TWI501034B - Coloring composition, color filter and color liquid crystal display element - Google Patents

Coloring composition, color filter and color liquid crystal display element Download PDF

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TWI501034B
TWI501034B TW099142913A TW99142913A TWI501034B TW I501034 B TWI501034 B TW I501034B TW 099142913 A TW099142913 A TW 099142913A TW 99142913 A TW99142913 A TW 99142913A TW I501034 B TWI501034 B TW I501034B
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group
mass
compound
meth
pigment
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TW099142913A
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TW201133141A (en
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Hiroyuki Komatsu
Yoshitaka Yamada
Seiji Kawagishi
Hideyuki Kamii
Seitarou Hattori
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Jsr Corp
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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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/201—Filters in the form of arrays
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/1303—Apparatus specially adapted to the manufacture of LCDs
    • 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

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Nonlinear Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)
  • Liquid Crystal (AREA)

Description

著色組成物、彩色濾光片及彩色液晶顯示元件Coloring composition, color filter, and color liquid crystal display element

本發明係關於著色組成物、彩色濾光片及彩色液晶顯示元件，更詳言之，係關於使用於著色層之形成之著色組成物、具有由該著色組成物所形成之著色層之彩色濾光片、以及具備該彩色濾光片之液晶顯示元件，該著色層對使用於透過型或者反射型之彩色液晶顯示裝置、彩色攝像管元件、有機EL顯示元件、電子紙等所使用之彩色濾光片極為有用。The present invention relates to a coloring composition, a color filter, and a color liquid crystal display element, and more particularly to a coloring composition for forming a colored layer, and a color filter having a colored layer formed of the colored composition. a light sheet and a liquid crystal display element including the color filter, the colored layer used for a transmissive or reflective type color liquid crystal display device, a color image sensor element, an organic EL display element, an electronic paper, or the like The light sheet is extremely useful.

先前，習知有在使用著色感放射線性組成物，製造彩色濾光片的時候，在基板上或者預先形成了所期望圖案之遮光層的基板上，塗布著色感放射線性組成物並予以乾燥後，藉由照射放射線、並顯影於乾燥塗膜成為所期望之圖案形狀(以下稱為「曝光」)，而獲得各色像素之方法(參照例如專利文獻1、專利文獻2)。又，習知有利用含有黑色材料的光聚合性組成物形成黑色矩陣之方法(參照例如專利文獻3)。再者，習知有使用著色樹脂組成物，以噴墨方式獲得各色像素之方法(參照例如專利文獻4)。Conventionally, when a color filter is manufactured using a coloring sensitizing radiation linear composition, a coloring sensitizing radiation linear composition is applied onto a substrate or a substrate on which a light shielding layer having a desired pattern is formed in advance, and dried. A method of obtaining a pixel of each color by irradiating a radiation and developing the dried coating film into a desired pattern shape (hereinafter referred to as "exposure") (see, for example, Patent Document 1 and Patent Document 2). Further, a method of forming a black matrix using a photopolymerizable composition containing a black material is known (see, for example, Patent Document 3). In addition, there is a method of obtaining a pixel of each color by an inkjet method using a colored resin composition (see, for example, Patent Document 4).

然而，在專利文獻5有提案一種感光性組成物，其顯影性優異，且作為可進行鮮明(sharp)的圖案化的彩色濾光片用著色糊，其係含有側鏈具有羧基及乙烯性不飽和基之丙烯酸系共聚物與多官能硫醇之感光性組成物。但是，在使用此等感光性組成物所形成之彩色濾光片，相對於其上所形成的ITO、IZO等之透明導電膜或SiNx膜、SiOx膜等之無機膜，會有密合性不充分的問題。However, Patent Document 5 proposes a photosensitive composition which is excellent in developability and which is a coloring paste for a color filter which can be sharply patterned, and has a carboxyl group and an ethyl group in a side chain. A photosensitive composition of a saturated acrylic copolymer and a polyfunctional thiol. However, in the color filter formed using the photosensitive composition, the adhesion is not improved with respect to the transparent conductive film such as ITO or IZO formed thereon or the inorganic film such as SiNx film or SiOx film. Full question.

又，近年，在彩色濾光片之技術領域中，降低曝光量並縮短節奏時間(takt time)雖為主流，不過在使用先前之著色感放射線性組成物，所形成之像素，正逐漸使耐溶劑性不充分的問題明顯存在化。吾人認為此等問題之背景，係欲對應於針對近年來彩色液晶顯示元件之高對比化、高亮度化及高色純度化之要求，而對多種著色感放射線性組成物所使用之顔料進行各式各樣微細化處理或表面處理；或在著色感放射線性組成物中所佔顔料之含有比率有愈趨變高之傾向等。Moreover, in recent years, in the technical field of color filters, although the amount of exposure is reduced and the takt time is shortened, although the previous color-sensing radioactive composition is used, the formed pixels are gradually becoming resistant. The problem of insufficient solvent properties is apparently present. We believe that the background of these problems is to meet the requirements for high contrast, high brightness, and high color purity of color liquid crystal display elements in recent years, and to use various pigments for the color-sensing radioactive composition. Various kinds of refining treatments or surface treatments; or the tendency of the content ratio of the pigments in the coloring sensitizing radiation composition to become higher.

[先行技術文獻][Advanced technical literature] 專利文獻Patent literature

專利文獻1　日本特開平2-144502號公報Patent Document 1 Japanese Patent Laid-Open No. 2-144502

專利文獻2　日本特開平3-53201號公報Patent Document 2 Japanese Patent Laid-Open No. 3-53201

專利文獻3　日本特開平6-35188號公報Patent Document 3 Japanese Patent Laid-Open No. Hei 6-35188

專利文獻4　日本特開2000-310706號公報Patent Document 4 Japanese Patent Laid-Open Publication No. 2000-310706

專利文獻5　日本特開平5-281734號公報Patent Document 5 Japanese Patent Laid-Open No. Hei 5-281734

本發明係根據以上之情事而完成者，其課題在於提供一種新穎著色組成物，其與透明導電膜或無機膜之密合性優異，再者在低曝光量中也可形成耐溶劑性優異的像素。The present invention has been made in view of the above circumstances, and an object of the invention is to provide a novel coloring composition which is excellent in adhesion to a transparent conductive film or an inorganic film, and which is excellent in solvent resistance even in a low exposure amount. Pixel.

本發明人等，經戮力研討之結果，首先發現藉由著色組成物中含有具有磺醯基(-SH)等反應性官能基的籠型倍半矽氧烷即可解決上述課題，因而完成本發明。As a result of the research, the inventors of the present invention have found that the above problem can be solved by including a caged sesquiterpene oxide having a reactive functional group such as a sulfonyl group (-SH) in the colored composition, and thus completed. this invention.

亦即，本發明係提供一種著色組成物，其特徵為含有具有選自由(A)著色劑、(B)黏合劑樹脂、(C)多官能性單體、以及(D)磺醯基及聚合性不飽和基所構成群組中之至少一種的籠型倍半矽氧烷(以下稱為「倍半矽氧烷(D)」)。That is, the present invention provides a coloring composition characterized by having a coloring agent selected from the group consisting of (A) coloring agent, (B) binder resin, (C) polyfunctional monomer, and (D) sulfonyl group and polymerization. A cage type sesquiterpene oxide (hereinafter referred to as "sesquioxane (D)") of at least one of the group consisting of unsaturated groups.

又，本發明係提供一種彩色濾光片、及具備該彩色濾光片之液晶顯示元件，該彩色濾光片係具備使用該著色組成物所形成之著色層。Moreover, the present invention provides a color filter and a liquid crystal display element including the color filter, wherein the color filter includes a coloring layer formed using the colored composition.

根據本發明之著色組成物，其可形成像素，該像素與透明導電膜或無機膜之密合性優異，進一步在低曝光量中耐溶劑性優異。而且，使用本發明之著色組成物所形成之著色層，電壓保持率高且電特性優異。According to the coloring composition of the present invention, a pixel can be formed, and the pixel is excellent in adhesion to a transparent conductive film or an inorganic film, and further excellent in solvent resistance at a low exposure amount. Further, the coloring layer formed by using the coloring composition of the present invention has high voltage holding ratio and excellent electrical characteristics.

因此，本發明之感放射線性組成物，可極為適當的使用於以電子工業領域中液晶顯示元件用彩色濾光片、固體攝像元件之色分解用彩色濾光片、有機EL顯示元件用彩色濾光片、電子紙用彩色濾光片為始之各種彩色濾光片之製造。Therefore, the radiation-sensitive linear composition of the present invention can be suitably used for color filters for liquid crystal display elements in the electronic industry, color filters for color separation of solid-state imaging devices, and color filters for organic EL display elements. Light sheets and color filters for electronic paper are manufactured from various color filters.

[本發明之最佳實施方式][Best Embodiment of the Invention] 著色組成物Coloring composition

茲就本發明詳細說明如下。The invention is described in detail below.

-(A)著色劑-- (A) colorant -

本發明中在(A)著色劑方面，若具有著色性並無特別限定，可按照彩色濾光片等用途而適宜選擇色彩或材質。具體言之，著色劑可使用顔料、染料及天然色素之任一種，不過在彩色濾光片由於係謀求耐熱性，故較佳為有機顔料、無機顔料。In the present invention, the coloring property of the coloring agent (A) is not particularly limited, and a color or a material can be appropriately selected depending on the use such as a color filter. Specifically, the coloring agent may be any of a pigment, a dye, and a natural pigment. However, since the color filter is heat-resistant, it is preferably an organic pigment or an inorganic pigment.

就上述有機顔料而言，可例舉例如色料索引(C.I.;The Society of Dyers and Colourists公司發行)中分類為色素之化合物，具體言之，可例舉下述帶色料索引(C.I.)編號之化合物。The above organic pigment may, for example, be a compound classified as a coloring matter in a color index (CI; issued by The Society of Dyers and Colourists), and specifically, the following coloring material index (CI) number may be mentioned. Compound.

C.I.色素黃12、C.I.色素黃13、C.I.色素黃14、C.I.色素黃17、C.I.色素黃20、C.I.色素黃24、C.I.色素黃31、C.I.色素黃55、C.I.色素黃83、C.I.色素黃93、C.I.色素黃109、C.I.色素黃110、C.I.色素黃138、C.I.色素黃139、C.I.色素黃150、C.I.色素黃153、C.I.色素黃154、C.I.色素黃155、C.I.色素黃166、C.I.色素黃168、C.I.色素黃180、C.I.色素黃211;C.I.色素橘5、C.I.色素橘13、C.I.色素橘14、C.I.色素橘24、C.I.色素橘34、C.I.色素橘36、C.I.色素橘38、C.I.色素橘40、C.I.色素橘43、C.I.色素橘46、C.I.色素橘49、C.I.色素橘61、C.I.色素橘64、C.I.色素橘68、C.I.色素橘70、C.I.色素橘71、C.I.色素橘72、C.I.色素橘73、C.I.色素橘74;C.I.色素紅1、C.I.色素紅2、C.I.色素紅5、C.I.色素紅17、C.I.色素紅31、C.I.色素紅32、C.I.色素紅41、C.I.色素紅122、C.I.色素紅123、C.I.色素紅144、C.I.色素紅149、C.I.色素紅166、C.I.色素紅168、C.I.色素紅170、C.I.色素紅171、C.I.色素紅175、C.I.色素紅176、C.I.色素紅177、C.I.色素紅178、C.I.色素紅179、C.I.色素紅180、C.I.色素紅185、C.I.色素紅187、C.I.色素紅202、C.1.色素紅206、C.I.色素紅207、C.I.色素紅209、C.I.色素紅214、C.I.色素紅220、C.I.色素紅221、C.I.色素紅224、C.I.色素紅242、C.I.色素紅243、C.I.色素紅254、C.I.色素紅255、C.I.色素紅262、C.I.色素紅264、C.I.色素紅272;C.I.色素紫1、C.I.色素紫19、C.I.色素紫23、C.I.色素紫29、C.I.色素紫32、C.I.色素紫36、C.I.色素紫38;C.I.色素藍15、C.I.色素藍15:3、C.I.色素藍15:4、C.I.色素藍15:6、C.I.色素藍60、C.I.色素藍80;C.I.色素綠7、C.I.色素綠36、C.I.色素綠58;C.I.色素棕23、C.I.色素棕25;C.I.色素黑1、C.I.色素黑7。CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 17, CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 55, CI Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 166, CI Pigment Yellow 168, CI Pigment Yellow 180, CI Pigment Yellow 211; CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, 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 61, CI pigment orange 64, CI pigment orange 68, CI pigment orange 70, CI pigment orange 71, CI pigment orange 72, CI pigment orange 73, CI pigment orange 74; CI pigment red 1, CI pigment red 2, CI pigment red 5, CI pigment red 17, CI pigment red 31, CI pigment red 32, CI pigment red 41, CI pigment red 122, CI pigment red 123, CI Pigment Red 144, CI Pigment Red 149, CI Pigment Red 166, CI Pigment Red 168, CI Pigment Red 170 CI Pigment Red 171, CI Pigment Red 175, CI Pigment Red 176, CI Pigment Red 177, CI Pigment Red 178, CI Pigment Red 179, CI Pigment Red 180, CI Pigment Red 185, CI Pigment Red 187, CI Pigment Red 202, C.1. Pigment Red 206, CI Pigment Red 207, CI Pigment Red 209, CI Pigment Red 214, CI Pigment Red 220, CI Pigment Red 221, CI Pigment Red 224, CI Pigment Red 242, CI Pigment Red 243, CI Pigment Red 254, CI pigment red 255, CI pigment red 262, CI pigment red 264, CI pigment red 272; CI pigment purple 1, CI pigment purple 19, CI pigment purple 23, CI pigment purple 29, CI pigment purple 32, CI pigment Violet 36, CI Pigment Violet 38; 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 Blue 80; CI Pigment Green 7, CI Pigment green 36, CI pigment green 58, CI pigment brown 23, CI pigment brown 25; CI pigment black 1, CI pigment black 7.

本發明中，有機顔料可以再結晶法、再沈澱法、溶劑洗淨法、昇華法、真空加熱法或該等組合予以精製使用。又，有機顔料較佳是與實質上不溶解水溶性無機鹽及水溶性無機鹽的水溶性有機溶劑一起，予以機械式捏合(kneading)之方法，亦即以所謂鹽磨法(salt milling)而使初級粒子微細化作使用。鹽磨法之方法，係例如揭示於日本特開平08-179111號公報之物。在使用使初級粒子微細化的有機顔料時，會有降低所形成著色層之耐溶劑性之傾向，不過若使用本發明之著色組成物時，則可解決此等問題。In the present invention, the organic pigment may be purified by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or the like. Further, the organic pigment is preferably subjected to mechanical kneading together with a water-soluble organic solvent which does not substantially dissolve the water-soluble inorganic salt and the water-soluble inorganic salt, that is, by so-called salt milling. The primary particles are made fine for use. The method of the salt milling method is disclosed, for example, in Japanese Laid-Open Patent Publication No. Hei 08-179111. When an organic pigment which refines the primary particles is used, the solvent resistance of the colored layer to be formed tends to be lowered. However, when the colored composition of the present invention is used, such problems can be solved.

又，就上述無機顔料而言，可例舉例如氧化鈦、硫酸鋇、碳酸鈣、鋅白、硫酸鉛、黃色鉛、鋅黃、氧化鐵(紅色氧化鐵(III))、鎘紅、群青、普魯士藍、氧化鉻綠、鈷綠、琥珀(ambers)、鈦黑、合成鐵黑、碳黑等。Further, the inorganic pigment may, for example, be titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, iron oxide (red iron oxide (III)), cadmium red, ultramarine blue, Prussian blue, chrome oxide green, cobalt green, ambers, titanium black, synthetic iron black, carbon black, and the like.

該等著色劑依照所期望，可以樹脂使該粒子表面改質作使用。就在使顔料之粒子表面改質之樹脂而言，例如記載於日本特開2001-108817號公報的展色劑樹脂，或市售之各種顔料分散用之樹脂。就碳黑表面之樹脂被覆方法而言，可採用例如日本特開平9-71733號公報、日本特開平9-95625號公報、日本特開平9-124969號公報等記載之方法。The colorants may be modified to use the surface of the particles as desired. The resin which is used to disperse the surface of the pigment particles is, for example, a resin resin described in JP-A-2001-108817, or a commercially available resin for dispersing various pigments. For the resin coating method of the surface of the carbon black, a method described in, for example, JP-A-H09-71733, JP-A-9-95625, JP-A-9-124969, and the like can be employed.

本發明中(A)著色劑可單獨使用或混合二種以上使用。In the present invention, the coloring agent (A) may be used singly or in combination of two or more.

將本發明之著色組成物使用於像素之形成之情形，由於在像素係謀求高精細的發色，就(A)著色劑而言，較佳是顯色性高的著色劑，具體言之可適當使用有機顔料。When the coloring composition of the present invention is used for the formation of a pixel, since a high-definition color development is required in the pixel system, the coloring agent (A) is preferably a coloring agent having high color rendering property, specifically, Appropriate use of organic pigments.

另一方面，在使用本發明之著色組成物於黑色矩陣之形成之情形，由於在黑色矩陣有要求遮光性，故就(A)著色劑而言較佳是使用有機顔料或碳黑。On the other hand, in the case of using the coloring composition of the present invention in the formation of a black matrix, since the black matrix is required to have light shielding properties, it is preferred to use an organic pigment or carbon black for the (A) coloring agent.

(A)著色劑之含量，由形成透明性及色純度優異的像素、或者遮光性優異的黑色矩陣之點，較佳為著色組成物之全固體成分中5至70質量%，更佳為5至60質量%。在此固體成分係指後述溶劑以外之成分。本發明之著色組成物，著色劑之含量，在著色組成物之全固體成分中，於成為30質量%以上之情形，亦可形成耐溶劑性優異的像素。(A) The content of the coloring agent is preferably from 5 to 70% by mass, more preferably from 5 to 70% by mass of the total solid content of the coloring composition, from the viewpoint of forming a pixel excellent in transparency and color purity or a black matrix having excellent light blocking properties. Up to 60% by mass. Here, the solid content means a component other than the solvent described later. In the coloring composition of the present invention, when the content of the coloring agent is 30% by mass or more in the total solid content of the coloring composition, a pixel excellent in solvent resistance can be formed.

