Evaluation of Adhesion The liquid composition (R1-1) was applied to the surface of the glass substrate by a spinner, and the applied composition was prebaked at 90 ° C for 4 minutes to form a coating film of 1.3 μm. The substrate was then cooled to room temperature, and the coated film was exposed to a high pressure mercury lamp at an exposure dose of 2000 J/m 2 . When the developing pressure (nozzle diameter is 1 mm) is 1 kgf/cm 2 , a 0.04% by weight aqueous solution of potassium hydroxide at 23 ° C is sprayed onto the coating film to perform spray development, and then baked at 220 ° C. The film lasted for 30 minutes. Then, the coating film was cross-cut in a 100-square form according to the JIS K5400 standard and adhesion evaluation was performed. When there is no square peeling, the evaluation result of these cases is ○; when 1 to 10 squares are peeled off, the evaluation result of these cases is △, and when more than 10 squares are peeled off, the evaluation of such cases The result is ×.
以相同於實例1之方式製備液體組成物(R1－2)，除了以5重量份的1－[9－乙基－6－(2－甲基苯甲醯基)－9H－咔唑－3－基]－乙酮－1－(O－醯肟)替代(D)光聚合作用起始劑之外。The liquid composition (R1-2) was prepared in the same manner as in Example 1, except that 5 parts by weight of 1-[9-ethyl-6-(2-methylbenzylidene)-9H-carbazole-3 was used. -yl]-ethanone-1-(O-oxime) is substituted for (D) photopolymerization initiator.
然後以相同於實例1之方式執行評估，除了以液體組成物(R1－2)替代液體組成物(R1－1)之外。表1顯示評估結果。Evaluation was then carried out in the same manner as in Example 1, except that the liquid composition (R1-2) was substituted for the liquid composition (R1-1). Table 1 shows the results of the evaluation.
混合100重量份之顏料分散物(R1)、12重量份(固體含量)之鹼溶性樹脂(B－1)、作為(C)多官能性單體之20重量份的六丙烯酸二新戊四醇酯、作為(D)光聚合作用起始劑之5重量份的2－甲基－1－[4－(甲基硫)苯基]－2－嗎啉丙－1－酮、作為固化劑之3重量份的雙酚A酚醛類環氧樹脂(商品名157S65，日本環氧樹脂股份有限公司提供)以及作為溶劑之丙二醇－甲基醚乙酸酯，以製備具有固體濃度25重量%之液體組成物(R1－3)。100 parts by weight of the pigment dispersion (R1), 12 parts by weight (solid content) of the alkali-soluble resin (B-1), and 20 parts by weight of the (C) polyfunctional monomer of dipentaerythritol hexaacrylate Ester, 5 parts by weight of 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinepropan-1-one as (D) photopolymerization initiator, as a curing agent 3 parts by weight of a bisphenol A phenolic epoxy resin (trade name: 157S65, supplied by Nippon Epoxy Co., Ltd.) and propylene glycol-methyl ether acetate as a solvent to prepare a liquid composition having a solid concentration of 25% by weight (R1-3).
然後以相同於實例1之方式執行評估，除了以液體組成物(R1－3)替代液體組成物(R1－1)之外。表1顯示評估結果。Evaluation was then carried out in the same manner as in Example 1, except that the liquid composition (R1-3) was substituted for the liquid composition (R1-1). Table 1 shows the results of the evaluation.
混合100重量份之顏料分散物(R1)、15重量份(固體含量)之鹼溶性樹脂(B－1)、作為(C)多官能性單體之20重量份的六丙烯酸二新戊四醇酯、作為(D)光聚合作用起始劑之5重量份的2－甲基－1－[4－(甲基硫)苯基]－2－嗎啉丙－1－酮、作為固化劑之1重量份的苯偏三酸酐和作為溶劑之丙二醇－甲基醚乙酸酯，以製備具有固體濃度25重量%之液體組成物(R1－4)。100 parts by weight of the pigment dispersion (R1), 15 parts by weight (solid content) of the alkali-soluble resin (B-1), and 20 parts by weight of the (C) polyfunctional monomer of dipentaerythritol hexaacrylate Ester, 5 parts by weight of 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinepropan-1-one as (D) photopolymerization initiator, as a curing agent 1 part by weight of trimellitic anhydride and propylene glycol-methyl ether acetate as a solvent to prepare a liquid composition (R1-4) having a solid concentration of 25% by weight.
