TWI743323B - Color material dispersion liquid for color filter, color resin composition for color filter, color filter, and display device - Google Patents
Color material dispersion liquid for color filter, color resin composition for color filter, color filter, and display device Download PDFInfo
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Abstract
Description
本發明係關於一種彩色濾光片用色材分散液、彩色濾光片用著色樹脂組成物、彩色濾光片、及顯示裝置。 The present invention relates to a color material dispersion liquid for color filters, a colored resin composition for color filters, a color filter, and a display device.
彩色濾光片通常係紅色、藍色、綠色之3色之像素以圖案狀形成於透明基板上而成者。為了提高色再現性,近年來,使用向上述3色中添加黃色而成之4色之像素以圖案狀形成而成之彩色濾光片之顯示器製品亦上市。於此種狀況下,彩色濾光片之進一步之高亮度化或高對比度化、色再現性之提高等要求提高。 The color filter is usually formed by forming three color pixels of red, blue, and green in a pattern on a transparent substrate. In order to improve color reproducibility, in recent years, display products using color filters formed by patterning pixels of four colors in which yellow is added to the above three colors have also been put on the market. Under such circumstances, the requirements for further enhancement of brightness or contrast of color filters, and improvement of color reproducibility have increased.
作為彩色濾光片中之像素之形成方法,已知有顏料分散法、染色法、電沈積法、印刷法等。其中,就分光特性、耐久性、圖案形狀及精度等觀點而言,具有平均優異之特性之顏料分散法被最廣泛地採用。 As a method of forming pixels in a color filter, a pigment dispersion method, a dyeing method, an electrodeposition method, a printing method, etc. are known. Among them, from the viewpoints of spectroscopic properties, durability, pattern shape, and accuracy, the pigment dispersion method with excellent average properties is most widely used.
於具有使用顏料分散法而形成之像素之彩色濾光片中,為了實現高亮度化或高對比度化,正在研究顏料之微細化。認為藉由使顏料微細化,穿透基於顏料粒子之彩色濾光片之光之散射被降低,從而達成高亮度化或高對比度化。 In a color filter with pixels formed using a pigment dispersion method, in order to achieve high brightness or high contrast, the miniaturization of pigments is being studied. It is thought that by miniaturizing the pigment, the scattering of light penetrating the color filter based on the pigment particles is reduced, thereby achieving high brightness or high contrast.
然而,經微細化之顏料粒子存在容易凝集之問題。尤其是吡咯并吡咯二酮系顏料若為了實現高對比度化而使顏料微細化,則存在於彩色濾光片之製造步驟中之高溫加熱時,顏料粒子容易凝集或結晶生長,於加熱步驟後,顏料之粒子以異物之形式於像素表面析出而導致對比度降低或作為缺陷而被識別出之問題。 However, the miniaturized pigment particles have a problem that they are easy to agglomerate. In particular, if the diketopyrrolopyrrole pigments are refined in order to achieve high contrast, the pigment particles tend to agglomerate or crystallize when heated at high temperatures in the manufacturing process of the color filter. After the heating process, Pigment particles are deposited on the surface of the pixel in the form of foreign matter, which leads to a decrease in contrast or a problem that is recognized as a defect.
作為顏料之微細化之嘗試,使用將顏料與於顏料骨架之一部分導入有取代基之顏料衍生物組合而成之顏料調配物。作為吡咯并吡咯二酮系顏料之顏料衍生物,使用吡咯并吡咯二酮系顏料之磺化物或其金屬鹽或者胺鹽等(例如專利文獻1)。 As an attempt to refine the pigment, a pigment formulation is used that combines a pigment and a pigment derivative with a substituent introduced into a part of the pigment skeleton. As the pigment derivative of the diketopyrrolopyrrole pigment, the sulfonate of the diketopyrrolopyrrole pigment or its metal salt or amine salt or the like is used (for example, Patent Document 1).