本發明中著色劑，可依照期望，與分散劑、分散助劑一起使用。就上述分散劑而言，可使用例如陽離子系、陰離子系、非離子系等適宜之分散劑，較佳為聚合物分散劑。具體言之，可例舉丙烯酸系共聚物、聚胺基甲酸酯、聚酯、聚乙烯亞胺、聚烯丙基胺等。The coloring agent in the present invention can be used together with a dispersing agent and a dispersing aid as desired. As the above dispersing agent, a suitable dispersing agent such as a cationic system, an anionic system or a nonionic system can be used, and a polymer dispersant is preferable. Specifically, an acrylic copolymer, a polyurethane, a polyester, a polyethyleneimine, a polyallylamine or the like can be exemplified.

此種分散劑可由商業方式取得，可例舉例如，丙烯酸系共聚物之Disperbyk-2000、Disperbyk-2001、BYK-LPN6919、BYK-LPN21116(以上為BYK公司製)；聚胺基甲酸酯之Disperbyk-161、Disperbyk-162、Disperbyk-165、Disperbyk-167、Disperbyk-170、Disperbyk-182(以上、BYK公司製)、Solsperse 76500(Lubrizol股份公司製)；聚乙烯亞胺之Solsperse 24000(Lubrizol股份公司製)；聚酯之Ajisper PB821、Ajisper PB822、Ajisper PB880(味之素Fine Techno股份有限公司製)等。Such a dispersing agent can be obtained commercially, and examples thereof include Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, and BYK-LPN21116 (manufactured by BYK Co., Ltd.) of an acrylic copolymer; Disperbyk of a polyurethane. -161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, BYK), Solsperse 76500 (manufactured by Lubrizol AG); Solsperse 24000 of polyethyleneimine (Lubrizol AG) A) Ajisper PB821, Ajisper PB822, Ajisper PB880 (manufactured by Ajinomoto Fine Techno Co., Ltd.) and the like.

該等分散劑可單獨使用或混合二種以上使用。分散劑之含量相對於(A)著色劑100質量份，通常為100質量份以下、較佳為1至70質量份、再佳為10至50質量份。分散劑之含量過多時，會有損及顯影性等之虞。These dispersing agents may be used singly or in combination of two or more. The content of the dispersant is usually 100 parts by mass or less, preferably 1 to 70 parts by mass, more preferably 10 to 50 parts by mass, per 100 parts by mass of the (A) colorant. When the content of the dispersant is too large, the developer property or the like may be impaired.

就上述分散助劑而言，可例舉例如顔料衍生物，具體言之，可例舉銅酞青、二酮基吡咯并吡咯、喹啉黃之磺酸衍生物等。The above-mentioned dispersing aid may, for example, be a pigment derivative, and specifically, a copper phthalocyanine, a diketopyrrolopyrrole or a quinoline yellow sulfonic acid derivative may, for example, be mentioned.

-(B)黏合劑樹脂-- (B) Adhesive Resin -

就本發明中(B)黏合劑樹脂而言，並無特別限定，較佳是具有羧基、酚性羥基、磺酸基等之酸性官能基的樹脂。要提高本發明所期望之效果就得將酸性官能基與進一步具有聚合性不飽和基的聚合物在全黏合劑樹脂中，較佳為含有10質量%以上，再佳為含有30質量%以上。The (B) binder resin in the present invention is not particularly limited, and is preferably a resin having an acidic functional group such as a carboxyl group, a phenolic hydroxyl group or a sulfonic acid group. In order to enhance the desired effect of the present invention, the acidic functional group and the polymer further having a polymerizable unsaturated group are preferably contained in the total binder resin in an amount of 10% by mass or more, more preferably 30% by mass or more.

就上述酸性官能基而言，可例舉羧基、酚性羥基、磺酸基等，不過由鹼可溶性及所得著色組成物之保存穩定性之點，較佳為羧基。The acidic functional group may, for example, be a carboxyl group, a phenolic hydroxyl group or a sulfonic acid group. However, a carboxyl group is preferred from the viewpoint of alkali solubility and storage stability of the obtained colored composition.

又，就上述聚合性不飽和基而言，可例舉乙烯芳基、(甲基)丙烯醯基、烯丙基等，不過由提高所期望之效果之點，較佳為(甲基)丙烯醯基。又，具有酸性官能基與聚合性不飽和基之聚合物，較佳是其側鏈具有聚合性不飽和基之物。Further, the polymerizable unsaturated group may, for example, be a vinyl aryl group, a (meth) acryl fluorenyl group or an allyl group, but is preferably a (meth) propylene from the viewpoint of improving a desired effect.醯基. Further, the polymer having an acidic functional group and a polymerizable unsaturated group is preferably one having a polymerizable unsaturated group in its side chain.

具有酸性官能基與聚合性不飽和基之聚合物，在滿足上述要件之範圍並無特別限定，例如，(b-1)在具有羧基之聚合性不飽和化合物之聚合物之羧基中，使具有環氧乙基的聚合性不飽和化合物反應所得聚合物(以下，稱為「黏合劑樹脂(b-1)」)；(b-2)在具有羥基的聚合性不飽和化合物與具有酸性官能基之聚合性不飽和化合物之共聚物之羥基中，使具有異氰酸基之聚合性不飽和化合物反應所得聚合物(以下稱為「黏合劑樹脂(b-2)」)；(b-3)在具有環氧乙基之聚合性不飽和化合物之聚合物之環氧乙基中，使具有羧基之聚合性不飽和化合物反應，再者，在由該反應所產生之羥基中，使酸酐反應所得聚合物(以下稱為「黏合劑樹脂(b-3)」)；(b-4)在環氧樹脂之環氧基中，使具有羧基之聚合性不飽和化合物反應，再者，在由該反應所產生的羥基中，使酸酐反應所得聚合物(以下稱為「黏合劑樹脂(b-4)」)；(b-5)在苯乙烯或其衍生物與順丁烯二酸酐或其酯之共聚物中，使具有羥基之聚合性不飽和化合物反應所得聚合物(以下稱為「黏合劑樹脂(b-5)」)等。The polymer having an acidic functional group and a polymerizable unsaturated group is not particularly limited as long as it satisfies the above requirements. For example, (b-1) has a carboxyl group of a polymer having a carboxyl group of a polymerizable unsaturated compound. a polymer obtained by reacting an epoxy group-containing polymerizable unsaturated compound (hereinafter referred to as "binder resin (b-1)"); (b-2) a polymerizable unsaturated compound having a hydroxyl group and having an acidic functional group a polymer obtained by reacting a polymerizable unsaturated compound having an isocyanate group in a hydroxyl group of a copolymer of a polymerizable unsaturated compound (hereinafter referred to as "adhesive resin (b-2)"); (b-3) In the epoxyethyl group of the polymer having a polymerizable unsaturated compound of an epoxy group, a polymerizable unsaturated compound having a carboxyl group is reacted, and further, an acid anhydride is reacted in a hydroxyl group produced by the reaction. a polymer (hereinafter referred to as "adhesive resin (b-3)"); (b-4) reacting a polymerizable unsaturated compound having a carboxyl group in an epoxy group of an epoxy resin, and further Among the hydroxyl groups produced by the reaction, the acid anhydride is reacted to obtain the polymer ( It is called "adhesive resin (b-4)"); (b-5) reacts a polymerizable unsaturated compound having a hydroxyl group in a copolymer of styrene or its derivative with maleic anhydride or its ester. The obtained polymer (hereinafter referred to as "adhesive resin (b-5)") or the like.

黏合劑樹脂(b-1)之製造所使用之具有羧基之聚合性不飽和化合物之聚合物，若有羧基則並無特別限定，其係聚合具有羧基的聚合性不飽和化合物所得。The polymer having a carboxyl group-containing polymerizable unsaturated compound used in the production of the binder resin (b-1) is not particularly limited as long as it has a carboxyl group, and is obtained by polymerizing a polymerizable unsaturated compound having a carboxyl group.

在具有羧基之聚合性不飽和化合物方面，可例舉例如，除了(甲基)丙烯酸或順丁烯二酸之外，加成內酯類於(甲基)丙烯酸的不飽和化合物；加成琥珀酸、順丁烯二酸、酞酸、或該等酐等之二元酸或其酐於(甲基)丙烯酸羥基烷酯的不飽和化合物等。該等亦可使用複數種。In the case of a polymerizable unsaturated compound having a carboxyl group, for example, an unsaturated compound of a (meth)acrylic acid added to a lactone other than (meth)acrylic acid or maleic acid; addition of amber An acid, a maleic acid, a citric acid, or a dibasic acid such as the anhydride or an anhydride thereof, an unsaturated compound of a hydroxyalkyl (meth)acrylate or the like. These can also be used in a plurality of types.

其中較佳為(甲基)丙烯酸、琥珀酸2-(甲基)丙烯醯氧乙酯、ω-羧基聚己內酯單(甲基)丙烯酸酯，再佳為(甲基)丙烯酸。Among them, preferred are (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinate, ω-carboxypolycaprolactone mono(meth)acrylate, and more preferably (meth)acrylic acid.

在黏合劑樹脂(b-1)之製造所使用之具有環氧乙基的聚合性不飽和化合物方面，可例舉例如具有：(甲基)丙烯酸環氧丙酯、烯丙基環氧丙醚、環氧丙基-α-乙基丙烯酸酯、巴豆醯基環氧丙醚、(異)巴豆酸環氧丙醚、N-(3,5-二甲基-4-環氧丙基)苄基丙烯醯胺、4-羥基丁基(甲基)丙烯酸酯環氧丙醚、對乙烯苄基環氧丙醚等之具有環氧丙基之不飽和化合物；2,3-環氧基環戊基、3,4-環氧基環己基、7,8-環氧[三環[5.2.1.0]癸-2-基]基等之脂環式環氧基與(甲基)丙烯醯基等之聚合性不飽和基的不飽和化合物。該等亦可使用複數種。The polymerizable unsaturated compound having an epoxy group used in the production of the binder resin (b-1) may, for example, be: glycidyl (meth)acrylate or allyl epoxidized ether. , epoxypropyl-α-ethyl acrylate, crotonyl epoxidized propyl ether, (iso) crotonic acid epoxidized ether, N-(3,5-dimethyl-4-epoxypropyl) benzyl An epoxy group-containing unsaturated compound such as acrylamide, 4-hydroxybutyl (meth) acrylate glycidyl ether, p-vinylbenzyl epoxidized propyl ether or the like; 2,3-epoxycyclopentane An alicyclic epoxy group such as a 3,4-epoxycyclohexyl group, a 7,8-epoxy[tricyclo[5.2.1.0]indol-2-yl] group, etc., and a (meth)acryloyl group A polymerizable unsaturated group of unsaturated compounds. These can also be used in a plurality of types.

黏合劑樹脂(b-2)之製造所使用之具有羥基之聚合性不飽和化合物、與具有酸性官能基之聚合性不飽和化合物之共聚物，若是具有羥基與酸性官能基，則並無特別限定，其係聚合至少具有羥基之聚合性不飽和化合物與具有酸性官能基之聚合性不飽和化合物所得。The copolymer of a polymerizable unsaturated compound having a hydroxyl group and a polymerizable unsaturated compound having an acidic functional group used for the production of the binder resin (b-2) is not particularly limited as long as it has a hydroxyl group and an acidic functional group. It is obtained by polymerizing a polymerizable unsaturated compound having at least a hydroxyl group and a polymerizable unsaturated compound having an acidic functional group.

在具有羥基與乙烯基之聚合性不飽和化合物方面，可例舉除了(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸羥基丙酯、單(甲基)丙烯酸甘油酯等之(甲基)丙烯酸羥基烷酯之外，尚有N-羥甲基丙烯醯胺、烯丙醇等。又，在具有酸性官能基之聚合性不飽和化合物方面，可例舉上述黏合劑樹脂(b-1)中所舉之具有羧基的聚合性不飽和化合物等。該等亦可使用複數種。The polymerizable unsaturated compound having a hydroxyl group and a vinyl group may, for example, be 4-hydroxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, or the like. In addition to the hydroxyalkyl (meth)acrylate such as (meth)acrylic acid acrylate, there are N-methylol acrylamide, allyl alcohol and the like. In addition, as the polymerizable unsaturated compound having an acidic functional group, a polymerizable unsaturated compound having a carboxyl group as exemplified in the above-mentioned binder resin (b-1) may, for example, be mentioned. These can also be used in a plurality of types.

黏合劑樹脂(b-2)之製造所使用之具有異氰酸基之聚合性不飽和化合物方面，可例舉例如異氰酸2-(甲基)丙烯醯基氧乙酯、(甲基)丙烯酸2-(2-異氰酸酯乙氧基)乙酯、異氰酸1,1-(雙丙烯醯基氧甲基)乙酯等。該等亦可使用複數種。The polymerizable unsaturated compound having an isocyanate group used for the production of the binder resin (b-2) may, for example, be 2-(methyl)propenyloxyethyl isocyanate or (methyl) 2-(2-Isocyanate ethoxy)ethyl acrylate, 1,1-(bisacryloyloxymethyl)ethyl isocyanate, and the like. These can also be used in a plurality of types.

黏合劑樹脂(b-3)之製造所使用之具有環氧乙基之聚合性不飽和化合物之聚合物，只要是具有環氧乙基的聚合物則佳，不過可例舉具有環氧乙基的聚(甲基)丙烯酸酯系共聚物、環氧乙基之聚苯乙烯系共聚物等。具有環氧乙基之聚(甲基)丙烯酸酯系共聚物，係具有環氧乙基的(甲基)丙烯酸酯與其他聚合性不飽和化合物之共聚物。具有環氧乙基之(甲基)丙烯酸酯方面，可例舉(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(3,4-環氧環己基)甲酯、4-羥基丁基(甲基)丙烯酸酯環氧丙醚等。該等亦可使用複數種。The polymer of the polymerizable unsaturated compound having an epoxy group used in the production of the binder resin (b-3) is preferably a polymer having an epoxy group, but may be exemplified by having an epoxy group. Poly(meth)acrylate copolymer, epoxyethylpolystyrene copolymer, and the like. A poly(meth)acrylate copolymer having an epoxy group is a copolymer of a (meth) acrylate having an epoxy group and another polymerizable unsaturated compound. Examples of the (meth) acrylate having an epoxy group include glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and (meth)acrylic acid (3, 4). - Epoxycyclohexyl)methyl ester, 4-hydroxybutyl (meth) acrylate glycidyl ether, and the like. These can also be used in a plurality of types.

又，構成具有環氧乙基之苯乙烯系共聚物之具有環氧乙基之苯乙烯類方面，可例舉鄰乙烯苄基環氧丙醚、間乙烯苄基環氧丙醚、對乙烯苄基環氧丙醚、2,4-二環氧丙基氧甲基苯乙烯、3,4,5-三環氧丙基甲基苯乙烯等之具有環氧丙基1至3個的苯乙烯類。該等亦可使用複數種。Further, examples of the styrene having an epoxy group and a styrene-based copolymer having an epoxy group include o-vinylbenzyl epoxidized propyl ether, m-vinyl benzyl epoxidized propyl ether, and p-vinyl benzyl. Styrene with a glycidyl group of 1,3,2-diepoxypropyloxymethylstyrene, 3,4,5-triepoxypropylmethylstyrene, etc. class. These can also be used in a plurality of types.

黏合劑樹脂(b-3)之製造所使用之具有羧基之聚合性不飽和化合物方面，可例舉(甲基)丙烯酸、ω-羧基-聚己內酯單(甲基)丙烯酸酯、琥珀酸2-(甲基)丙烯醯基乙酯等。該等亦可使用複數種。The polymerizable unsaturated compound having a carboxyl group used for the production of the binder resin (b-3) may, for example, be (meth)acrylic acid, ω-carboxy-polycaprolactone mono(meth)acrylate or succinic acid. 2-(Methyl) propylene decyl ethyl ester or the like. These can also be used in a plurality of types.

黏合劑樹脂(b-3)之製造所使用之酸酐方面，可例舉例如丙二酸酐、順丁烯二酸酐、檸康酸酐、琥珀酸酐、戊二酸酐、戊烯二酸酐、伊康酸酐、二羥乙酸酐、酞酸酐、環己烷-1,2-二羧酸酐、4-環己烯-1,2-二羧酸酐、聯苯二甲酸酐等之多元酸酐。該等亦可使用複數種。Examples of the acid anhydride used in the production of the binder resin (b-3) include malonic anhydride, maleic anhydride, citraconic anhydride, succinic anhydride, glutaric anhydride, glutaconic anhydride, and itaconic anhydride. A polybasic acid anhydride such as dihydroxyacetic anhydride, decanoic anhydride, cyclohexane-1,2-dicarboxylic anhydride, 4-cyclohexene-1,2-dicarboxylic anhydride, or phthalic anhydride. These can also be used in a plurality of types.

此外，黏合劑樹脂(b-1)之製造所使用之具有羧基之聚合性不飽和化合物之聚合物，黏合劑樹脂(b-2)之製造所使用之具有羥基之聚合性不飽和化合物與具有酸性官能基之聚合性不飽和化合物之共聚物，及黏合劑樹脂(b-3)之製造所使用之具有環氧乙基之聚合性不飽和化合物之聚合物中，可使與各聚合性不飽和化合物可共聚的其他聚合性不飽和化合物予以共聚。Further, a polymer having a carboxyl group-containing polymerizable unsaturated compound used for the production of the binder resin (b-1), a polymerizable unsaturated compound having a hydroxyl group used for the production of the binder resin (b-2), and having A copolymer of a polymerizable unsaturated compound having an acidic functional group and a polymer having an epoxyethyl group-containing polymerizable unsaturated compound used in the production of the binder resin (b-3) can be used without any polymerization property. Other polymerizable unsaturated compounds copolymerizable with the saturated compound are copolymerized.