然後以相同於實例1之方式執行評估，除了以液體組成物(R1－4)替代液體組成物(R1－1)之外。表1顯示評估結果。Evaluation was then carried out in the same manner as in Example 1, except that the liquid composition (R1-4) was substituted for the liquid composition (R1-1). Table 1 shows the results of the evaluation.
以相同於實例1之方式製備液體組成物(R1－5)，除了以15重量份(固體含量)的鹼溶性樹脂(B－2)替代鹼溶性樹脂(B－1)之外。The liquid composition (R1-5) was prepared in the same manner as in Example 1, except that 15 parts by weight (solid content) of the alkali-soluble resin (B-2) was used in place of the alkali-soluble resin (B-1).
然後以相同於實例1之方式執行評估，除了以液體組成物(R1－5)替代液體組成物(R1－1)之外。表1顯示評估結果。Evaluation was then carried out in the same manner as in Example 1, except that the liquid composition (R1-5) was substituted for the liquid composition (R1-1). Table 1 shows the results of the evaluation.
以相同於實例1之方式製備液體組成物(R2－1)，除了以100重量份的顏料分散物(R2)替代顏料分散物(R1)之外。The liquid composition (R2-1) was prepared in the same manner as in Example 1, except that 100 parts by weight of the pigment dispersion (R2) was used instead of the pigment dispersion (R1).
然後以相同於實例1之方式執行評估，除了以液體組成物(R2－1)替代液體組成物(R1－1)之外。表1顯示評估結果。Evaluation was then carried out in the same manner as in Example 1, except that the liquid composition (R2-1) was substituted for the liquid composition (R1-1). Table 1 shows the results of the evaluation.
以相同於實例1之方式製備液體組成物(R2－2)，除了以100重量份的顏料分散物(R2)替代顏料分散物(R1)且以15重量份(固體含量)的鹼溶性樹脂(B－2)替代鹼溶性樹脂(B－1)之外。The liquid composition (R2-2) was prepared in the same manner as in Example 1, except that 100 parts by weight of the pigment dispersion (R2) was substituted for the pigment dispersion (R1) and 15 parts by weight (solid content) of the alkali-soluble resin ( B-2) In place of the alkali-soluble resin (B-1).
然後以相同於實例1之方式執行評估，除了以液體組成物(R2－2)替代液體組成物(R1－1)之外。表1顯示評估結果。Evaluation was then carried out in the same manner as in Example 1, except that the liquid composition (R2-2) was substituted for the liquid composition (R1-1). Table 1 shows the results of the evaluation.
混合100重量份之顏料分散物(G1)、20重量份(固體含量)之鹼溶性樹脂(B－1)、作為(C)多官能性單體之10重量份的六丙烯酸二新戊四醇酯、作為(D)光聚合作用起始劑之10重量份的2－苯甲基－2－二甲基胺基－1－(4嗎啉基苯基)－丁－1酮以及作為溶劑之丙二醇－甲基醚乙酸酯，以製備具有固體濃度25重量%之液體組成物(G1－1)。100 parts by weight of the pigment dispersion (G1), 20 parts by weight (solid content) of the alkali-soluble resin (B-1), and 10 parts by weight of the (C) polyfunctional monomer of dipentaerythritol hexaacrylate Ester, 10 parts by weight of 2-benzyl-2-dimethylamino-1-(4morpholinylphenyl)-butan-1one as (D) photopolymerization initiator and as a solvent Propylene glycol-methyl ether acetate to prepare a liquid composition (G1-1) having a solid concentration of 25% by weight.
然後以相同於實例1之方式執行評估，除了以液體組成物(G1－1)替代液體組成物(R1－1)之外。表1顯示評估結果。Evaluation was then carried out in the same manner as in Example 1, except that the liquid composition (G1-1) was substituted for the liquid composition (R1-1). Table 1 shows the results of the evaluation.
以相同於實例8之方式製備液體組成物(G2－1)，除了以100重量份的顏料分散物(G2)替代顏料分散物(G1)之外。The liquid composition (G2-1) was prepared in the same manner as in Example 8, except that 100 parts by weight of the pigment dispersion (G2) was used instead of the pigment dispersion (G1).
然後以相同於實例1之方式執行評估，除了以液體組成物(G2－1)替代液體組成物(R1－1)之外。表1顯示評估結果。Evaluation was then carried out in the same manner as in Example 1, except that the liquid composition (G2-1) was substituted for the liquid composition (R1-1). Table 1 shows the results of the evaluation.