此等其他聚合性不飽和化合物方面，可例舉例如N-苯基順丁烯二醯亞胺、N-環己基順丁烯二醯亞胺等N-位置取代順丁烯二醯亞胺；苯乙烯、α-甲基苯乙烯、對羥基-α-甲基苯乙烯、乙烯合萘等之芳香族乙烯化合物；(甲基)丙烯酸甲基酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸異酯、三環[5.2.1.02,6 ]癸烷-8-基(甲基)丙烯酸酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸4-羥基苯酯、對酚之環氧乙烷改性(甲基)丙烯酸酯等之(甲基)丙烯酸酯等。又，聚合物(b-1)之製造所使用之具有羧基之聚合性不飽和化合物之聚合物，聚合物(b-3)之製造所使用之具有環氧乙基之聚合性不飽和化合物之聚合物中，可例舉使(甲基)丙烯酸2-羥基乙酯、單(甲基)丙烯酸甘油酯等之具有羥基之聚合性不飽和化合物予以共聚者。該等亦可使用複數種。The other polymerizable unsaturated compound may, for example, be an N-position-substituted maleimide such as N-phenylmaleimide or N-cyclohexylmethyleneimine; An aromatic vinyl compound such as styrene, α-methylstyrene, p-hydroxy-α-methylstyrene or vinyl naphthalene; methyl (meth)acrylate, n-butyl (meth)acrylate, (a) 2-ethylhexyl acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylate Ester, tricyclo[5.2.1.0 2,6 ]decane-8-yl (meth) acrylate, dicyclopentenyl (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, A (meth) acrylate such as an oxirane-modified ethylene (meth) acrylate or the like. Further, a polymer of a polymerizable unsaturated compound having a carboxyl group used for the production of the polymer (b-1), and a polymerizable unsaturated compound having an epoxy group used for the production of the polymer (b-3) The polymer may be a copolymerized polymerizable unsaturated compound having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate or glycerol mono(meth)acrylate. These can also be used in a plurality of types.

黏合劑樹脂(b-4)之製造所使用之環氧樹脂方面，可例舉雙酚A型環氧樹脂、雙酚A型環氧樹脂之醇性羥基與環氧氯丙烷之反應所得環氧樹脂、雙酚F型環氧樹脂、雙酚F型環氧樹脂之醇性羥基與環氧氯丙烷之反應所得環氧樹脂、雙酚S型環氧樹脂、聯苯基環氧丙醚、酚系酚醛清漆型環氧樹脂、甲酚系酚醛清漆型環氧樹脂、異三聚氰酸三環氧丙酯、參酚甲烷型環氧樹脂、茀環氧樹脂、脂環式環氧樹脂、二環戊二烯型環氧樹脂等。又亦可使用共聚型之環氧樹脂。The epoxy resin used in the production of the binder resin (b-4) may, for example, be an epoxy obtained by reacting an alcoholic hydroxyl group of a bisphenol A epoxy resin or a bisphenol A epoxy resin with epichlorohydrin. Epoxy resin, bisphenol S type epoxy resin, biphenyl epoxidized propyl ether, phenol obtained by reacting alcoholic hydroxyl group of phenolic bisphenol F type epoxy resin and bisphenol F type epoxy resin with epichlorohydrin A novolac type epoxy resin, a cresol novolac type epoxy resin, a triglycidyl isocyanate, a phenolic methane type epoxy resin, an anthracene epoxy resin, an alicyclic epoxy resin, A cyclopentadiene type epoxy resin or the like. A copolymer type epoxy resin can also be used.

黏合劑樹脂(b-4)之製造所使用之具有羧基之聚合性不飽和化合物及酸酐方面，可例舉與該黏合劑樹脂(b-3)之製造中所使用之物相同之物。The polymerizable unsaturated compound having a carboxyl group and the acid anhydride used in the production of the binder resin (b-4) may be the same as those used in the production of the binder resin (b-3).

黏合劑樹脂(b-5)之製造所使用之苯乙烯或其衍生物與順丁烯二酸酐之共聚物方面，可例舉例如苯乙烯、間甲氧基苯乙烯、對甲氧基苯乙烯等；與順丁烯二酸酐、或者順丁烯二酸單甲酯、順丁烯二酸單乙酯、順丁烯二酸單-正丙酯、順丁烯二酸單-異丙酯、順丁烯二酸單-正丁酯、順丁烯二酸單-異丁酯、順丁烯二酸單-三級丁酯等之順丁烯二酸單低級烷酯之共聚物。The copolymer of styrene or a derivative thereof and maleic anhydride used for the production of the binder resin (b-5) may, for example, be styrene, m-methoxystyrene or p-methoxystyrene. And; with maleic anhydride, or monomethyl maleate, monoethyl maleate, mono-n-propyl maleate, mono-isopropyl maleate, A copolymer of maleic acid mono-lower alkyl maleate, mono-isobutyl maleate, mono-tert-butyl maleate or the like.

黏合劑樹脂(b-5)之製造所使用之具有羥基之聚合性不飽和化合物方面，可例舉(甲基)丙烯酸羥基烷酯、N-羥甲基丙烯醯胺、烯丙基醇等。The polymerizable unsaturated compound having a hydroxyl group used for the production of the binder resin (b-5) may, for example, be a hydroxyalkyl (meth)acrylate, N-methylol acrylamide or allyl alcohol.

本發明中，黏合劑樹脂，可單獨使用具有酸性官能基，或不具聚合性不飽和基的聚合物，亦可與具有酸性官能基及聚合性不飽和基的聚合物一起使用。此等黏合劑樹脂之具體例方面，可例舉例如日本特開平7-140654號公報、日本特開平9-311444號公報、日本特開平10-31308號公報、日本特開平10-300922號公報、日本特開平11-174224號公報、日本特開平11-258415號公報、日本特開2000-56118號公報、日本特開2002-296778、日本特開2004-101728等所揭示之共聚物。In the present invention, as the binder resin, a polymer having an acidic functional group or a non-polymerizable unsaturated group may be used alone, or a polymer having an acidic functional group and a polymerizable unsaturated group may be used together. Specific examples of such a binder resin include, for example, JP-A-7-140654, JP-A-H09-311444, JP-A-10-31308, and JP-A-10-300922. A copolymer disclosed in JP-A-H07-174224, JP-A-H11-258415, JP-A-2000-56118, JP-A-2002-296778, and JP-A-2004-101728.

本發明中黏合劑樹脂之酸價，較佳為10至200KOH/mg，更佳為20至150KOH/mg，再佳為30至150KOH/mg。The acid value of the binder resin in the present invention is preferably from 10 to 200 KOH/mg, more preferably from 20 to 150 KOH/mg, still more preferably from 30 to 150 KOH/mg.

本發明中以黏合劑樹脂之凝膠滲透層析法(GPC、溶離溶劑：四氫呋喃)測定的換算聚苯乙烯重量平均分子量(以下稱為「Mw」)，較佳為1,000至100,000、再佳為3,000至50,000。在此情形，Mw過小時，則所得被膜之殘膜率等降低，或有損及圖案形狀、耐熱性等，又，會有電特性惡化之虞，另一方面，Mw過大時，則解像度降低，或有損及圖案形狀，又會有狹縫式噴嘴方式所致塗布時易於產生乾燥異物之虞。In the present invention, the weight average molecular weight of the converted polystyrene (hereinafter referred to as "Mw") measured by gel permeation chromatography (GPC, solvent: tetrahydrofuran) of the binder resin is preferably 1,000 to 100,000, and more preferably 3,000 to 50,000. In this case, when the Mw is too small, the residual film ratio of the obtained film is lowered, or the pattern shape, heat resistance, and the like are impaired, and the electrical characteristics are deteriorated. On the other hand, when the Mw is too large, the resolution is lowered. Or it may damage the shape of the pattern, and there will be a problem that the drying of foreign matter is likely to occur during coating due to the slit nozzle method.

又，本發明中黏合劑樹脂之Mw，與以凝膠滲透層析法(GPC、溶離溶劑：四氫呋喃)測定的換算聚苯乙烯數量平均分子量(以下稱為「Mn」)之比(Mw/Mn)，較佳為1.0至5.0，更佳為1.0至3.0。Further, in the present invention, the ratio of the Mw of the binder resin to the number average molecular weight (hereinafter referred to as "Mn") of the converted polystyrene measured by gel permeation chromatography (GPC, solvent: tetrahydrofuran) (Mw/Mn) It is preferably from 1.0 to 5.0, more preferably from 1.0 to 3.0.

本發明中黏合劑樹脂可以習知之方法製造，不過可藉由例如日本特開2003-222717號公報、日本特開2006-259680號公報、國際公開第07/029871號要約等所揭示之方法，來控制其構造或Mw、Mw/Mn。又，具有上述酸性官能基與聚合性不飽和基的聚合物，可以習知之方法，例如日本特開平5-19467號公報、日本特開平5-61196號公報、日本特開平6-230212號公報、日本特開平7-207211號公報、日本特開2008-181095號公報等所揭示之方法來製造。In the present invention, the binder resin can be produced by a known method, but it can be obtained by a method disclosed in, for example, Japanese Laid-Open Patent Publication No. 2003-222717, Japanese Patent Laid-Open No. Hei. No. 2006-259680, and International Publication No. 07/029871. Control its structure or Mw, Mw / Mn. In addition, a polymer having the above-mentioned acidic functional group and a polymerizable unsaturated group can be obtained by a conventional method, for example, JP-A-H05-19467, JP-A-H05-61196, JP-A-6-230212, It is produced by the method disclosed in Japanese Laid-Open Patent Publication No. Hei 7-207211, and the Japanese Patent Publication No. 2008-181095.

本發明中，黏合劑樹脂可單獨使用，或混合二種以上使用。In the present invention, the binder resin may be used singly or in combination of two or more.

本發明中，相對於(A)著色劑100質量份，黏合劑樹脂之含量較佳為10至1,000質量份、再佳為20至500質量份。在此情形，黏合劑樹脂之含量過少時，會有例如鹼顯影性降低，或在未曝光部之基板上或者遮光層上發生殘渣或表面污斑之虞，另一方面，過多時，則相對而言因顔料濃度降低，故會有達成作為薄膜之目的的色濃度造成困難之虞。In the present invention, the content of the binder resin is preferably from 10 to 1,000 parts by mass, more preferably from 20 to 500 parts by mass, per 100 parts by mass of the (A) colorant. In this case, when the content of the binder resin is too small, for example, alkali developability may be lowered, or residue or surface stain may occur on the substrate of the unexposed portion or on the light shielding layer. On the other hand, when it is too large, it is relatively In view of the fact that the concentration of the pigment is lowered, it is difficult to achieve a color density which is a purpose of the film.

-(C)多官能性單體--(C) Polyfunctional monomer -

本發明中(C)多官能性單體只要是具有2個以上可聚合之基之單體則無特別限定。可聚合之基方面，可例舉例如乙烯性不飽和基、環氧乙基、氧雜環丁烷基、N-烷氧基甲基胺基等。本發明中，(C)多官能性單體方面，較佳為具有2個以上(甲基)丙烯醯基的化合物、或具有2個以上N-烷氧基甲基胺基的化合物。In the present invention, the (C) polyfunctional monomer is not particularly limited as long as it is a monomer having two or more polymerizable groups. The polymerizable group may, for example, be an ethylenically unsaturated group, an epoxyethyl group, an oxetanyl group or an N-alkoxymethylamino group. In the present invention, the (C) polyfunctional monomer is preferably a compound having two or more (meth)acryl fluorenyl groups or a compound having two or more N-alkoxymethylamino groups.

上述具有2個以上(甲基)丙烯醯基的化合物之具體例方面，可例舉脂肪族聚羥基化合物與(甲基)丙烯酸之酯、經己內酯改性的多官能(甲基)丙烯酸酯、經氧化烯改性的多官能(甲基)丙烯酸酯、使具有羥基之(甲基)丙烯酸酯與多官能異氰酸酯反應所得多官能胺基甲酸酯(甲基)丙烯酸酯、使具有羥基之(甲基)丙烯酸酯與酸酐反應所得具有羧基之多官能(甲基)丙烯酸酯等。Specific examples of the compound having two or more (meth) acrylonitrile groups may, for example, be an ester of an aliphatic polyhydroxy compound and (meth)acrylic acid or a polyfunctional (meth)acrylic acid modified with caprolactone. An ester, an oxyalkylene-modified polyfunctional (meth) acrylate, a polyfunctional urethane (meth) acrylate obtained by reacting a hydroxyl group-containing (meth) acrylate with a polyfunctional isocyanate, and having a hydroxyl group A polyfunctional (meth) acrylate having a carboxyl group obtained by reacting a (meth) acrylate with an acid anhydride.

在此，上述脂肪族聚羥基化合物方面，可例舉例如乙二醇、丙二醇、聚乙二醇、聚丙二醇般之二價脂肪族聚羥基化合物；甘油、三羥甲基丙烷、新戊四醇、二新戊四醇般之3價以上脂肪族聚羥基化合物。具有上述羥基的(甲基)丙烯酸酯方面，可例舉例如(甲基)丙烯酸2-羥基乙酯、二(甲基)丙烯酸三羥甲基丙酯、三(甲基)丙烯酸新戊四醇酯、五(甲基)丙烯酸二新戊四醇酯、二甲基丙烯酸甘油酯等。上述多官能異氰酸酯方面，可例舉例如甲苯二異氰酸酯、二異氰酸六亞甲酯、二異氰酸二苯基亞甲酯、二異氰酸異佛爾酮酯等。酸酐方面，可例舉例如琥珀酸酐、順丁烯二酸酐、戊二酸酐、伊康酸酐、酞酸酐、六氫酞酸酐般之二鹼式酸之酐；均苯四酸酐、聯苯基四羧酸二酐、二苯酮四羧酸二酐般之四元酸二酐。Here, the aliphatic polyhydroxy compound may, for example, be a divalent aliphatic polyhydroxy compound such as ethylene glycol, propylene glycol, polyethylene glycol or polypropylene glycol; glycerin, trimethylolpropane or neopentyl alcohol; An aliphatic polyhydroxy compound having a trivalent or higher valence of dipentaerythritol. The (meth) acrylate having the above hydroxyl group may, for example, be 2-hydroxyethyl (meth)acrylate, trimethylolpropyl di(meth)acrylate, or neopentaerythritol tri(meth)acrylate. Ester, dipentaerythritol penta(meth)acrylate, glyceryl dimethacrylate, and the like. The polyfunctional isocyanate may, for example, be toluene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate or isophorone diisocyanate. The acid anhydride may, for example, be an anhydride of a dibasic acid such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride or hexahydrophthalic anhydride; pyromellitic anhydride or biphenyl tetracarboxylic acid; A tetrabasic acid dianhydride similar to acid dianhydride and benzophenone tetracarboxylic dianhydride.

又上述經己內酯改性的官能(甲基)丙烯酸酯方面，可例舉例如日本特開11-44955號公報之段落[0015]至[0018]記載之化合物。上述經氧化烯改性的多官能(甲基)丙烯酸酯方面，可例舉雙酚A之環氧乙烷及/或環氧丙烷改性二(甲基)丙烯酸酯、異三聚氰酸之環氧乙烷及/或環氧丙烷改性三(甲基)丙烯酸酯、三羥甲基丙烷之環氧乙烷及/或環氧丙烷改性三(甲基)丙烯酸酯、新戊四醇之環氧乙烷及/或環氧丙烷改性三(甲基)丙烯酸酯、新戊四醇之環氧乙烷及/或環氧丙烷改性四(甲基)丙烯酸酯、二新戊四醇之環氧乙烷及/或環氧丙烷改性五(甲基)丙烯酸酯、二新戊四醇之環氧乙烷及/或環氧丙烷改性六(甲基)丙烯酸酯等。Further, the above-mentioned caprolactone-modified functional (meth) acrylate may, for example, be a compound described in paragraphs [0015] to [0018] of JP-A-11-44955. The above oxyalkylene-modified polyfunctional (meth) acrylate may, for example, be an ethylene oxide and/or propylene oxide-modified di(meth)acrylate of bisphenol A or an iso-cyanuric acid. Ethylene oxide and/or propylene oxide modified tri(meth)acrylate, trimethylolpropane ethylene oxide and/or propylene oxide modified tri(meth)acrylate, neopentyl alcohol Ethylene oxide and/or propylene oxide modified tri(meth)acrylate, neopentyl alcohol ethylene oxide and/or propylene oxide modified tetra(meth)acrylate, dipentaerythritol Ethylene oxide and/or propylene oxide modified penta (meth) acrylate, dipentaerythritol ethylene oxide and/or propylene oxide modified hexa (meth) acrylate, and the like.

又，上述具有2個以上N-烷氧基甲基胺基的化合物方面，可例舉例如具有三聚氰胺構造、苯并鳥糞胺構造、脲構造的化合物等。此外，三聚氰胺構造、苯并鳥糞胺構造係指包含三聚氰胺、苯并鳥糞胺或該等縮合物在內之概念。具有2個以上N-烷氧基甲基胺基的化合物之具體例方面，可例舉N,N,N,N,N,N-六(烷氧基甲基)三聚氰胺、N,N,N,N-四(烷氧基甲基)苯并鳥糞胺、N,N,N,N-四(烷氧基甲基)乙炔脲等。Further, the compound having two or more N-alkoxymethylamino groups may, for example, be a compound having a melamine structure, a benzoguanamine structure, or a urea structure. Further, the melamine structure and the benzoguanamine structure refer to a concept including melamine, benzoguanamine or the like. Specific examples of the compound having two or more N-alkoxymethylamino groups may, for example, be N,N,N,N,N,N-hexa(alkoxymethyl)melamine, N,N,N. , N-tetrakis(alkoxymethyl)benzoguanamine, N,N,N,N-tetrakis(alkoxymethyl)acetylene urea, and the like.

該等多官能性單體中，較佳為3價以上脂肪族聚羥基化合物與(甲基)丙烯酸之酯、經己內酯改性的多官能(甲基)丙烯酸酯、多官能胺基甲酸酯(甲基)丙烯酸酯及具有羧基之多官能(甲基)丙烯酸酯、N,N,N,N,N,N-六(烷氧基甲基)三聚氰胺、N,N,N,N-四(烷氧基甲基)苯并鳥糞胺。在3價以上脂肪族聚羥基化合物與(甲基)丙烯酸之酯之中，尤以三丙烯酸三羥甲基丙酯、三丙烯酸新戊四醇酯、五丙烯酸二新戊四醇酯、六丙烯酸二新戊四醇酯；而在具有羧基之多官能(甲基)丙烯酸酯中，尤以使三丙烯酸新戊四醇酯與琥珀酸酐反應所得化合物、使五丙烯酸二新戊四醇酯與琥珀酸酐反應所得化合物，就著色層之強度高、著色層之表面平滑性優異，且未曝光部之基板上及遮光層上表面污斑、膜殘留等難以發生之觀點為特佳。Among these polyfunctional monomers, a trivalent or higher aliphatic polyhydroxy compound and an ester of (meth)acrylic acid, a caprolactone-modified polyfunctional (meth)acrylate, and a polyfunctional amine group are preferable. Acid ester (meth) acrylate and polyfunctional (meth) acrylate having carboxyl group, N, N, N, N, N, N-hexa(alkoxymethyl) melamine, N, N, N, N - Tetrakis(alkoxymethyl)benzoguanamine. Among the trivalent or higher aliphatic polyhydroxy compounds and (meth)acrylic acid esters, especially trimethylolpropyl triacrylate, neopentyl glycol triacrylate, dipentaerythritol pentaacrylate, hexaacrylic acid Dipentaerythritol ester; and in a polyfunctional (meth) acrylate having a carboxyl group, in particular, a compound obtained by reacting neopentyl glycol triacrylate with succinic anhydride, diam pentaerythritol pentaacrylate and amber The compound obtained by the acid anhydride reaction is excellent in the strength of the colored layer and the surface smoothness of the colored layer, and it is particularly preferable that the surface of the unexposed portion and the surface of the light-shielding layer are less likely to be stained or left.

本發明中(C)多官能性單體可單獨使用，或混合二種以上使用。In the present invention, the (C) polyfunctional monomer may be used singly or in combination of two or more.

本發明中相對於(B)黏合劑樹脂100質量份，(C)多官能性單體之含量較佳為5至500質量份，特佳為20至300質量份。在該情形，多官能性單體之含量過少時，會有無法獲得充分硬化性之虞。另一方面，多官能性單體之含量過多時，在本發明之著色組成物中提供鹼顯影性之情形，會有鹼顯影性降低、未曝光部之基板上或者遮光層上易於發生表面污斑、膜殘留等之傾向。In the present invention, the content of the (C) polyfunctional monomer is preferably from 5 to 500 parts by mass, particularly preferably from 20 to 300 parts by mass, per 100 parts by mass of the (B) binder resin. In this case, when the content of the polyfunctional monomer is too small, sufficient curability may not be obtained. On the other hand, when the content of the polyfunctional monomer is too large, the alkali developability is provided in the coloring composition of the present invention, and the alkali developability is lowered, and the surface of the unexposed portion or the light shielding layer is liable to be surface-stained. The tendency of spots, membrane residues, etc.

-倍半矽氧烷(D)-- sesquioxane (D)-

本發明之著色組成物，其特徵在於倍半矽氧烷(D)，亦即其係含有具有選自由磺醯基及聚合性不飽和基所構成群組中之至少一種的籠型倍半矽氧烷。習知的磺醯基(-SH)係以自由基或陽離子方式加成於乙烯性不飽和鍵，不過本發明人等係首先發現使具有立體規則性之倍半矽氧烷構造經由磺基或聚合性不飽和基，組入於上述(C)多官能性單體等之交聯構造，即顯現極其優異的與無機膜之密合性或耐溶劑性。The coloring composition of the present invention is characterized by a sesquiterpene oxide (D), that is, a cage type sesquiterpene having at least one selected from the group consisting of a sulfonyl group and a polymerizable unsaturated group. Oxytomane. The conventional sulfonyl group (-SH) is added to the ethylenically unsaturated bond by radical or cationic means, but the inventors first discovered that the sesquioxane structure having stereoregularity is via a sulfo group or The polymerizable unsaturated group is incorporated in the crosslinked structure of the above (C) polyfunctional monomer or the like, that is, it exhibits an extremely excellent adhesion to an inorganic film or solvent resistance.

本發明中，倍半矽氧烷(D)係包含下述式(D-1)至(D-4)所示完全籠型之倍半矽氧烷，同時亦包含下述式(D-5)至(D-6)所示籠的一部分為開口的不完全的籠型之倍半矽氧烷在內之概念。In the present invention, the sesquiterpene oxide (D) comprises a completely caged sesquiterpene oxide represented by the following formulas (D-1) to (D-4), and also contains the following formula (D-5). Part of the cage shown to (D-6) is the concept of an incomplete cage sesquioxane.

(上述式中，R係互為獨立地表示1價有機基，但，全部之R中至少二個係具有選自由磺醯基及聚合性不飽和基所構成群組中之至少一種之基)。(In the above formula, R is a monovalent organic group independently of each other, and at least two of all R have a group selected from at least one of a group consisting of a sulfonyl group and a polymerizable unsaturated group) .

上述式中，具有磺醯基之基方面，並無特別限定，較佳為具有磺醯基之碳數1至8之烴基，特佳為具有磺醯基之碳數1至8之烷基，其具體例方面，可例舉氫硫基甲基、2-氫硫基乙基、3-氫硫基丙基、1,4-二氫硫基-2-丁基、1,2-二氫硫基乙基、2-氫硫基甲基-3-氫硫基丙基等，不過特佳為3-氫硫基丙基。In the above formula, the group having a sulfonyl group is not particularly limited, and is preferably a hydrocarbon group having 1 to 8 carbon atoms having a sulfonyl group, particularly preferably an alkyl group having 1 to 8 carbon atoms having a sulfonyl group. Specific examples thereof include a thiomethyl group, a 2-hydrothioethyl group, a 3-hydrothiopropyl group, a 1,4-dihydrothio-2-butyl group, and a 1,2-dihydro group. Thioethyl, 2-hydrothiomethyl-3-hydrothiopropyl, etc., but particularly preferably 3-hydrothiopropyl.

又，上述式中，具有聚合性不飽和基的基方面，並無特別限定，較佳為乙烯基、乙烯芳基、(甲基)丙烯醯氧基烷基、烯丙基基，特佳為(甲基)丙烯醯氧基烷基，其具體例方面，可例舉3-(甲基)丙烯醯氧基丙基、2-(甲基)丙烯醯氧基乙基、(甲基)丙烯醯氧基甲基等。Further, in the above formula, the group having a polymerizable unsaturated group is not particularly limited, and is preferably a vinyl group, a vinyl aryl group, a (meth) acryloxyalkyl group or an allyl group, and particularly preferably (Meth) propylene methoxyalkyl group, and specific examples thereof include 3-(meth) propylene methoxy propyl group, 2-(meth) propylene methoxyethyl group, and (meth) propylene group.醯oxymethyl and the like.

又，上述式中，具有磺醯基等之基以外的1價有機基方面，可例舉例如可具有取代基的碳數1至6之烷基、可具有取代基之碳數6至18之芳基等。In the above formula, the monovalent organic group other than the group having a sulfonyl group or the like may, for example, be an alkyl group having 1 to 6 carbon atoms which may have a substituent, and a carbon number of 6 to 18 which may have a substituent. Aryl and the like.

本發明中，上述碳數1至6之烷基方面，較佳為碳數1至5之烷基，特佳為甲基、乙基、正丙基、異丙基、戊基。又，上述碳數6至18之芳基方面，較佳為碳數6至10之芳基，特佳為苯基。In the present invention, the alkyl group having 1 to 6 carbon atoms is preferably an alkyl group having 1 to 5 carbon atoms, particularly preferably a methyl group, an ethyl group, a n-propyl group, an isopropyl group or a pentyl group. Further, in the above aryl group having 6 to 18 carbon atoms, an aryl group having 6 to 10 carbon atoms is preferable, and a phenyl group is particularly preferable.

上述碳數1至6之烷基之取代基方面，可例舉例如環氧乙基、環氧丙氧基、3,4-環氧環己基、氧雜環丁烷-3-基、氧雜環丁烷-3-基甲基氧基、2,3-環硫基丙基氧基、羧基、羥基、羥苯基羰氧基、異氰酸基、胺基、脲基等。本發明中，碳數1至6之烷基係非取代，或具有環氧乙基、環氧丙氧基、3,4-環氧環己基、氧雜環丁烷-3-基或具有氧雜環丁烷-3-基甲基氧基作為取代基。The substituent of the above alkyl group having 1 to 6 carbon atoms may, for example, be an epoxyethyl group, a glycidoxy group, a 3,4-epoxycyclohexyl group, an oxetan-3-yl group or an oxa group. Cyclobutane-3-ylmethyloxy, 2,3-epoxypropyloxy, carboxy, hydroxy, hydroxyphenylcarbonyloxy, isocyanato, amine, ureido, and the like. In the present invention, the alkyl group having 1 to 6 carbon atoms is unsubstituted or has an epoxy group, a glycidoxy group, a 3,4-epoxycyclohexyl group, an oxetan-3-yl group or an oxygen group. A heterocyclic butan-3-ylmethyloxy group is used as a substituent.

此外，在上述氧雜環丁烷-3-基或氧雜環丁烷-3-基甲基氧基之3位碳亦可取代以甲基、乙基、正丙基等之碳數1至6之烷基。Further, the carbon at the 3-position of the above oxetane-3-yl or oxetane-3-ylmethyloxy group may be substituted with a carbon number of methyl, ethyl, n-propyl or the like to 1 6 alkyl.

又，上述碳數6至18之芳基之取代基方面，可例舉例如鹵素原子、羥基、氰基、硝基或碳數1至6之烷基等。Further, the substituent of the aryl group having 6 to 18 carbon atoms may, for example, be a halogen atom, a hydroxyl group, a cyano group, a nitro group or an alkyl group having 1 to 6 carbon atoms.

倍半矽氧烷(D)，係例如藉由將含有下述式所示之化合物(以下稱為「化合物(d1)」)之矽烷化合物在鹼性觸媒存在下，予以水解來製造。The sesquiterpene oxide (D) is produced, for example, by hydrolyzing a decane compound containing a compound represented by the following formula (hereinafter referred to as "compound (d1)") in the presence of a basic catalyst.

RSiX3 　(d1)RSiX 3 (d1)

(上述式中，R表示具有磺醯基或聚合性不飽和基的基，X表示水解性基)(In the above formula, R represents a group having a sulfonyl group or a polymerizable unsaturated group, and X represents a hydrolyzable group)

上述式中X方面，只要是水解性基則並無特別限定，可例舉例如烷氧基、環烷氧基、芳氧基、醯氧基、鹵素原子、氫原子等。該等中，由反應性之點，較佳為烷氧基、環烷氧基、芳氧基、醯氧基，再佳為甲氧基、乙氧基、正丙氧基、異丙氧基、正丁基、異丁基、三級丁基、環己氧基、苯氧基、乙醯氧基，特佳為甲氧基、乙氧基。The X in the above formula is not particularly limited as long as it is a hydrolyzable group, and examples thereof include an alkoxy group, a cycloalkoxy group, an aryloxy group, a decyloxy group, a halogen atom, and a hydrogen atom. Among these, from the viewpoint of reactivity, an alkoxy group, a cycloalkoxy group, an aryloxy group, a decyloxy group, and more preferably a methoxy group, an ethoxy group, a n-propoxy group or an isopropoxy group are preferred. , n-butyl, isobutyl, tert-butyl, cyclohexyloxy, phenoxy, ethoxylated, particularly preferably methoxy, ethoxy.

此外，X在上述式中，亦可為全部相同之基、亦可為2種以上不同的基。Further, X may be all the same groups or two or more different groups in the above formula.

化合物(d1)之適當具體例方面，可例舉3-氫硫基丙基三甲氧基矽烷、3-氫硫基丙基三乙氧基矽烷、3-氫硫基丙基三丙氧基矽烷、3-氫硫基丙基三丁氧基矽烷、1,4-二氫硫基-2-(三甲氧基矽烷基)丁烷、1,4-二氫硫基-2-(三乙氧基矽烷基)丁烷、1,4-二氫硫基-2-(三丙氧基矽烷基)丁烷、1,4-二氫硫基-2-(三丁氧基矽烷基)丁烷、2-氫硫基甲基-3-氫硫基丙基三三甲氧基矽烷、2-氫硫基甲基-3-氫硫基丙基三乙氧基矽烷、2-氫硫基甲基-3-氫硫基丙基三丙氧基矽烷、2-氫硫基甲基-3-氫硫基丙基三丁氧基矽烷、1,2-二氫硫基乙基三甲氧基矽烷、1,2-二氫硫基乙基三三乙氧基矽烷、1,2-二氫硫基乙基三丙氧基矽烷、1,2-二氫硫基乙基三丁氧基矽烷、乙烯三甲氧基矽烷、乙烯三乙氧基矽烷、(甲基)丙烯醯氧基甲基三甲氧基矽烷、(甲基)丙烯醯氧基甲基三乙氧基矽烷、2-(甲基)丙烯醯氧基乙基三甲氧基矽烷、2-(甲基)丙烯醯氧基乙基三乙氧基矽烷、3-(甲基)丙烯醯氧基丙基三甲氧基矽烷、3-(甲基)丙烯醯氧基丙基三乙氧基矽烷、對乙烯苯基三甲氧基矽烷、對乙烯苯基三乙氧基矽烷等。Specific examples of the compound (d1) include 3-hydrothiopropyltrimethoxydecane, 3-hydrothiopropyltriethoxydecane, and 3-hydrothiopropyltripropoxydecane. , 3-hydrothiopropyl tributoxy decane, 1,4-dihydrothio-2-(trimethoxydecyl)butane, 1,4-dihydrothio-2-(triethoxy) Base alkyl)butane, 1,4-dihydrothio-2-(tripropoxydecyl)butane, 1,4-dihydrothio-2-(tributyloxydecane)butane 2-Hydroxythiomethyl-3-hydrothiopropyltritrimethoxydecane, 2-hydrothiomethyl-3-hydrothiopropyltriethoxydecane, 2-hydrothiomethyl 3-Benzylthiopropyltripropoxydecane, 2-hydrothiomethyl-3-hydrothiopropyltributoxydecane, 1,2-dihydrothioethyltrimethoxydecane 1,2-dihydrothioethyltritriethoxydecane, 1,2-dihydrothioethyltripropoxydecane, 1,2-dihydrothioethyltributoxydecane, Ethylene trimethoxy decane, ethylene triethoxy decane, (meth) propylene methoxymethyl trimethoxy decane, (meth) propylene methoxymethyl triethoxy decane, 2- (methyl) Acryloxyethyltrimethyl Base decane, 2-(meth) propylene methoxyethyl triethoxy decane, 3-(methyl) propylene methoxy propyl trimethoxy decane, 3-(methyl) propylene methoxy propyl Triethoxy decane, p-vinyl phenyl trimethoxy decane, p-vinyl phenyl triethoxy decane, and the like.

倍半矽氧烷(D)可為上述化合物(d1)之水解縮合物，亦可為上述化合物(d1)與下述式所示矽烷化合物(以下稱為「化合物(d2)」)之水解縮合物。The sesquioxane (D) may be a hydrolysis condensate of the above compound (d1), or may be a hydrolysis condensation of the above compound (d1) with a decane compound of the following formula (hereinafter referred to as "compound (d2)"). Things.

R1 SiX1 3 　(d2)R 1 SiX 1 3 (d2)

(上述式中，R1 表示可具有取代基之碳數1至6之烷基或可具有取代基之碳數6至18之芳基、X1 表示水解性基)(In the above formula, R 1 represents an alkyl group having 1 to 6 carbon atoms which may have a substituent or an aryl group having 6 to 18 carbon atoms which may have a substituent, and X 1 represents a hydrolyzable group)

化合物(d2)之適當具體例方面，可例舉甲基三甲氧基矽烷、甲基三乙氧基矽烷、乙基三甲氧基矽烷、乙基三乙氧基矽烷、苯基三甲氧基矽烷、苯基三乙氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基三乙氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、2-(3,4-環氧環己基)乙基三乙氧基矽烷、3-(3’-乙基氧雜環丁烷-3’-基)丙基三甲氧基矽烷、3-(3’-乙基氧雜環丁烷-3’-基)丙基三乙氧基矽烷、(3-乙基氧雜環丁烷-3-基甲基氧)丙基三甲氧基矽烷、(3-乙基氧雜環丁烷-3-基甲基氧)丙基三乙氧基矽烷等。Specific examples of the compound (d2) include methyltrimethoxydecane, methyltriethoxydecane, ethyltrimethoxydecane, ethyltriethoxydecane, and phenyltrimethoxydecane. Phenyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, 2-(3,4-epoxycyclohexyl)B Trimethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltriethoxy decane, 3-(3'-ethyloxetane-3'-yl)propyltrimethoxy Decane, 3-(3'-ethyloxetane-3'-yl)propyltriethoxydecane, (3-ethyloxetan-3-ylmethyloxy)propyltrimethyl Oxydecane, (3-ethyloxetan-3-ylmethyloxy)propyltriethoxydecane, and the like.

倍半矽氧烷(D)中，由化合物(d1)所衍生之構成單位之含有率，根據化合物(d1)及(d2)所衍生之重複單位之合計，通常為5至100重量%，較佳為10至100重量%，特佳為20至100重量%。藉由使由化合物(d1)所衍生構成單位之含有率設定於上述範圍，即可形成與無機膜之密合性、耐溶劑性、電特性優異的著色層。In the sesquioxane (D), the content of the constituent unit derived from the compound (d1) is usually from 5 to 100% by weight based on the total of the repeating units derived from the compounds (d1) and (d2). It is preferably from 10 to 100% by weight, particularly preferably from 20 to 100% by weight. By setting the content ratio of the constituent unit derived from the compound (d1) to the above range, a coloring layer excellent in adhesion to an inorganic film, solvent resistance, and electrical properties can be obtained.

就由化合物(d1)等來製造倍半矽氧烷(D)之更具體方法，可以日本特開平11-29640號公報、日本特開2004-143449號公報等作為參考。A more specific method for producing sesquiterpene oxide (D) from the compound (d1) or the like can be referred to JP-A-11-29640, JP-A-2004-143449, and the like.