以相同於實例8之方式製備液體組成物(G1－2)，除了以20重量份(固體含量)的鹼溶性樹脂(B－2)替代鹼溶性樹脂(B－1)之外。The liquid composition (G1-2) was prepared in the same manner as in Example 8, except that 20 parts by weight (solid content) of the alkali-soluble resin (B-2) was used in place of the alkali-soluble resin (B-1).
然後以相同於實例1之方式執行評估，除了以液體組成物(G1－2)替代液體組成物(R1－1)之外。表1顯示評估結果。Evaluation was then carried out in the same manner as in Example 1, except that the liquid composition (G1-2) was substituted for the liquid composition (R1-1). Table 1 shows the results of the evaluation.
以相同於實例8之方式製備液體組成物(G2－2)，除了以100重量份的顏料分散物(G2)替代顏料分散物(G1)且以20重量份(固體含量)的鹼溶性樹脂(B－2)替代鹼溶性樹脂(B－1)之外。The liquid composition (G2-2) was prepared in the same manner as in Example 8, except that 100 parts by weight of the pigment dispersion (G2) was substituted for the pigment dispersion (G1) and 20 parts by weight (solid content) of the alkali-soluble resin ( B-2) In place of the alkali-soluble resin (B-1).
然後以相同於實例1之方式執行評估，除了以液體組成物(G2－2)替代液體組成物(R1－1)之外。表1顯示評估結果。Evaluation was then carried out in the same manner as in Example 1, except that the liquid composition (G2-2) was substituted for the liquid composition (R1-1). Table 1 shows the results of the evaluation.
混合100重量份之顏料分散物(B1)、15重量份(固體含量)之鹼溶性樹脂(B－1)、作為(C)多官能性單體之15重量份的六丙烯酸二新戊四醇酯、作為(D)光聚合作用起始劑之4重量份的2－甲基－1－[4－(甲基硫)苯基]－2－嗎啉丙－1－酮與1重量份的2,4－二乙基硫蒽酮以及作為溶劑之丙二醇－甲基醚乙酸酯，以製備具有固體濃度25重量%之液體組成物(B1－1)。100 parts by weight of the pigment dispersion (B1), 15 parts by weight (solid content) of the alkali-soluble resin (B-1), and 15 parts by weight of the (C) polyfunctional monomer of dipentaerythritol hexaacrylate Ester, 4 parts by weight of 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinepropan-1-one as (D) photopolymerization initiator, and 1 part by weight 2,4-Diethylthioxanthone and propylene glycol-methyl ether acetate as a solvent to prepare a liquid composition (B1-1) having a solid concentration of 25% by weight.
然後以相同於實例1之方式執行評估，除了以液體組成物(B1－1)替代液體組成物(R1－1)之外。表1顯示評估結果。Evaluation was then carried out in the same manner as in Example 1, except that the liquid composition (B1-1) was substituted for the liquid composition (R1-1). Table 1 shows the results of the evaluation.
以相同於實例12之方式製備液體組成物(B2－1)，除了以100重量份的顏料分散物(B2)替代顏料分散物(B1)之外。The liquid composition (B2-1) was prepared in the same manner as in Example 12 except that 100 parts by weight of the pigment dispersion (B2) was used instead of the pigment dispersion (B1).
然後以相同於實例1之方式執行評估，除了以液體組成物(B2－1)替代液體組成物(R1－1)之外。表1顯示評估結果。Evaluation was then carried out in the same manner as in Example 1, except that the liquid composition (B2-1) was substituted for the liquid composition (R1-1). Table 1 shows the results of the evaluation.
以相同於實例12之方式製備液體組成物(B1－2)，除了以15重量份(固體含量)的鹼溶性樹脂(B－2)替代鹼溶性樹脂(B－1)之外。The liquid composition (B1-2) was prepared in the same manner as in Example 12 except that the alkali-soluble resin (B-1) was replaced with 15 parts by weight (solid content) of the alkali-soluble resin (B-2).
然後以相同於實例1之方式執行評估，除了以液體組成物(B1－2)替代液體組成物(R1－1)之外。表1顯示評估結果。Evaluation was then carried out in the same manner as in Example 1, except that the liquid composition (B1-2) was substituted for the liquid composition (R1-1). Table 1 shows the results of the evaluation.