倍半矽氧烷(D)之Mw，通常為300至50,000，較佳為500至30,000。Mw過小時，會有損及本發明所期望效果之虞，另一方面，過大時，則會有使塗布性或著色劑之分散性惡化之虞。The Mw of the sesquioxane (D) is usually from 300 to 50,000, preferably from 500 to 30,000. When the Mw is too small, the effect of the present invention may be impaired. On the other hand, when it is too large, the coating property or the dispersibility of the colorant may be deteriorated.

本發明中，倍半矽氧烷(D)之含量，相對於(C)多官能性單體100質量份，較佳為1至50質量份，更佳為2至30質量份。在該情形，倍半矽氧烷(D)之含量過少時，會有損及本發明所期望效果之虞，另一方面過多時，會有與其他成分之互溶性降低，或鹼顯影性降低，且易於發生未曝光部之基板上或者遮光層上之表面污斑、膜殘留等之傾向。In the present invention, the content of the sesquiterpene oxide (D) is preferably from 1 to 50 parts by mass, more preferably from 2 to 30 parts by mass, per 100 parts by mass of the (C) polyfunctional monomer. In this case, when the content of the sesquiterpene oxide (D) is too small, the desired effect of the present invention may be impaired, and when it is too large, the miscibility with other components may be lowered or the alkali developability may be lowered. Moreover, there is a tendency that surface stains, film residues, and the like on the substrate of the unexposed portion or on the light shielding layer are likely to occur.

-(E)光聚合引發劑--(E) Photopolymerization Initiator -

在本發明之著色組成物，藉由使之含有光聚合引發劑，而可對著色組成物提供感放射線性。在此所謂「放射線」，係含有可視光線、紫外線、遠紫外線、電子束、X線等之意。In the colored composition of the present invention, by providing a photopolymerization initiator, the coloring composition can be provided with a radiation sensitivity. Here, "radiation" means visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, and the like.

本發明中(E)光聚合引發劑，係藉由可視光線、紫外線、遠紫外線、電子束、X線等放射線之曝光，而可開始上述(C)多官能性單體及視情形所使用的單官能性單體之聚合而得之活性物種，並使活性物種產生的化合物。In the (E) photopolymerization initiator of the present invention, the above-mentioned (C) polyfunctional monomer and, as the case may be, may be used by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, or X-ray. A compound obtained by polymerization of a monofunctional monomer to give an active species and a compound produced by the active species.

此種光聚合引發劑方面，可例舉例如乙醯苯系化合物、聯咪唑系化合物、三系化合物、O-醯基肟系化合物、鎓鹽系化合物、安息香系化合物、二苯酮系化合物、α-二酮系化合物、多核醌系化合物、酮系化合物、二重氮系化合物、醯亞胺磺酸根基系化合物等。Examples of such a photopolymerization initiator include an acetophenone-based compound, a biimidazole-based compound, and the like. a compound, an O-mercapto oxime compound, a guanidine salt compound, a benzoin compound, a benzophenone compound, an α-diketone compound, a polynuclear ruthenium compound, A ketone compound, a disazo compound, a quinone sulfonate compound, or the like.

本發明中，光聚合引發劑可單獨使用，或混合二種以上使用。光聚合引發劑方面，較佳為選自噻噸酮系化合物、乙醯苯系化合物、聯咪唑系化合物、三系化合物、O-醯基肟系化合物之群組中至少一種，要提高本發明所期望之效果，就得使O-醯基肟系化合物，在全光聚合引發劑中，較佳為含有50質量%以上，再佳為含有75質量%以上。In the present invention, the photopolymerization initiator may be used singly or in combination of two or more. The photopolymerization initiator is preferably selected from the group consisting of a thioxanthone compound, an acetophenone compound, a biimidazole compound, and three. At least one of the group of the compound and the O-mercapto lanthanide compound, in order to enhance the desired effect of the present invention, the O-mercapto lanthanide compound preferably contains 50% of the all-photopolymerization initiator. More preferably, the mass is more than 75% by mass.

上述O-醯基肟系化合物，只要具有醯基肟構造(>C=N-O-CO-)的光聚合引發劑，則並無特別限定，可例舉例如國際公開第2002/100903號要約、國際公開第2006/018973號要約、國際公開第2008/078678號要約等記載之化合物。O-醯基肟系化合物之具體例方面可例舉1,2-辛二酮,1-[4-(苯硫基)苯基]-,2-(O-苯甲醯基肟)、乙酮,1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-,1-(O-乙醯基肟)、乙酮,1-[9-乙基-6-(2-甲基-4-四氫呋喃基甲氧基苯甲醯基)-9H-咔唑-3-基]-,1-(O-乙醯基肟)、乙酮,1-[9-乙基-6-{2-甲基-4-(2,2-二甲基-1,3-二氧雜戊環基)甲氧基苯甲醯基}-9H-咔唑-3-基]-,1-(O-乙醯基肟)。本發明中，在O-醯基肟系化合物方面，由可提高所期望效果之點，較佳為具有咔唑構造之化合物。The O-mercapto fluorene-based compound is not particularly limited as long as it has a fluorenyl fluorene structure (>C=NO-CO-), and may be, for example, International Publication No. 2002/100903, International The compounds described in the offer No. 2006/018973, International Publication No. 2008/078678, and the like are disclosed. Specific examples of the O-indenyl lanthanide compound may be exemplified by 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoguanidinopurine), and B. Ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(O-ethylindenyl), ethyl ketone, 1- [9-Ethyl-6-(2-methyl-4-tetrahydrofurylmethoxybenzylidene)-9H-indazol-3-yl]-, 1-(O-ethylindenyl), B Ketone, 1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzylidene]-9H -oxazol-3-yl]-, 1-(O-ethylindenyl). In the present invention, the O-mercapto fluorene-based compound is preferably a compound having a carbazole structure because it can improve the desired effect.

本發明中，O-醯基肟系化合物可單獨使用，或混合二種以上使用。In the present invention, the O-indenyl lanthanide compounds may be used singly or in combination of two or more.

又，上述噻噸酮系化合物之具體例方面，可例舉噻噸酮、2-氯噻噸酮、2-甲基噻噸酮、2-異丙基噻噸酮、4-異丙基噻噸酮、2,4-二氯噻噸酮、2,4-二甲基噻噸酮、2,4-二乙基噻噸酮、2,4-二異丙基噻噸酮等。Further, specific examples of the above thioxanthone-based compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and 4-isopropylthiophene. Tons of ketone, 2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and the like.

又，上述乙醯苯系化合物之具體例方面，可例舉2-甲基-1-[4-(甲硫基)苯基]-2-啉丙烷-1-酮、2-苄基-2-二甲基胺基-1-(4-啉苯基)丁烷-1-酮、2-(4-甲基苄基)-2-(二甲基胺基)-1-(4-啉苯基)丁烷-1-酮、1-羥基-環己基苯基酮等。Further, specific examples of the above acetophenone-based compound include 2-methyl-1-[4-(methylthio)phenyl]-2- Tropicpropan-1-one, 2-benzyl-2-dimethylamino-1-(4- Phenylphenyl)butan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4- Phenylphenyl)butan-1-one, 1-hydroxy-cyclohexyl phenyl ketone, and the like.

又，上述聯咪唑系化合物之具體例方面，可例舉2,2’-雙(2-氯苯基)-4,4’,5,5’-四苯基-1,2’-聯咪唑、2,2’-雙(2,4-二氯苯基)-4,4’,5,5’-四苯基-1,2’-聯咪唑、2,2’-雙(2,4,6-三氯苯基)-4,4’,5,5’-四苯基-1,2’-聯咪唑等。Further, specific examples of the biimidazole-based compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole. , 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4 , 6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, and the like.

此外，在使用聯咪唑系化合物作為光聚合引發劑之情形，以併用氫供予體者，由改良感度之觀點較佳。在此所謂「氫供予體」係指相對於以曝光而自聯咪唑系化合物發生的自由基，供予氫原子的化合物之意。氫供予體方面，可例舉例如2-氫硫基苯并噻唑、2-氫硫基苯并唑等之硫醇系氫供予體、4,4’-雙(二甲基胺基)二苯酮、4,4’-雙(二乙基胺基)二苯酮等之胺系氫供予體。本發明中，氫供予體可單獨使用，或混合二種以上使用，不過亦可組合一種以上硫醇系氫供予體與一種以上胺系氫供予體來使用，再者，從改良感度之觀點較佳。Further, in the case of using a biimidazole-based compound as a photopolymerization initiator, it is preferred from the viewpoint of improving sensitivity in order to use a hydrogen donor in combination. The term "hydrogen donor" as used herein means a compound which supplies a hydrogen atom with respect to a radical generated from a biimidazole compound by exposure. The hydrogen donor may, for example, be 2-hydrothiobenzothiazole or 2-hydrothiobenzophenone. A thiol-based hydrogen donor such as oxazole, an amine-based hydrogen supply such as 4,4'-bis(dimethylamino)benzophenone or 4,4'-bis(diethylamino)benzophenone Subject. In the present invention, the hydrogen donor may be used singly or in combination of two or more kinds, but one or more thiol-based hydrogen donors and one or more amine-based hydrogen donors may be used in combination, and further, from the improved sensitivity The viewpoint is better.

又，上述三系化合物之具體例方面，可例舉2,4,6-參(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)伸乙基]-4,6-雙(三氯甲基)-s-三、2-[2-(呋喃-2-基)伸乙基]-4,6-雙(三氯甲基)-s-三、2-[2-(4-二乙基胺基-2-甲基苯基)伸乙基]-4,6-雙(三氯甲基)-s-三、2-[2-(3,4-二甲氧基苯基)伸乙基]-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)-4,6-雙(三氯甲基)-s-三、2-(4-正丁氧基苯基)-4,6-雙(三氯甲基)-s-三等之具有鹵甲基的三系化合物。Again, the above three Specific examples of the compound can be exemplified by 2,4,6-para(trichloromethyl)-s-three. 2-methyl-4,6-bis(trichloromethyl)-s-three ,2-[2-(5-methylfuran-2-yl)extended ethyl]-4,6-bis(trichloromethyl)-s-three ,2-[2-(furan-2-yl)extended ethyl]-4,6-bis(trichloromethyl)-s-three 2-[2-(4-Diethylamino-2-methylphenyl)-extended ethyl]-4,6-bis(trichloromethyl)-s-three ,2-[2-(3,4-dimethoxyphenyl)extended ethyl]-4,6-bis(trichloromethyl)-s-three , 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-three , 2-(4-ethoxystyrene)-4,6-bis(trichloromethyl)-s-three ,2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-three Three of the halomethyl groups a compound.

本發明中，在使用乙醯苯系化合物等之聯咪唑系化合物以外光聚合引發劑之情形，可併用增感劑。此種增感劑方面，可例舉例如4,4’-雙(二甲基胺基)二苯酮、4,4’-雙(二乙基胺基)二苯酮、4-二乙基胺基乙醯苯、4-二甲基胺基丙醯苯、4-二甲基胺基苯甲酸乙酯、4-二甲基胺基苯甲酸2-乙基己酯、2,5-雙(4-二乙基胺基苯亞甲基)環己酮、7-二乙基胺基-3-(4-二乙基胺基苯甲醯基)香豆素、4-(二乙基胺基)查耳酮等。In the present invention, in the case of using a photopolymerization initiator other than the biimidazole compound such as an acetophenone-based compound, a sensitizer may be used in combination. As such a sensitizer, for example, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4-diethyl group can be exemplified. Aminoethyl benzene, 4-dimethylamino propyl benzene, ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-double (4-Diethylaminobenzylidene)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzimidyl)coumarin, 4-(diethyl Amino) chalcone and the like.

本發明中，相對於(C)多官能性單體100質量份，光聚合引發劑之含量較佳為0.01至120質量份，特佳為1至100質量份。在該情形，光聚合引發劑之含量過少時，會有曝光所致硬化不充分之虞，另一方面過多時，則所形成之著色層在顯影時會有自基板易於脫落的傾向。In the present invention, the content of the photopolymerization initiator is preferably from 0.01 to 120 parts by mass, particularly preferably from 1 to 100 parts by mass, per 100 parts by mass of the (C) polyfunctional monomer. In this case, when the content of the photopolymerization initiator is too small, the curing due to exposure may be insufficient. On the other hand, when the amount is too large, the colored layer formed tends to fall off from the substrate during development.

-(F)熱聚合引發劑--(F) Thermal polymerization initiator -

本發明中，藉由在著色組成物中含有(F)熱聚合引發劑，而可提高著色層與無機膜之密合性或耐溶劑性。熱聚合引發劑方面，可例舉例如偶氮系化合物、有機過氧化物、過氧化氫等。該等中，較佳為偶氮系化合物。In the present invention, by containing (F) a thermal polymerization initiator in the colored composition, the adhesion between the colored layer and the inorganic film or the solvent resistance can be improved. The thermal polymerization initiator may, for example, be an azo compound, an organic peroxide or hydrogen peroxide. Among these, an azo compound is preferred.

上述偶氮系化合物方面，較佳為2,2’-偶氮雙異丁腈、2,2’-偶氮雙(2-甲基丁腈)、1,1’-偶氮雙(環己烯-1-1-腈(carbonitrile))、2,2’-偶氮雙(2,4-二甲基戊腈)、1-[(1-氰基-1-甲基乙基)偶氮]甲醯胺(2-(胺甲醯基偶氮)異丁腈)、2,2-偶氮雙{2-甲基-N-[1,1-雙(羥甲基)-2-羥乙基]丙醯胺}、2,2’-偶氮雙[N-(2-丙烯基)-2-甲基丙醯胺]、2,2’-偶氮雙[N-(2-丙烯基)-2-乙基丙醯胺]、2,2’-偶氮雙[N-丁基-2-甲基丙醯胺]、2,2’-偶氮雙(N-環己基-2-甲基丙醯胺)、2,2’-偶氮雙(二甲基-2-甲基丙醯胺)、2,2’-偶氮雙(二甲基-2-甲基丙酸酯)、2,2’-偶氮雙(2,4,4-三甲基戊烯)等，該等中，較佳為2,2’-偶氮雙異丁腈、2,2’-偶氮雙(2,4-二甲基戊腈)。In terms of the above azo compound, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis (cyclohexane) are preferred. Benzene-1-carbonitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 1-[(1-cyano-1-methylethyl)azo Methionamine (2-(aminomercaptoazo)isobutyronitrile), 2,2-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyl Ethyl]propanolamine}, 2,2'-azobis[N-(2-propenyl)-2-methylpropionamide], 2,2'-azobis[N-(2-propene) 2-ethylpropionamide], 2,2'-azobis[N-butyl-2-methylpropionamide], 2,2'-azobis(N-cyclohexyl-2 -methylpropanamide), 2,2'-azobis(dimethyl-2-methylpropanamide), 2,2'-azobis(dimethyl-2-methylpropionate , 2,2'-azobis(2,4,4-trimethylpentene), etc., among these, preferably 2,2'-azobisisobutyronitrile, 2,2'-even Nitrogen bis(2,4-dimethylvaleronitrile).

本發明中，熱聚合引發劑之含量，相對於(C)多官能性單體100質量份，較佳為0.1至10質量份、更佳為1至5質量份。In the present invention, the content of the thermal polymerization initiator is preferably 0.1 to 10 parts by mass, more preferably 1 to 5 parts by mass, per 100 parts by mass of the (C) polyfunctional monomer.

-添加劑--additive-

本發明之著色組成物，可依照需要進一步含有其他添加劑。The colored composition of the present invention may further contain other additives as needed.

上述其他添加劑方面，有例如玻璃、氧化鋁等之填充劑；聚乙烯醇、聚(氟烷基丙烯酸酯)類等之高分子化合物；非離子系界面活性劑、陽離子系界面活性劑、陰離子系界面活性劑等界面活性劑；乙烯三甲氧基矽烷、乙烯三乙氧基矽烷、乙烯參(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-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基甲基二甲氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-氯丙基甲基二甲氧基矽烷、3-氯丙基三甲氧基矽烷、3-甲基丙烯醯氧丙基三甲氧基矽烷、3-氫硫基丙基三甲氧基矽烷等之密合促進劑；2,2-硫基雙(4-甲基-6-三級丁酚)、2,6-二-三級丁基酚等之抗氧化劑；2-(3-三級丁基-5-甲基-2-羥基苯基)-5-氯苯并***、烷氧基二苯酮類等之紫外線吸收劑；聚丙烯酸鈉等之抗凝聚劑；丙二酸、己二酸、伊康酸、檸康酸、反丁烯二酸、中康酸、2-胺基乙醇、3-胺基-1-丙醇、5-胺基-1-戊醇、3-胺基-1,2-丙二醇、2-胺基-1,3-丙二醇、4-胺基-1,2-丁二醇等之殘渣改善劑；琥珀酸單[2-(甲基)丙烯醯氧乙基]酯、酞酸單[2-(甲基)丙烯醯氧乙基]酯、ω-羧基聚己內酯單(甲基)丙烯酸酯等之顯影性改善劑等。Examples of the other additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly(fluoroalkyl acrylate); nonionic surfactants, cationic surfactants, and anionic systems; Surfactant such as surfactant; ethylene trimethoxy decane, ethylene triethoxy decane, ethylene ginseng (2-methoxyethoxy) decane, N-(2-aminoethyl)-3-amino Propylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropane Propyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyl An adhesion promoter such as dimethoxy decane, 3-chloropropyltrimethoxy decane, 3-methyl propylene oxypropyl trimethoxy decane, 3-hydrothiopropyltrimethoxy decane; , an antioxidant such as 2-thiobis(4-methyl-6-tertiary butyl phenol) or 2,6-di-tertiary butyl phenol; 2-(3-tertiary butyl-5-methyl UV of -2-hydroxyphenyl)-5-chlorobenzotriazole, alkoxybenzophenone, etc. Absorbent; anti-agglomerating agent such as sodium polyacrylate; malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1 -propanol, 5-amino-1-pentanol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, etc. Residue improver; succinic acid mono [2-(methyl) propylene oxiranyl] ester, citric acid mono [2-(methyl) propylene oxiranyl] ester, ω-carboxy polycaprolactone single (A A developer improving agent such as acrylate or the like.

-溶劑-- solvent -

本發明之著色組成物係以上述(A)至(D)成分作為必須成分，可依照需要含有上述添加劑成分，不過通常係調配溶劑，並調製作為液狀組成物。In the coloring composition of the present invention, the above-mentioned components (A) to (D) are essential components, and the above-mentioned additive component may be contained as necessary, but usually, a solvent is prepared and prepared as a liquid component.

該溶劑方面，係將構成感放射線性組成物的(A)至(D)成分或添加劑成分予以分散或溶解，且只要不與該等成分反應，並具有適度之揮發性之物就可適宜地選擇使用。In terms of the solvent, the components (A) to (D) or the additive component constituting the radiation sensitive composition are dispersed or dissolved, and as long as they do not react with the components and have moderate volatility, they are suitably used. Choose to use.

此種溶劑方面，可例舉例如：乙二醇單甲醚、乙二醇單***、乙二醇單-正丙醚、乙二醇單-正丁醚、二乙二醇單甲醚、二乙二醇單***、二乙二醇單-正丙醚、二乙二醇單-正丁醚、三乙二醇單甲醚、三乙二醇單***、丙二醇單甲醚、丙二醇單***、丙二醇單-正丙醚、丙二醇單-正丁醚、二丙二醇單甲醚、二丙二醇單***、二丙二醇單-正丙醚、二丙二醇單-正丁醚、三丙二醇單甲醚、三丙二醇單***等之(聚)伸烷二醇單烷醚類；乙二醇單甲醚乙酸酯、乙二醇單***乙酸酯、二乙二醇單甲醚乙酸酯、二乙二醇單***乙酸酯、丙二醇單甲醚乙酸酯、丙二醇單***乙酸酯、乙酸3-甲氧基丁酯、乙酸3-甲基-3-甲氧基丁酯等之(聚)伸烷二醇單烷醚乙酸酯類；二乙二醇二甲醚、二乙二醇甲***、二乙二醇二***、四氫呋喃等其他醚類；甲乙酮、環己酮、2-庚酮、3-庚酮等之酮類；二乙酸丙二醇酯、二乙酸1,3-伸丁二醇酯、二乙酸1,6-己烷二醇酯等二乙酸酯類；乳酸甲酯、乳酸乙酯等之乳酸烷酯類；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-甲基丁烷酸甲酯、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、乙醯乙酸甲酯、乙醯乙酸乙酯、2-側氧丁酸乙酯等之其他酯類；甲苯、二甲苯等之芳香族烴類；N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基吡咯啶酮等之醯胺或內醯胺類等。Examples of such a solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, and Ethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, Propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol single (poly)alkylene glycol monoalkyl ethers such as diethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol single Ethyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, etc. Alcohol monoalkyl ether acetates; diethylene glycol dimethyl ether, diethylene glycol methyl ether, diethylene glycol diethyl ether, tetrahydrofuran and other ethers; methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-glycol ketone a ketone; a diacetate such as propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate; an alkyl lactate such as methyl lactate or ethyl lactate; Ethyl 2-hydroxy-2-methylpropanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxyl Ethyl propionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl propionate, 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, butyric acid Other esters of propyl ester, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate, ethyl 2-oxobutanoate, etc. An aromatic hydrocarbon such as toluene or xylene; a decylamine or an indoleamine such as N,N-dimethylformamide, N,N-dimethylacetamide or N-methylpyrrolidone; Wait.

該等溶劑中，由溶解性、顔料分散性、塗布性等觀點，較佳為丙二醇單甲醚、乙二醇單甲醚乙酸酯、丙二醇單甲醚乙酸酯、丙二醇單***乙酸酯、乙酸3-甲氧基丁酯、二乙二醇二甲醚、二乙二醇甲***、環己酮、2-庚酮、3-庚酮、二乙酸1,3-伸丁二醇酯、二乙酸1,6-己二醇酯、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。Among these solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate are preferred from the viewpoints of solubility, pigment dispersibility, and coating properties. , 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butylene glycol diacetate 1,6-hexanediol diacetate, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propionic acid 3- Methyl-3-methoxybutyl ester, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, isopropyl butyrate, butyric acid N-butyl ester, ethyl pyruvate, and the like.

該溶劑可單獨使用，或混合二種以上使用。These solvents may be used singly or in combination of two or more.

又，與該溶劑一起，可併用苄基***、二-正己醚、丙酮基丙酮、異佛爾酮、己酸、辛酸、1-辛醇、1-壬醇、苄醇、乙酸苄酯、苯甲酸乙酯、草酸二乙酯、順丁烯二酸二乙酯、γ-丁內酯、碳酸乙烯酯、碳酸丙烯酯、乙二醇單苯醚乙酸酯等之高沸點溶劑。Further, together with the solvent, benzyl ether, di-n-hexyl ether, acetone acetone, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, benzene may be used in combination. A high boiling point solvent such as ethyl formate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate or ethylene glycol monophenyl ether acetate.

該等高沸點溶劑可單獨使用，或混合二種以上使用。These high boiling point solvents may be used singly or in combination of two or more.

溶劑之含量，並無特別限定，由所得感放射線性組成物之塗布性、穩定性等之觀點，除去該組成物之溶劑的各成分之合計濃度，通常為5至50重量%，較佳為10至40重量%。The content of the solvent is not particularly limited, and the total concentration of each component of the solvent in which the composition is removed is usually from 5 to 50% by weight, preferably from 5 to 50% by weight, based on the coatability and stability of the obtained radiation sensitive composition. 10 to 40% by weight.

彩色濾光片Color filter

本發明之彩色濾光片，係具有使用本發明之著色組成物所形成之著色層之物。The color filter of the present invention has a coloring layer formed using the colored composition of the present invention.

在製造彩色濾光片之方法，第一可例舉其次之方法。首先，在基板之表面上，可依照需要形成遮光層(黑色矩陣)，以將形成像素的部分加以劃分。接著，在該基板上，例如塗布分散有紅色之著色劑的本發明之著色感放射線性組成物之液狀組成物後，進行預烘烤，使溶劑蒸發，並形成塗膜。接著，在該塗膜，經由光罩予以曝光後，使用鹼顯影液予以顯影，將塗膜之未曝光部予以溶解除去。其後，藉由事後烘烤，來形成像素陣列，其係使紅色像素圖案以預定之配列配置。In the method of manufacturing a color filter, the first method can be exemplified. First, on the surface of the substrate, a light shielding layer (black matrix) may be formed as needed to divide the portion where the pixels are formed. Next, on the substrate, for example, a liquid composition of the color-sensing radiation composition of the present invention in which a red coloring agent is dispersed is applied, and then pre-baked to evaporate the solvent to form a coating film. Next, after the coating film was exposed through a photomask, it was developed using an alkali developing solution, and the unexposed portion of the coating film was dissolved and removed. Thereafter, the pixel array is formed by post-baking, which causes the red pixel patterns to be arranged in a predetermined arrangement.

接著，使用分散有綠色或藍色之著色劑的各著色感放射線性組成物之液狀組成物，與上述相同，進行各液狀組成物之塗布、預烘烤、曝光、顯影及後烘烤，將綠色之像素陣列及藍色之像素陣列在同一基板上依順序形成。藉此，可獲得紅色、綠色及藍色三原色之像素陣列被配置於基板上的彩色濾光片。但在本發明中，形成各色之像素之順序，並非限定於上述之物。Next, using the liquid composition of each coloring radiation-releasing composition in which a green or blue coloring agent is dispersed, coating, prebaking, exposure, development, and post-baking of each liquid composition are carried out in the same manner as described above. The green pixel array and the blue pixel array are sequentially formed on the same substrate. Thereby, a color filter in which pixel arrays of three primary colors of red, green, and blue are arranged on the substrate can be obtained. However, in the present invention, the order in which the pixels of the respective colors are formed is not limited to the above.

又，黑色矩陣係將以濺鍍或蒸鍍而成膜的鉻等之金屬薄膜，利用光刻法，藉由製成所期望之圖案而形成，不過可使用分散有黑色之著色劑的著色感放射線性組成物之液狀組成物，與上述像素之形成之情形同樣地形成。Further, the black matrix is formed by forming a desired pattern by photolithography using a metal thin film such as chromium which is formed by sputtering or vapor deposition, but a coloring feeling in which a black coloring agent is dispersed can be used. The liquid composition of the radiation linear composition is formed in the same manner as in the case of forming the above-described pixels.

在形成彩色濾光片時所使用的基板方面，可例舉例如玻璃、矽、聚碳酸酯、聚酯、芳香族聚醯胺、聚醯胺醯亞胺、聚醯亞胺等。Examples of the substrate used in forming the color filter include glass, ruthenium, polycarbonate, polyester, aromatic polyamide, polyamidimide, and polyimine.

又，在該等基板，依照所期望，可預先實施矽烷偶合劑等所致藥品處理、電漿處理、離子電鍍、濺鍍、氣相反應法、真空蒸鍍等適宜之前處理。Further, in these substrates, a suitable pretreatment such as a drug treatment such as a decane coupling agent, a plasma treatment, an ion plating, a sputtering, a gas phase reaction method, or a vacuum vapor deposition may be performed in advance.

在將感放射線性組成物之液狀組成物塗布於基板時，可採用噴灑法、輥塗布法、旋轉塗布法(旋轉塗布法)、狹縫式模塗布法、棒塗布法等適宜之塗布法，特佳為旋轉塗布法、狹縫式模塗布法。When the liquid composition of the radiation sensitive composition is applied to a substrate, a suitable coating method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, or a bar coating method may be employed. Particularly preferred is a spin coating method or a slit mold coating method.

預烘烤，通常係組合減壓乾燥與加熱乾燥來進行。減壓乾燥，通常係進行至達到50至200Pass為止。又，加熱乾燥之條件，通常係於70至110℃，1至10分鐘左右。The prebaking is usually carried out by combining vacuum drying and heat drying. Drying under reduced pressure is usually carried out until it reaches 50 to 200 Pass. Further, the conditions of heat drying are usually from 70 to 110 ° C for about 1 to 10 minutes.

塗布厚度，在乾燥後之膜厚，通常為0.1至10μm，較佳為0.2至8.0μm，特佳為0.2至6.0μm。The coating thickness, the film thickness after drying, is usually from 0.1 to 10 μm, preferably from 0.2 to 8.0 μm, particularly preferably from 0.2 to 6.0 μm.

在形成像素及/或黑色矩陣時所使用之放射線之光源方面，可例舉例如氙燈、鹵素燈、鎢燈、高壓汞燈、超高壓汞燈、金屬鹵素燈、中壓汞燈、低壓汞燈等之燈光源或氬離子雷射、YAG雷射、XeCl準分子雷射、氮雷射等之雷射光源等，不過較佳是波長在190至450nm之範圍的放射線。The light source of the radiation used in forming the pixel and/or the black matrix may, for example, be a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, or a low pressure mercury lamp. Such as a light source or a argon ion laser, a YAG laser, a XeCl excimer laser, a nitrogen laser, etc., but preferably a radiation having a wavelength in the range of 190 to 450 nm.

放射線之曝光量，較佳為10至10,000J/m2 。由本發明之著色感放射線性組成物所形成之著色層即使低於600J/m2 、曝光量，亦具有充分的耐溶劑性。The amount of exposure of the radiation is preferably from 10 to 10,000 J/m 2 . The coloring layer formed of the color-sensing radiation composition of the present invention has sufficient solvent resistance even if it is less than 600 J/m 2 and an exposure amount.

又，該鹼顯影液方面，較佳為例如碳酸鈉、氫氧化鈉、氫氧化鉀、氫氧化四甲銨、膽鹼、1,8-二氮雜二環-[5.4.0]-7-十一烯、1,5-二氮雜二環-[4.3.0]-5-壬烯等之水溶液。Further, as the alkali developer, for example, sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline or 1,8-diazabicyclo-[5.4.0]-7- is preferred. An aqueous solution of undecene, 1,5-diazabicyclo-[4.3.0]-5-nonene or the like.

在該鹼顯影液中，可適量添加例如甲醇、乙醇等之水溶性有機溶劑或界面活性劑等。此外，在鹼顯影後，通常予以水洗。A water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the alkali developer in an appropriate amount. Further, after alkali development, it is usually washed with water.

在顯影處理法方面，可適用沖洗顯影法、噴灑顯影法、浸漬顯影法、浸置式(puddle)(盛液)顯影法等。顯影條件較佳在常溫、5至300秒。In the development processing method, a rinse development method, a spray development method, a immersion development method, a puddle development method, or the like can be applied. The developing conditions are preferably at room temperature for 5 to 300 seconds.

後烘烤之條件，通常在180至280℃、10至60分鐘左右。The post-baking conditions are usually from 180 to 280 ° C for about 10 to 60 minutes.

如此所形成之像素之膜厚，通常為0.5至5.0μm，較佳為1.0至3.0μm。The film thickness of the pixel thus formed is usually 0.5 to 5.0 μm, preferably 1.0 to 3.0 μm.

又，在製造彩色濾光片之第二方法方面，習知是日本特開平7-318723號公報、日本特開2000-310706號公報等所揭示之以噴墨方式獲得各色像素之方法。在該方法中，首先，在基板之表面上，形成兼具遮光功能的隔壁。接著，在所形成之隔壁內，例如藉由噴墨裝置，將分散有紅色著色劑的本發明之著色組成物之液狀組成物排出後，進行預烘烤，使溶劑蒸發。接著，該塗膜可依照需要予以曝光後，藉由後烘烤，予以硬化，並形成紅色之像素圖案。In the second method of producing a color filter, a method of obtaining pixels of each color by an inkjet method disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. In this method, first, a partition wall having a light blocking function is formed on the surface of the substrate. Next, in the formed partition, the liquid composition of the colored composition of the present invention in which the red coloring agent is dispersed is discharged by, for example, an inkjet device, and then prebaked to evaporate the solvent. Then, the coating film can be exposed as needed, and then cured by post-baking to form a red pixel pattern.

接著，使用分散有綠色或藍色之著色劑的各著色組成物之液狀組成物，與上述相同，依順序使綠色之像素圖案及藍色之像素圖案形成於同一基板上。藉此，可獲得使紅色、綠色及藍色之三原色之像素圖案配置於基板上的彩色濾光片。但是，在本發明中，形成各色之像素的順序，並非限定於上述之物。Next, a liquid composition of each coloring composition in which a green or blue coloring agent is dispersed is used, and in the same manner as described above, a green pixel pattern and a blue pixel pattern are sequentially formed on the same substrate. Thereby, a color filter in which pixel patterns of three primary colors of red, green, and blue are disposed on the substrate can be obtained. However, in the present invention, the order in which the pixels of the respective colors are formed is not limited to the above.

此外，上述隔壁不僅遮光功能，由於亦可達成排出於劃分內的各色之著色組成物不致混色之功能，故相較於上述第一之方法所使用之黑色矩陣，膜厚較厚。因此，隔壁通常係使用黑色感放射線性組成物來形成。Further, the partition wall not only has a light-shielding function, but also has a function of not mixing colors of the coloring compositions of the respective colors discharged in the division, so that the film thickness is thicker than that of the black matrix used in the first method. Therefore, the partition walls are usually formed using a black radiation-sensitive linear composition.

形成彩色濾光片時所使用之基板或放射線之光源、又，預烘烤或後烘烤之方法或條件則與上述第一方法相同。如此以噴墨方式所形成像素之膜厚則與隔壁之高度同程度。The method or condition for pre-baking or post-baking of the substrate or the source of radiation used in forming the color filter is the same as the first method described above. The film thickness of the pixel formed by the ink jet method is the same as the height of the partition wall.

在如此所得之彩色濾光片上，可依照需要形成保護膜後，以濺鍍形成透明導電膜。透明導電膜方面，可例舉由氧化錫所組成NESA膜(美國PPG公司之註冊商標)、由氧化銦-氧化錫所組成ITO膜、由氧化銦-氧化鋅所組成IZO膜等。又，保護膜方面，可例舉由熱硬化性樹脂組成物所形成之有機膜、SiNx膜、SiOx膜等之無機膜。On the color filter thus obtained, a protective film can be formed as needed, and a transparent conductive film can be formed by sputtering. The transparent conductive film may, for example, be a NESA film composed of tin oxide (registered trademark of PPG, USA), an ITO film composed of indium oxide-tin oxide, or an IZO film composed of indium oxide-zinc oxide. Further, the protective film may, for example, be an organic film formed of a thermosetting resin composition, an inorganic film such as a SiNx film or an SiOx film.

使用本發明之著色組成物所形成之彩色濾光片，與透明導電膜或者SiNx膜、SiOx膜等之無機膜之密合性優異。The color filter formed using the coloring composition of the present invention is excellent in adhesion to an inorganic film such as a transparent conductive film or a SiNx film or an SiOx film.

本發明之彩色濾光片，在彩色液晶顯示元件、彩色攝像管元件、彩色感測器、有機EL顯示元件、電子紙等極為有用。The color filter of the present invention is extremely useful in a color liquid crystal display element, a color image pickup tube element, a color sensor, an organic EL display element, an electronic paper, or the like.

彩色液晶顯示元件Color liquid crystal display element

本發明之彩色液晶顯示元件係具備本發明之彩色濾光片之物。The color liquid crystal display element of the present invention is provided with the color filter of the present invention.

本發明之彩色液晶顯示元件，係採用適宜之構造。例如，彩色濾光片的構造，可採用形成於與配置有薄膜電晶體(TFT)的驅動用基板不相同的基板上，經由液晶層使驅動用基板與形成了彩色濾光片的基板為相向的構造，再者其構造，亦可採用經由液晶層，使在配置有薄膜電晶體(TFT)的驅動用基板之表面上形成彩色濾光片的基板，與形成透明電極的基板為相向的構造。後者之構造，可使開口率格外地提高，具有可獲得明亮且高精細的液晶顯示元件之優點。The color liquid crystal display element of the present invention is suitably constructed. For example, the structure of the color filter may be formed on a substrate different from the substrate on which the thin film transistor (TFT) is disposed, and the substrate for driving may be opposed to the substrate on which the color filter is formed via the liquid crystal layer. In addition, the structure may be such that a substrate on which a color filter is formed on the surface of a driving substrate on which a thin film transistor (TFT) is disposed via a liquid crystal layer and a substrate having a transparent electrode are opposed to each other. . The latter structure allows the aperture ratio to be exceptionally improved, and has the advantage of obtaining a bright and high-definition liquid crystal display element.