以相同於實例12之方式製備液體組成物(B2－2)，除了以100重量份的顏料分散物(B2)替代顏料分散物(B1)且以15重量份(固體含量)的鹼溶性樹脂(B－2)替代鹼溶性樹脂(B－1)之外。The liquid composition (B2-2) was prepared in the same manner as in Example 12 except that 100 parts by weight of the pigment dispersion (B2) was substituted for the pigment dispersion (B1) and 15 parts by weight (solid content) of the alkali-soluble resin ( B-2) In place of the alkali-soluble resin (B-1).
然後以相同於實例1之方式執行評估，除了以液體組成物(B2－2)替代液體組成物(R1－1)之外。表1顯示評估結果。Evaluation was then carried out in the same manner as in Example 1, except that the liquid composition (B2-1) was substituted for the liquid composition (R1-1). Table 1 shows the results of the evaluation.
以相同於實例1之方式製備液體組成物(R1－6)，除了以15重量份(固體含量)的鹼溶性樹脂(B－3)替代鹼溶性樹脂(B－1)之外。The liquid composition (R1-6) was prepared in the same manner as in Example 1 except that 15 parts by weight (solid content) of the alkali-soluble resin (B-3) was used in place of the alkali-soluble resin (B-1).
然後以相同於實例1之方式執行評估，除了以液體組成物(R1－6)替代液體組成物(R1－1)之外。表2顯示評估結果。Evaluation was then carried out in the same manner as in Example 1, except that the liquid composition (R1-6) was substituted for the liquid composition (R1-1). Table 2 shows the results of the evaluation.
以相同於實例2之方式製備液體組成物(R1－7)，除了以15重量份(固體含量)的鹼溶性樹脂(B－3)替代鹼溶性樹脂(B－1)之外。The liquid composition (R1-7) was prepared in the same manner as in Example 2 except that the alkali-soluble resin (B-1) was replaced with 15 parts by weight (solid content) of the alkali-soluble resin (B-3).
然後以相同於實例1之方式執行評估，除了以液體組成物(R1－7)替代液體組成物(R1－1)之外。表2顯示評估結果。Evaluation was then carried out in the same manner as in Example 1, except that the liquid composition (R1-7) was substituted for the liquid composition (R1-1). Table 2 shows the results of the evaluation.
以相同於實例3之方式製備液體組成物(R1－8)，除了以12重量份(固體含量)的鹼溶性樹脂(B－3)替代鹼溶性樹脂(B－1)之外。The liquid composition (R1-8) was prepared in the same manner as in Example 3 except that the alkali-soluble resin (B-1) was replaced with 12 parts by weight (solid content) of the alkali-soluble resin (B-3).
然後以相同於實例1之方式執行評估，除了以液體組成物(R1－8)替代液體組成物(R1－1)之外。表2顯示評估結果。Evaluation was then carried out in the same manner as in Example 1, except that the liquid composition (R1-8) was substituted for the liquid composition (R1-1). Table 2 shows the results of the evaluation.
以相同於實例4之方式製備液體組成物(R1－9)，除了以15重量份(固體含量)的鹼溶性樹脂(B－3)替代鹼溶性樹脂(B－1)之外。The liquid composition (R1-9) was prepared in the same manner as in Example 4 except that 15 parts by weight (solid content) of the alkali-soluble resin (B-3) was used in place of the alkali-soluble resin (B-1).
然後以相同於實例1之方式執行評估，除了以液體組成物(R1－9)替代液體組成物(R1－1)之外。表2顯示評估結果。Evaluation was then carried out in the same manner as in Example 1, except that the liquid composition (R1-9) was substituted for the liquid composition (R1-1). Table 2 shows the results of the evaluation.
以相同於實例6之方式製備液體組成物(R2－3)，除了以15重量份(固體含量)的鹼溶性樹脂(B－3)替代鹼溶性樹脂(B－1)之外。The liquid composition (R2-3) was prepared in the same manner as in Example 6, except that 15 parts by weight (solid content) of the alkali-soluble resin (B-3) was used in place of the alkali-soluble resin (B-1).
然後以相同於實例1之方式執行評估，除了以液體組成物(R2－3)替代液體組成物(R1－1)之外。表2顯示評估結果。Evaluation was then carried out in the same manner as in Example 1, except that the liquid composition (R2-3) was substituted for the liquid composition (R1-1). Table 2 shows the results of the evaluation.
以相同於實例8之方式製備液體組成物(G1－3)，除了以20重量份(固體含量)的鹼溶性樹脂(B－3)替代鹼溶性樹脂(B－1)之外。The liquid composition (G1-3) was prepared in the same manner as in Example 8, except that 20 parts by weight (solid content) of the alkali-soluble resin (B-3) was used in place of the alkali-soluble resin (B-1).