本發明之彩色液晶顯示元件，長期可靠度優異。The color liquid crystal display element of the present invention is excellent in long-term reliability.

[實施例][Examples]

茲例舉實施例，進一步具體說明本發明。但本發明並非受下述實施例所限定。The invention will be further described in detail by way of examples. However, the invention is not limited by the following examples.

著色劑分散液之調製Modulation of colorant dispersion 調製例1Modulation example 1

使用作為(A)著色劑之C.I.色素綠58/C.I.色素黃150=60/40(質量比)混合物15.0質量份、作為分散劑之BYK-LPN21116(BYK公司製)11.2質量份(固體成分濃度40質量%)、作為溶劑之丙二醇單甲醚乙酸酯73.8質量份，以珠磨進行混合‧分散12小時來調製著色劑分散液(A-1)。15.0 parts by mass of a mixture of CI color green 58/CI pigment yellow 150=60/40 (mass ratio) as a coloring agent (A), and 11.2 parts by mass of BYK-LPN21116 (manufactured by BYK) as a dispersing agent (solid content concentration 40) The mass%) and 73.8 parts by mass of propylene glycol monomethyl ether acetate as a solvent were mixed by a bead mill and dispersed for 12 hours to prepare a colorant dispersion (A-1).

調製例2Modulation example 2

使用作為(A)著色劑之C.I.色素綠36/C.I.色素黃150=60/40(質量比)混合物15.0質量份、作為分散劑之BYK-LPN21116(BYK公司製)11.2質量份(固體成分濃度40質量%)、作為溶劑之丙二醇單甲醚乙酸酯73.8質量份，以珠磨進行混合‧分散12小時，來調製著色劑分散液(A-2)。15.0 parts by mass of a mixture of CI Pigment Green 36/CI Pigment Yellow 150=60/40 (mass ratio) as a coloring agent (A), and 11.2 parts by mass of BYK-LPN21116 (manufactured by BYK Co., Ltd.) as a dispersing agent (solid content concentration 40) The mass%) and 73.8 parts by mass of propylene glycol monomethyl ether acetate as a solvent were mixed by a bead mill and dispersed for 12 hours to prepare a colorant dispersion (A-2).

調製例3Modulation example 3

使用作為(A)著色劑之C.I.色素紅242/C.I.色素紅177/C.I.色素黃139=22/72/6(質量比)混合物15.0質量份、作為分散劑之Solsperse 76500(Lubrizol股份公司製)4.0質量份(換算固體成分)、作為溶劑之丙二醇單甲醚乙酸酯/丙二醇單***=80/20(質量比)混合物，以珠磨進行混合‧分散12小時，以使固體成分濃度成為19質量%，來調製著色劑分散液(A-3)。As a coloring agent (C), a pigment red 242/CI pigment red 177/CI pigment yellow 139=22/72/6 (mass ratio) mixture was used in an amount of 15.0 parts by mass, and Solsperse 76500 (manufactured by Lubrizol Co., Ltd.) 4.0 as a dispersing agent. A mass fraction (converted solid content), a mixture of propylene glycol monomethyl ether acetate / propylene glycol monoethyl ether = 80/20 (mass ratio) as a solvent, mixed by bead milling, dispersed for 12 hours, so that the solid content concentration became 19 masses. % to prepare a colorant dispersion (A-3).

使用作為(A)著色劑之C.I.色素藍15:4/C.I.色素紫23=85/15(質量比)混合物12.0質量份、作為分散劑之BYK-LPN21116(BYK公司製)11.2質量份(固體成分濃度40質量%)、作為溶劑之丙二醇單甲醚乙酸酯76.8質量份，以珠磨進行混合‧分散12小時，來調製著色劑分散液(A-4)。12.0 parts by mass of a mixture of CI Pigment Blue 15:4/CI Pigment Violet 23=85/15 (mass ratio) as a coloring agent, and 11.2 parts by mass of BYK-LPN21116 (manufactured by BYK Corporation) as a dispersing agent (solid content) The concentration of 40% by mass) and 76.8 parts by mass of propylene glycol monomethyl ether acetate as a solvent were mixed by bead milling and dispersed for 12 hours to prepare a colorant dispersion (A-4).

黏合劑樹脂之合成Synthesis of adhesive resin 合成例1Synthesis Example 1

在具備冷卻管與攪拌機之燒瓶中，將對乙烯苄基環氧丙醚44質量份、N-苯基順丁烯二醯亞胺40質量份、甲基丙烯酸苄酯16質量份溶解於丙二醇單甲醚乙酸酯300質量份，再者，裝入2,2’-偶氮雙異丁腈8質量份及α-甲基苯乙烯二聚物8質量份，以氮取代。其後，一面緩緩地攪拌，一面進行氮發泡，同時使反應溶液升溫至80℃，保持該溫度，進行5小時聚合。In a flask equipped with a cooling tube and a stirrer, 44 parts by mass of ethylene benzyl glycidyl ether, 40 parts by mass of N-phenyl maleimide, and 16 parts by mass of benzyl methacrylate were dissolved in propylene glycol. 300 parts by mass of methyl ether acetate, and further, 8 parts by mass of 2,2'-azobisisobutyronitrile and 8 parts by mass of α-methylstyrene dimer were charged and substituted with nitrogen. Thereafter, while slowly stirring, nitrogen foaming was carried out while the reaction solution was heated to 80 ° C, and the temperature was maintained, and polymerization was carried out for 5 hours.

接著，在該反應溶液，添加甲基丙烯酸17質量份、對甲氧酚0.5質量份及溴化四丁銨4.4質量份，在120℃之溫度進行9小時反應。再者，添加琥珀酸酐18.5質量份，以100℃之溫度進行6小時反應後，在照樣保持反應溶液溫度於85℃下，進行水洗2次，藉由減壓濃縮，而獲得黏合劑樹脂溶液(固體成分濃度=33.0質量%)。所得之黏合劑樹脂，Mw=7,800、Mn=5,000。將該黏合劑樹脂溶液製成「黏合劑樹脂溶液(E-1)」。Next, 17 parts by mass of methacrylic acid, 0.5 parts by mass of p-methoxyphenol, and 4.4 parts by mass of tetrabutylammonium bromide were added to the reaction solution, and the reaction was carried out at a temperature of 120 ° C for 9 hours. Further, 18.5 parts by mass of succinic anhydride was added, and the reaction was carried out at a temperature of 100 ° C for 6 hours, and then the reaction solution was kept at a temperature of 85 ° C for 2 times, and concentrated under reduced pressure to obtain a binder resin solution ( Solid content concentration = 33.0% by mass). The resulting binder resin had Mw = 7,800 and Mn = 5,000. This binder resin solution was made into "adhesive resin solution (E-1)".

合成例2Synthesis Example 2

在具備冷卻管、攪拌機的燒瓶中，裝入2,2’-偶氮雙異丁腈3質量份及丙二醇單甲醚乙酸酯200質量份，接著，裝入甲基丙烯酸15質量份、N-苯基順丁烯二醯亞胺30質量份、甲基丙烯酸苄酯35質量份、苯乙烯20質量份及α-甲基苯乙烯二聚物(鏈轉移劑)5質量份，在經氮取代後，一面緩緩地攪拌，一面使反應溶液升溫至80℃，保持該溫度，並進行3小時聚合。其後，將反應溶液升溫至100℃，追加2,2’-偶氮雙異丁腈0.5質量份，再者繼續1小時聚合，而可獲得黏合劑樹脂溶液(固體成分濃度=32.5重量%)。所得之黏合劑樹脂，Mw=12,000、Mn=5,800。將該黏合劑樹脂溶液製成「黏合劑樹脂溶液(B-2)」。3 parts by mass of 2,2'-azobisisobutyronitrile and 200 parts by mass of propylene glycol monomethyl ether acetate were placed in a flask equipped with a cooling tube and a stirrer, and then 15 parts by mass of methacrylic acid and N were charged. 30 parts by mass of phenyl maleimide, 35 parts by mass of benzyl methacrylate, 20 parts by mass of styrene, and 5 parts by mass of α-methylstyrene dimer (chain transfer agent) in nitrogen After the substitution, the reaction solution was heated to 80 ° C while stirring slowly, and the temperature was maintained, and polymerization was carried out for 3 hours. Thereafter, the reaction solution was heated to 100 ° C, 0.5 parts by mass of 2,2'-azobisisobutyronitrile was added, and further polymerization was continued for 1 hour to obtain a binder resin solution (solid content concentration = 32.5 wt%). . The resulting binder resin had Mw = 12,000 and Mn = 5,800. This binder resin solution was made into "adhesive resin solution (B-2)".

倍半矽氧烷(D)之合成Synthesis of sesquioxane (D) 合成例3Synthesis Example 3

在氮大氣環境下，於三口燒瓶中裝入丙二醇單甲醚乙酸酯27.1質量份及3-氫硫基丙基三甲氧基矽烷23.2質量份，一面攪拌，一面加溫至60℃。在該溶液，添加丙二酸之0.2質量%水溶液9.6質量份，在60℃進行2小時反應。其後，在減壓下將水、甲醇餾除，相對於所得之產物添加丙二醇單甲醚乙酸酯以使全量成為75質量份為止。接著，將混合了三乙胺4.5質量份與丙二醇單甲醚乙酸酯70.5質量份的溶液，使用滴下漏斗，經1小時滴下。再者，在60℃進行2小時反應，在減壓下餾除水、三乙胺，而獲得具有磺基丙基的倍半矽氧烷。所得之倍半矽氧烷以GPC測定的結果，則Mw=5,200、Mn=2,500。又，以液體層析質量分析(LC-MS)所得之倍半矽氧烷可確認含有籠型倍半矽氧烷。將該籠型倍半矽氧烷製成「倍半矽氧烷(D-1)」。Under a nitrogen atmosphere, 27.1 parts by mass of propylene glycol monomethyl ether acetate and 23.2 parts by mass of 3-hydrothiopropyltrimethoxydecane were placed in a three-necked flask, and the mixture was heated to 60 ° C while stirring. To the solution, 9.6 parts by mass of a 0.2% by mass aqueous solution of malonic acid was added, and the reaction was carried out at 60 ° C for 2 hours. Thereafter, water and methanol were distilled off under reduced pressure, and propylene glycol monomethyl ether acetate was added to the obtained product so that the total amount became 75 parts by mass. Next, a solution of 4.5 parts by mass of triethylamine and 70.5 parts by mass of propylene glycol monomethyl ether acetate was mixed, and the mixture was dropped over 1 hour using a dropping funnel. Further, the reaction was carried out at 60 ° C for 2 hours, and water and triethylamine were distilled off under reduced pressure to obtain a sesquioxane having a sulfopropyl group. When the obtained sesquiterpene oxide was measured by GPC, Mw = 5,200 and Mn = 2,500. Further, the sesquiterpene oxide obtained by liquid chromatography mass spectrometry (LC-MS) was confirmed to contain a caged sesquiterpene oxide. This cage type sesquiterpene alkane was made into "sesquioxane (D-1)".

合成例4Synthesis Example 4

依照日本特開2004-143449號公報之段落[0030]之記載，獲得含有上述式(D-1)中R為3-甲基丙烯醯氧基丙基之化合物、上述式(D-2)中R為3-甲基丙烯醯氧基丙基之化合物、上述式(D-3)中R為3-甲基丙烯醯氧基丙基之化合物、上述式(D-5)中R為3-甲基丙烯醯氧基丙基之化合物及上述式(D-6)中R為3-甲基丙烯醯氧基丙基之化合物的籠型倍半矽氧烷之混合物。將該籠型倍半矽氧烷製成「倍半矽氧烷(D-2)」。According to the paragraph [0030] of JP-A-2004-143449, a compound containing the 3-methylpropenyloxypropyl group in the above formula (D-1) is obtained, and the above formula (D-2) is obtained. R is a compound of 3-methylpropenyloxypropyl group, a compound of the above formula (D-3) wherein R is a 3-methylpropenyloxypropyl group, and R in the above formula (D-5) is 3- A mixture of a methacryloxypropyl group compound and a cage type sesquiterpoxide of a compound of the above formula (D-6) wherein R is a 3-methylpropenyloxypropyl group. This cage type sesquiterpene alkane was made into "sesquioxane (D-2)".

合成例5Synthesis Example 5

於氮大氣環境下，在三口燒瓶中，裝入丙二醇單甲醚27.1質量份、3-氫硫基丙基三甲氧基矽烷12.6質量份及3-甲基丙烯醯氧基丙基三甲氧基矽烷5.3質量份，一面攪拌，一面加溫至50℃。在該溶液，添加草酸之0.2質量%水溶液5.8質量份，在50℃進行1小時反應。其後，在減壓下餾除水、甲醇，相對於所得之產物，添加丙二醇單甲醚，以使全量成為90質量份為止。接著，一面攪拌該溶液，一面加溫至70℃，並添加混合了氫氧化四甲銨25質量%水溶液4.7質量份、純水2.3質量份及丙二醇單甲醚6.3質量份的溶液，在70℃進行3小時反應。所得之產物在10℃以下冷卻，一面攪拌，一面添加順丁烯二酸之10質量%丙二醇單甲醚溶液14g。接著，添加乙酸丁酯，以分液漏斗水洗3次，使用乾燥劑，予以脫水後，在減壓下餾除水、乙酸丁酯，而獲得具有磺基丙基與甲基丙烯醯氧基丙基的倍半矽氧烷。GPC測定所得之倍半矽氧烷，結果為Mw=2,150、Mn=1,750。又，可確認藉由液體層析質量分析(LC-MS)所得之倍半矽氧烷含有籠型倍半矽氧烷。將該籠型倍半矽氧烷製成「倍半矽氧烷(D-3)」。In a three-necked flask, 27.1 parts by mass of propylene glycol monomethyl ether, 12.6 parts by mass of 3-hydrothiopropyltrimethoxydecane, and 3-methylpropenyloxypropyltrimethoxydecane were placed in a three-necked atmosphere. 5.3 parts by mass, while stirring, while warming to 50 °C. To the solution, 5.8 parts by mass of a 0.2% by mass aqueous solution of oxalic acid was added, and the reaction was carried out at 50 ° C for 1 hour. Thereafter, water and methanol were distilled off under reduced pressure, and propylene glycol monomethyl ether was added to the obtained product so that the total amount became 90 parts by mass. Next, while stirring the solution, the mixture was heated to 70 ° C, and a solution of 4.7 parts by mass of a 25 mass % aqueous solution of tetramethylammonium hydroxide, 2.3 parts by mass of pure water, and 6.3 parts by mass of propylene glycol monomethyl ether was added thereto at 70 ° C. The reaction was carried out for 3 hours. The obtained product was cooled at 10 ° C or lower, and while stirring, 14 g of a 10% by mass propylene glycol monomethyl ether solution of maleic acid was added. Next, butyl acetate was added, and the mixture was washed three times with a separatory funnel, and after dehydration using a desiccant, water and butyl acetate were distilled off under reduced pressure to obtain a sulfopropyl group and a methacryloxy group. A sesquiterpene oxide. The obtained sesquiterpene oxide was measured by GPC, and as a result, Mw was 2,150 and Mn was 1,750. Further, it was confirmed that the sesquiterpene oxide obtained by liquid chromatography mass spectrometry (LC-MS) contained cage sesquioxanes. This cage type sesquiterpene alkane was made into "sesquioxane (D-3)".

合成例6Synthesis Example 6

在氮大氣環境下，於三口燒瓶中裝入丙二醇單丙醚42.2質量份、純水4.5質量份及三乙胺3.2質量份，一面攪拌，一面加溫至55℃。將混合了3-氫硫基丙基三甲氧基矽烷4.9質量份、正丁基三甲氧基矽烷3.0質量份及丙二醇單丙醚42.2質量份的溶液，使用滴下漏斗，經2小時滴下。再者，藉由在55℃進行1小時反應，在減壓下餾除甲醇、水、三乙胺，而獲得具有磺基丙基與正丁基的倍半矽氧烷。GPC測定所得之倍半矽氧烷，結果為Mw=3,250、Mn=1,900。又，藉由液體層析質量分析(LC-MS)可確認所得之倍半矽氧烷含有籠型倍半矽氧烷。將該籠型倍半矽氧烷製成「倍半矽氧烷(D-4)」。In a nitrogen atmosphere, 42.2 parts by mass of propylene glycol monopropyl ether, 4.5 parts by mass of pure water, and 3.2 parts by mass of triethylamine were placed in a three-necked flask, and the mixture was heated to 55 ° C while stirring. A solution of 4.9 parts by mass of 3-hydrothiopropyltrimethoxydecane, 3.0 parts by mass of n-butyltrimethoxydecane, and 42.2 parts by mass of propylene glycol monopropyl ether was mixed, and the mixture was dropped over 2 hours using a dropping funnel. Further, by carrying out a reaction at 55 ° C for 1 hour, methanol, water and triethylamine were distilled off under reduced pressure to obtain a sesquioxane having a sulfopropyl group and n-butyl group. The obtained sesquiterpene oxide was measured by GPC, and as a result, Mw = 3,250 and Mn = 1,900. Further, it was confirmed by liquid chromatography mass spectrometry (LC-MS) that the obtained sesquiterpene oxide contained cage type sesquiterpene oxide. This cage type sesquiterpene alkane was made into "sesquioxane (D-4)".

非籠型之倍半矽氧烷之合成Synthesis of non-cage sesquioxanes 比較合成例1Comparative Synthesis Example 1

在氮大氣環境下，於三口燒瓶中裝入3-氫硫基丙基三甲氧基矽烷32.6質量份及正丁基三甲氧基矽烷31.9質量份，添加甲基異丁酮100質量份，予以溶解，所得之溶液以磁攪拌器一面攪拌一面加溫至60℃。在該溶液，將含有1質量%之草酸的8.6質量份之草酸水溶液經1小時連續添加，在60℃進行4小時反應。其後，在減壓下餾除水、甲醇、甲基異丁酮。將所得之產物溶解於甲苯，以分液漏斗經3次水洗，使用乾燥劑予以脫水後，藉由在減壓下餾除甲苯，而獲得具有磺基丙基與正丁基的倍半矽氧烷。藉由GPC測定可確認所得之倍半矽氧烷為無規型或梯型。將該倍半矽氧烷製成「倍半矽氧烷(d-2)」。32.6 parts by mass of 3-hydrothiopropyltrimethoxydecane and 31.9 parts by mass of n-butyltrimethoxydecane were placed in a three-necked flask under nitrogen atmosphere, and 100 parts by mass of methyl isobutyl ketone was added thereto to dissolve. The resulting solution was heated to 60 ° C while stirring with a magnetic stirrer. In the solution, 8.6 parts by mass of an aqueous solution of oxalic acid containing 1% by mass of oxalic acid was continuously added over 1 hour, and the reaction was carried out at 60 ° C for 4 hours. Thereafter, water, methanol, and methyl isobutyl ketone were distilled off under reduced pressure. The obtained product was dissolved in toluene, washed with water three times with a separating funnel, and dehydrated with a drying agent, and then toluene was distilled off under reduced pressure to obtain a sesquioxide containing sulfopropyl group and n-butyl group. alkyl. It was confirmed by GPC measurement that the obtained sesquiterpene oxide was a random type or a ladder type. This sesquiterpene alkane was made into "sesquioxanes (d-2)".

實施例1Example 1

將作為(A)著色劑之著色劑分散液(A-1)200質量份；作為(B)黏合劑樹脂之黏合劑樹脂溶液(B-1)90質量份；作為(C)多官能性單體之己內酯改性六丙烯酸二新戊四醇酯(日本化藥公司製、商品名KAYARAD DPCA-60)30質量份與以六丙烯酸二新戊四醇酯作為主成分之多官能丙烯酸酯(日本化藥公司製、商品名KAYARAD MAX-3510)30質量份；作為(D)成分之倍半矽氧烷(D-1)5質量份(換算固體成分)；作為(E)光聚合引發劑之2-苄基-2-二甲基胺基-1-(4-啉基苯基)丁烷-1-酮(Ciba特用化學品公司製、商品名Irgacure 369)25質量份、2,2’-雙(2-氯苯基)-4,4’,5,5’-四苯基-1,2’-聯咪唑(Hodogaya化學工業公司製、商品名B-CIM)2質量份、2,4-二乙基噻噸酮(日本化藥公司製、商品名CAYACURE DETX-S)2質量份；及作為溶劑之丙二醇單甲醚乙酸酯予以混合，來調製固體成分濃度20質量%之液狀組成物(S-1)。200 parts by mass of the colorant dispersion (A-1) as the coloring agent (A); 90 parts by mass of the binder resin solution (B-1) as (B) binder resin; as (C) polyfunctional single 30 parts by mass of caprolactone-modified dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD DPCA-60) and a multifunctional acrylate having dipentaerythritol hexaacrylate as a main component 30 parts by mass of (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD MAX-3510); 5 parts by mass of sesquioxane (D-1) as component (D) (converted solid content); (E) photopolymerization initiation 2-benzyl-2-dimethylamino-1-(4- 25 parts by mass of morphylphenyl)butan-1-one (manufactured by Ciba Specialty Chemicals, trade name Irgacure 369), 2,2'-bis(2-chlorophenyl)-4,4',5, 2'-tetraphenyl-1,2'-biimidazole (manufactured by Hodogaya Chemical Co., Ltd., trade name: B-CIM) 2 parts by mass, 2,4-diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd., trade name CAYACURE DETX-S) 2 parts by mass; and propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a liquid composition (S-1) having a solid concentration of 20% by mass.

關於液狀組成物(S-1)，依照下述之順序，進行評價。評價結果如表2所示。The liquid composition (S-1) was evaluated in the following order. The evaluation results are shown in Table 2.

密合性評價Adhesion evaluation

在表面形成有防止鈉離子之溶離的SiO2 膜之直徑4英吋之鈉玻璃基板上，使用旋轉塗布機塗布液狀組成物(S-1)後，以熱板，在90℃進行1分鐘預烘烤，形成膜厚2.5μm之塗膜。接著，使用高壓汞燈，並不經由光罩，而在塗膜中以含有365nm、405nm及436nm之各波長的放射線以600J/m2 之曝光量曝光。其後，藉由在塗膜以顯影壓1kgf/cm2 (噴嘴徑1mm)排出23℃、0.04%碳酸鈉水溶液，而進行沖洗顯影後，進一步，在230℃進行20分鐘後烘烤，在基板上形成綠色之硬化膜。The liquid composition (S-1) was applied onto a 4 inch-diameter sodium glass substrate having a SiO 2 film on the surface thereof to prevent elution of sodium ions, and then subjected to a hot plate at 90 ° C for 1 minute. Prebaking was carried out to form a coating film having a film thickness of 2.5 μm. Next, a high-pressure mercury lamp was used, and the exposure was performed at a exposure amount of 600 J/m 2 in the coating film with radiation having wavelengths of 365 nm, 405 nm, and 436 nm. Thereafter, after the film was discharged at 23 ° C and a 0.04% sodium carbonate aqueous solution at a developing pressure of 1 kgf/cm 2 (nozzle diameter: 1 mm), the film was rinsed and developed, and further baked at 230 ° C for 20 minutes to be baked on the substrate. A green cured film is formed thereon.

在所得之硬化膜上，使用ITO濺鍍裝置(Ulvac公司製)，製作ITO膜，以使膜厚成為500，依照JIS K5400規格，進行交叉切割成為100個棋盤眼狀的密合性試驗。只要是棋盤眼不致剝離而殘存的個數為90個以上，則評價為○；只要是80個以上低於90個，則評價為△；只要是低於80個則評價為×。評價結果如表2所示。只要棋盤眼不剝離，且殘存的個數為90個以上則可謂良好。An ITO film was formed on the obtained cured film by using an ITO sputtering apparatus (manufactured by Ulvac Co., Ltd.) so that the film thickness became 500. According to the JIS K5400 specification, the cross-cutting was performed to obtain an adhesion test of 100 checkerboard eyes. The evaluation is ○ as long as it is 90 or more, and the evaluation is △ as long as it is 80 or more and less than 90, and is × as long as it is less than 80. The evaluation results are shown in Table 2. As long as the checkerboard eye is not peeled off, and the number of remaining leaves is 90 or more, it is good.

耐溶劑性之評價Evaluation of solvent resistance

在表面形成有防止鈉離子之溶離的SiO2 膜之直徑4英吋之鈉玻璃基板上，使用旋轉塗布機塗布液狀組成物(S-1)後，以熱板，於90℃進行1分鐘預烘烤，形成膜厚2.5μm之塗膜。接著，在將該基板冷卻於室溫後，使用高壓汞燈，經由光罩，在塗膜中將含有365nm、405nm及436nm之各波長的放射線以600J/m2 之曝光量曝光。其後，相對於該基板，藉由將由23℃之0.04重量%碳酸鈉水溶液所組成之顯影液以顯影壓1kgf/cm2 (噴嘴直徑1mm)排出，而進行沖洗顯影後，進一步於230℃進行20分鐘後烘烤，在基板上形成200×200μm之點圖案。The liquid composition (S-1) was applied onto a 4 inch-diameter sodium glass substrate having a SiO 2 film on the surface thereof to prevent dissolution of sodium ions, and then subjected to a hot plate at 90 ° C for 1 minute. Prebaking was carried out to form a coating film having a film thickness of 2.5 μm. Next, after the substrate was cooled to room temperature, radiation containing wavelengths of 365 nm, 405 nm, and 436 nm was exposed to an exposure amount of 600 J/m 2 in a coating film through a photomask using a high pressure mercury lamp. Thereafter, the developing solution composed of a 0.04% by weight sodium carbonate aqueous solution at 23 ° C was discharged at a developing pressure of 1 kgf/cm 2 (nozzle diameter: 1 mm) with respect to the substrate, and then subjected to rinsing and development, and further at 230 ° C. After 20 minutes of baking, a dot pattern of 200 x 200 μm was formed on the substrate.

將所得之基板，在25℃之N-甲基吡咯啶酮各自浸漬30分鐘，浸漬前後之點圖案係以掃描型電子顯微鏡觀察，在圖案上無變化，且在浸漬前後之膜厚比(浸漬後膜厚×100/浸漬前之膜厚)為95%以上之情形則評價為○；在浸漬前後之膜厚比低於95%，或者在確認圖案之一部分有剝落(chipping)之情形則評價為△；在浸漬後圖案全部從基板剝離之情形則評價為×。評價結果如表2所示。The obtained substrate was each immersed in N-methylpyrrolidone at 25 ° C for 30 minutes, and the dot pattern before and after the immersion was observed by a scanning electron microscope, and there was no change in the pattern, and the film thickness ratio before and after the immersion (impregnation) When the film thickness after the film thickness × 100 / film thickness before immersion is 95% or more, it is evaluated as ○; when the film thickness ratio before and after immersion is less than 95%, or when it is confirmed that there is chipping in one of the patterns, evaluation is performed. It is Δ; the case where the pattern is completely peeled off from the substrate after immersion is evaluated as ×. The evaluation results are shown in Table 2.

電壓保持率之評價Evaluation of voltage retention

在表面形成防止鈉離子之溶離的SiO2 膜，進一步在蒸鍍ITO(銦-氧化錫合金)電極成所定形狀的鈉玻璃基板上，使用旋轉塗布機，塗布液狀組成物(S-1)後，在90℃之潔淨烘箱內，進行10分鐘預烘烤，形成膜厚2.0μm之塗膜。An SiO 2 film for preventing dissolution of sodium ions is formed on the surface, and a liquid composition (S-1) is further applied onto a soda glass substrate having a predetermined shape by vapor deposition of an ITO (indium-tin oxide alloy) electrode using a spin coater. Thereafter, prebaking was carried out for 10 minutes in a clean oven at 90 ° C to form a coating film having a film thickness of 2.0 μm.

接著，使用高壓汞燈，不經由光罩，而在塗膜將含有365nm、405nm及436nm之各波長的放射線以600J/m2 之曝光量曝光。其後，在由23℃之0.04重量%碳酸鈉水溶液所組成顯影液使該基板浸漬1分鐘，予以顯影後，以超純水洗淨並風乾，再者，在230℃進行20分鐘後烘烤，使塗膜硬化，在基板上形成綠色之像素。Next, using a high-pressure mercury lamp, radiation containing wavelengths of 365 nm, 405 nm, and 436 nm was exposed to an exposure amount of 600 J/m 2 in the coating film without passing through a photomask. Thereafter, the substrate was immersed in a developing solution composed of a 0.04% by weight aqueous sodium carbonate solution at 23 ° C for 1 minute, developed, washed with ultrapure water and air-dried, and further baked at 230 ° C for 20 minutes. The film is hardened to form green pixels on the substrate.

接著，將形成該像素的基板與僅蒸鍍ITO電極成預定形狀之基板，以混合了0.018mm之玻璃珠的密封劑貼合後，注入默克公司製液晶MLC6608(商品名)，來製作液晶晶胞。Next, the substrate on which the pixel is formed and the substrate on which the ITO electrode is deposited only in a predetermined shape are bonded together with a sealant in which glass beads of 0.018 mm are mixed, and then injected into a liquid crystal MLC6608 (trade name) manufactured by Merck to produce a liquid crystal. Unit cell.

接著，將液晶晶胞放入60℃之恆溫層，以東陽Technical公司製液晶電壓保持率測定系統VHR-1A型(商品名)測定液晶晶胞之電壓保持率。此時之外加電壓為5.0V之方形波、測定頻率為60Hz。在此，電壓保持率係指(16.7毫秒後以液晶晶胞電位差/0毫秒外加的電壓)之值。評價結果如表2所示。Then, the liquid crystal cell was placed in a constant temperature layer at 60 ° C, and the voltage holding ratio of the liquid crystal cell was measured by a liquid crystal voltage retention ratio measurement system VHR-1A (trade name) manufactured by Toyo Corporation. At this time, a square wave having a voltage of 5.0 V was applied, and the measurement frequency was 60 Hz. Here, the voltage holding ratio refers to a value (a voltage applied by a liquid crystal cell potential difference / 0 milliseconds after 16.7 milliseconds). The evaluation results are shown in Table 2.

實施例2至14及比較例1至3Examples 2 to 14 and Comparative Examples 1 to 3

除了使液狀組成物之各成分之種類及量成為表1所示以外，其他則與實施例1同樣地，調製液狀組成物(S-2)至(S-17)。The liquid compositions (S-2) to (S-17) were prepared in the same manner as in Example 1 except that the types and amounts of the respective components of the liquid composition were as shown in Table 1.

接著，除了各自使用液狀組成物(S-2)至(S-17)以替代液狀組成物(S-1)以外，其他則與實施例1同樣地進行評價。結果如表2所示。Next, the evaluation was carried out in the same manner as in Example 1 except that the liquid compositions (S-2) to (S-17) were used instead of the liquid composition (S-1). The results are shown in Table 2.

表1中，各成分係如下述。In Table 1, each component is as follows.

C-1：己內酯改性六丙烯酸二新戊四醇酯(日本化藥公司製、商品名KAYARAD DPCA-60)C-1: Caprolactone-modified dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD DPCA-60)

C-2：六丙烯酸二新戊四醇酯與五丙烯酸二新戊四醇酯之混合物(日本化藥公司製、商品名KAYARAD MAX-3510)C-2: a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD MAX-3510)

D-5：具有磺醯基之籠型倍半矽氧烷之市售品(磺醯基當量=206g/eq)D-5: Commercial product of cage sesquiterpene having a sulfonyl group (sulfonyl equivalent = 206 g/eq)

d-1：新戊四醇肆(3-氫硫基丙酸酯)D-1: neopentyl alcohol oxime (3-hydrothiopropionate)

E-1:2-苄基-2-二甲基胺基-1-(4-啉苯基)丁烷-1-酮(Ciba特用化學品公司製、商品名Irgacure 369)E-1: 2-benzyl-2-dimethylamino-1-(4- Phenanylphenyl)butan-1-one (manufactured by Ciba Specialty Chemicals, trade name Irgacure 369)

E-2：乙酮,1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-,1-(O-乙醯基肟)(Ciba特用化學品公司製、商品名Irgacure OXE02)E-2: ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(O-ethylindenyl) ( Ciba special chemical company, trade name Irgacure OXE02)

E-3:2,2’-雙(2-氯苯基)-4,4’,5,5’-四苯基-1,2’-聯咪唑(Hodogaya化學工業公司製、商品名B-CIM)E-3: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (manufactured by Hodogaya Chemical Co., Ltd., trade name B- CIM)

E-4:2,4-二乙基噻噸酮(日本化藥公司製、商品名CAYACURE DETX-S)E-4: 2,4-diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd., trade name CAYACURE DETX-S)

E-5:1-羥基-環己基苯基酮(Ciba特用化學品公司製、商品名Irgacure 184)E-5: 1-hydroxy-cyclohexyl phenyl ketone (manufactured by Ciba Specialty Chemicals, trade name Irgacure 184)

F-1：偶氮異丁腈(大塚化學工業公司製、商品名AIBN)F-1: azoisobutyronitrile (manufactured by Otsuka Chemical Industry Co., Ltd., trade name AIBN)

由表2可知，使用含有(D)具有磺醯基及/或聚合性不飽和基的籠型倍半矽氧烷的本發明著色組成物所形成之像素，與透明導電膜或無機膜之密合性優異，在低曝光量中亦顯示優異耐溶劑性，再者電壓保持率亦高。As is clear from Table 2, the pixel formed by the colored composition of the present invention containing (D) the cage sesquiterpoxysilane having a sulfonyl group and/or a polymerizable unsaturated group is densely bonded to the transparent conductive film or the inorganic film. Excellent in compatibility, excellent solvent resistance in low exposure, and high voltage retention.

Claims (7)

一種彩色濾光片之著色層形成用著色組成物，其特徵為含有選自由(A)著色劑、(B)黏合劑樹脂、(C)多官能性單體、以及(D)磺醯基及聚合性不飽和基所構成群組中之至少一種之籠型倍半矽氧烷。 A coloring composition for forming a color layer of a color filter, characterized by containing a coloring agent selected from the group consisting of (A) a coloring agent, (B) a binder resin, (C) a polyfunctional monomer, and (D) a sulfonyl group and A cage type sesquiterpene oxide of at least one of the group consisting of polymerizable unsaturated groups. 如申請專利範圍第1項之彩色濾光片之著色層形成用著色組成物，其中(A)著色劑的含量為該著色組成物之全固體成分中5至70質量%。 The coloring composition for forming a color layer of the color filter of claim 1, wherein the content of the (A) coloring agent is 5 to 70% by mass based on the total solid content of the coloring composition. 如申請專利範圍第1項之彩色濾光片之著色層形成用著色組成物，其中(B)黏合劑樹脂含有具有酸性官能基與聚合性不飽和基的聚合物。 The colored composition for forming a color layer of the color filter of claim 1, wherein the (B) binder resin contains a polymer having an acidic functional group and a polymerizable unsaturated group. 如申請專利範圍第1至3項中任一項之彩色濾光片之著色層形成用著色組成物，其進一步含有(E)光聚合引發劑。 The colored composition for forming a color layer of the color filter according to any one of claims 1 to 3, further comprising (E) a photopolymerization initiator. 如申請專利範圍第4項之彩色濾光片之著色層形成用著色組成物，其中該(E)光聚合引發劑係含有O-醯基肟系化合物。 The colored composition for forming a color layer of the color filter of claim 4, wherein the (E) photopolymerization initiator contains an O-fluorenyl fluorene compound. 一種彩色濾光片，其係具備使用如申請專利範圍第1至5項中任一項之彩色濾光片之著色層形成用著色組成物所形成之著色層而成。 A color filter comprising a coloring layer formed by using a colored composition for forming a color layer of a color filter according to any one of claims 1 to 5. 一種液晶顯示元件，其具備如申請專利範圍第6項之彩色濾光片。A liquid crystal display element comprising the color filter of item 6 of the patent application.
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