然後以相同於實例1之方式執行評估，除了以液體組成物(G1－3)替代液體組成物(R1－1)之外。表2顯示評估結果。Evaluation was then carried out in the same manner as in Example 1, except that the liquid composition (G1-3) was substituted for the liquid composition (R1-1). Table 2 shows the results of the evaluation.
以相同於實例9之方式製備液體組成物(G2－3)，除了以20重量份(固體含量)的鹼溶性樹脂(B－3)替代鹼溶性樹脂(B－1)之外。The liquid composition (G2-3) was prepared in the same manner as in Example 9 except that 20 parts by weight (solid content) of the alkali-soluble resin (B-3) was used in place of the alkali-soluble resin (B-1).
然後以相同於實例1之方式執行評估，除了以液體組成物(G2－3)替代液體組成物(R1－1)之外。表2顯示評估結果。Evaluation was then carried out in the same manner as in Example 1, except that the liquid composition (G2-3) was substituted for the liquid composition (R1-1). Table 2 shows the results of the evaluation.
以相同於實例12之方式製備液體組成物(B1－3)，除了以15重量份(固體含量)的鹼溶性樹脂(B－3)替代鹼溶性樹脂(B－1)之外。The liquid composition (B1-3) was prepared in the same manner as in Example 12 except that 15 parts by weight (solid content) of the alkali-soluble resin (B-3) was used in place of the alkali-soluble resin (B-1).
然後以相同於實例1之方式執行評估，除了以液體組成物(B1－3)替代液體組成物(R1－1)之外。表2顯示評估結果。Evaluation was then carried out in the same manner as in Example 1, except that the liquid composition (B1-3) was substituted for the liquid composition (R1-1). Table 2 shows the results of the evaluation.
以相同於實例13之方式製備液體組成物(B2－3)，除了以15重量份(固體含量)的鹼溶性樹脂(B－3)替代鹼溶性樹脂(B－1)之外。The liquid composition (B2-3) was prepared in the same manner as in Example 13 except that 15 parts by weight (solid content) of the alkali-soluble resin (B-3) was used in place of the alkali-soluble resin (B-1).
然後以相同於實例1之方式執行評估，除了以液體組成物(B2－3)替代液體組成物(R1－1)之外。表2顯示評估結果。Evaluation was then carried out in the same manner as in Example 1, except that the liquid composition (B2-3) was substituted for the liquid composition (R1-1). Table 2 shows the results of the evaluation.
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| JP2006090516A JP4635935B2 (en) | 2006-03-29 | 2006-03-29 | Radiation-sensitive composition for forming colored layer, color filter, and color liquid crystal display element |
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| JP (1) | JP4635935B2 (en) |
| KR (1) | KR101674677B1 (en) |
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| JP5157522B2 (en) * | 2008-02-28 | 2013-03-06 | Ｊｓｒ株式会社 | Radiation-sensitive composition for forming colored layer, color filter, and color liquid crystal display element |
| JP5235546B2 (en) * | 2008-07-23 | 2013-07-10 | 富士フイルム株式会社 | Photosensitive resin composition, light-shielding color filter, method for producing the same, and solid-state imaging device |
| TW201031713A (en) * | 2009-02-13 | 2010-09-01 | Toyo Ink Mfg Co | The coloring composition for color filters and color filters |
| CN102033427A (en) * | 2009-09-30 | 2011-04-27 | 富士胶片株式会社 | Colored photosensitive resin composition for ultraviolet laser, pattern forming method, color filter, method for manufacturing color filter, and display device |
| CN102073216A (en) * | 2009-11-18 | 2011-05-25 | 富士胶片株式会社 | Colored photosensitive resin composition, pattern forming method, manufacture method for color filter, color filter, and display apparatus |
| JP5121912B2 (en) * | 2010-11-24 | 2013-01-16 | 富士フイルム株式会社 | Colored photosensitive resin composition, pattern forming method, color filter manufacturing method, color filter, and display device including the same |
| TW201235783A (en) * | 2010-12-10 | 2012-09-01 | Sumitomo Chemical Co | Photosensitive resin composition |
| JP5935462B2 (en) * | 2011-05-10 | 2016-06-15 | 日立化成株式会社 | Photosensitive element, resist pattern forming method, printed wiring board manufacturing method |
| CN104081280B (en) * | 2012-01-31 | 2019-05-31 | 三菱化学株式会社 | Coloring photosensitive combination, black light spacer and colour filter |
| JP6157111B2 (en) * | 2012-12-26 | 2017-07-05 | 東京応化工業株式会社 | Colored photosensitive resin composition, color filter, and color liquid crystal display element |
| US9783626B2 (en) | 2013-09-09 | 2017-10-10 | Boe Technology Group Co., Ltd. | Alkali-soluble resin, method for preparing the same and photosensitive resin composition comprising the same |
| CN103467646B (en) * | 2013-09-09 | 2015-12-02 | 京东方科技集团股份有限公司 | Alkali soluble resin and preparation method thereof |
| CN103980416B (en) * | 2014-05-15 | 2016-06-08 | 京东方科技集团股份有限公司 | Alkali soluble resin, Photosensitve resin composition and their preparation method |
| CN105388705B (en) * | 2014-09-01 | 2020-09-22 | 东友精细化工有限公司 | Colored photosensitive resin composition |
| KR101687586B1 (en) | 2014-10-31 | 2016-12-19 | 연세대학교 산학협력단 | Apparatus and Method of Instantaneous Levitator Using High Temperature Superconducting Coils |
| CN112485967A (en) * | 2020-12-29 | 2021-03-12 | 安徽邦铭新材料科技有限公司 | Photoresist composition for TFT-LCD |
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| WO2006008995A1 (en) * | 2004-07-15 | 2006-01-26 | Taiyo Ink Manufacturing Co., Ltd. | Photocurable/thermosetting resin composition and cured product thereof |
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| JP2891418B2 (en) | 1988-11-26 | 1999-05-17 | 凸版印刷株式会社 | Color filter and manufacturing method thereof |
| JPH0812292B2 (en) | 1989-07-20 | 1996-02-07 | 凸版印刷株式会社 | Heat resistant color filter and manufacturing method thereof |
| JPH08259876A (en) | 1995-03-24 | 1996-10-08 | Japan Synthetic Rubber Co Ltd | Organic pigment dispersed liquid for color filter |
| JP3867177B2 (en) * | 1997-04-30 | 2007-01-10 | Ｊｓｒ株式会社 | Radiation sensitive composition for color filter |
| JP2002014466A (en) * | 2000-06-28 | 2002-01-18 | Taiyo Ink Mfg Ltd | Photosensitive resin composition |
| JP2002356602A (en) * | 2000-07-28 | 2002-12-13 | Sekisui Chem Co Ltd | Colored resin emulsion, ink for ink-jet printing, electrodeposition liquid and color filter |
| JP2003307614A (en) * | 2002-02-15 | 2003-10-31 | Jsr Corp | Semitransmission type color filter, radiation sensitive composition and color liquid crystal display element |
| JP4428911B2 (en) * | 2002-07-05 | 2010-03-10 | Ｊｓｒ株式会社 | Radiation sensitive composition for color filter, color filter and color liquid crystal display element |
| JP4046023B2 (en) * | 2003-06-23 | 2008-02-13 | Ｊｓｒ株式会社 | Curable resin composition, protective film and method for forming protective film |
| JP4315013B2 (en) * | 2003-08-01 | 2009-08-19 | Ｊｓｒ株式会社 | Radiation-sensitive resin composition, interlayer insulating film and microlens, and production method thereof |
| JP4492393B2 (en) * | 2005-03-08 | 2010-06-30 | チッソ株式会社 | Photosensitive composition and display element using the same |
| JP2006306956A (en) * | 2005-04-27 | 2006-11-09 | Chisso Corp | Photocurable composition and display element using the same |
| JP2006322982A (en) * | 2005-05-17 | 2006-11-30 | Hitachi Chem Co Ltd | Coloring composition, photosensitive coloring resin composition, sensitization liquid for forming coloring image, and method of manufacturing coloring image, method of manufacturing color filter, and color filter |
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| WO2006008995A1 (en) * | 2004-07-15 | 2006-01-26 | Taiyo Ink Manufacturing Co., Ltd. | Photocurable/thermosetting resin composition and cured product thereof |
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| KR101674677B1 (en) | 2016-11-09 |
| TW200809408A (en) | 2008-02-16 |
| SG136105A1 (en) | 2007-10-29 |
| CN101046630A (en) | 2007-10-03 |
| KR20070098609A (en) | 2007-10-05 |
| CN101046630B (en) | 2012-04-18 |
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| JP2007264377A (en) | 2007-10-11 |
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