又,於專利文獻2中記載有一種顏料衍生物之選擇或設計方法,其係於在顏料中對顏料衍生物進行處理而成之顏料組成物中,賦予分散性良好之顏料組成物之顏料衍生物之選擇或設計方法,其特徵在於包含:對顏料衍生物之偶極矩進行測定或計算之步驟;及根據該經測定或計算所得之偶極矩之數值選擇顏料衍生物或根據該偶極矩之數值對顏料衍生物進行設計之步驟。並且,揭示有於在作為吡咯并吡咯二酮系顏料之C.I.顏料紅254中對顏料衍生物進行處理而成之顏料組成物中,對分散性及儲存穩定性進行評價所得之結果,於使用C.I.顏料紅254之磺酸單取代體、C.I.顏料紅264之磺酸單取代體鋁鹽、C.I.顏料黃138之磺酸單取代體作為顏料衍生物之情形時,顯示分散性及儲存穩定性良好,於使用C.I.顏料紅255之磺酸雙取代體、C.I.顏料紅177之磺酸雙取代體作為顏料衍生物之情形時,顯示分散性及儲存穩定性較差。 In addition,
於專利文獻3中記載有如下:為了能夠提高彩色濾光片用顏料油墨之色品質、低黏度化及防止產生異物,於包含顏料與 樹脂清漆之顏料組成物中,含有包含碸基之顏料分子成分與不包含碸基之顏料分子成分之顏料複合體,並將該顏料複合體中之總顏料分子換算之每1個分子之平均碸基導入個數設為0.05~0.5。
專利文獻1:日本專利特開平7-173406號公報 Patent Document 1: Japanese Patent Laid-Open No. 7-173406
專利文獻2:日本專利特開2012-77192號公報 Patent Document 2: Japanese Patent Laid-Open No. 2012-77192
專利文獻3:日本專利特開2007-23266號公報 Patent Document 3: Japanese Patent Laid-Open No. 2007-23266
然而,使用使習知之色材分散液中含有黏合劑成分之著色樹脂組成物而形成之著色層存在後烘烤後對比度降低之問題。本發明係鑒於上述實際情況而完成者,目的在於提供一種可形成對比度提高之著色層之彩色濾光片用色材分散液。又,本發明之目的在於提供一種可形成對比度提高之著色層之彩色濾光片用著色樹脂組成物。又,本發明之目的在於提供一種具有使用該彩色濾光片用著色樹脂組成物而形成之對比度提高之著色層之彩色濾光片。又,本發明之目的在於提供一種使用該彩色濾光片之顯示裝置。 However, the coloring layer formed by using the coloring resin composition containing the binder component in the conventional color material dispersion liquid has the problem of lowering the contrast after post-baking. The present invention was completed in view of the above-mentioned actual situation, and its object is to provide a color material dispersion liquid for color filters that can form a coloring layer with improved contrast. Another object of the present invention is to provide a colored resin composition for a color filter that can form a colored layer with improved contrast. Furthermore, the object of the present invention is to provide a color filter having a coloring layer with improved contrast formed by using the colored resin composition for a color filter. Moreover, the object of the present invention is to provide a display device using the color filter.
本發明之彩色濾光片用色材分散液係含有色材、色素衍生物、分散劑、及溶劑者,其特徵在於:上述色材包含吡咯并吡咯二酮系色材,上述色素衍生物係包含吡咯并吡咯二酮系色材之單磺化衍生 物與吡咯并吡咯二酮系色材之二磺化衍生物之混合物,並且上述單磺化衍生物之莫耳相對於上述單磺化衍生物與上述二磺化衍生物之莫耳之合計之比{單磺化衍生物/(單磺化衍生物+二磺化衍生物)}為0.10以上且0.90以下,上述分散劑係具有下述通式(I)所表示之構成單元之聚合體。 The color material dispersion liquid for color filters of the present invention contains a color material, a pigment derivative, a dispersant, and a solvent, and is characterized in that the color material includes a diketopyrrolopyrrole color material, and the pigment derivative system Contains a mixture of a monosulfonated derivative of a diketopyrrolopyrrole color material and a disulfonated derivative of a diketopyrrolopyrrole color material, and the molar ratio of the above-mentioned monosulfonated derivative is relative to the above-mentioned monosulfonated derivative The ratio {monosulfonated derivative/(monosulfonated derivative+disulfonated derivative)} of the total molar ratio of the substance to the above-mentioned disulfonated derivative is 0.10 or more and 0.90 or less. The above-mentioned dispersant system has the following A polymer of the structural unit represented by the general formula (I).
(通式(I)中,R1表示氫原子或甲基,A表示2價之連結基,R2及R3分別獨立地表示氫原子或可包含雜原子之烴基,R2及R3可相互鍵結而形成環結構。) (In the general formula (I), R 1 represents a hydrogen atom or a methyl group, A represents a divalent linking group, R 2 and R 3 each independently represent a hydrogen atom or a hydrocarbon group that may contain a heteroatom, R 2 and R 3 may They are bonded to each other to form a ring structure.)
本發明之彩色濾光片用著色樹脂組成物係含有色材、色素衍生物、分散劑、黏合劑成分、及溶劑者,其特徵在於:上述色材包含吡咯并吡咯二酮系色材,上述色素衍生物係包含吡咯并吡咯二酮系色材之單磺化衍生物與吡咯并吡咯二酮系色材之二磺化衍生物之混合物,並且上述單磺化衍生物之莫耳相對於上述單磺化衍生物與上述二磺化衍生物之莫耳之合計之比{單磺化衍生物/(單磺化衍生物+二磺化衍生物)}為0.10以上且0.90以下,上述分散劑係具有上述通式(I)所表示之構成單元之聚合體。 The colored resin composition for a color filter of the present invention contains a color material, a pigment derivative, a dispersant, a binder component, and a solvent, and is characterized in that the color material includes a diketopyrrolopyrrole color material. The pigment derivative is a mixture of the monosulfonated derivative of the diketopyrrolopyrrole color material and the disulfonated derivative of the diketopyrrolopyrrole color material, and the mole of the monosulfonated derivative is relative to the above The ratio of the total molar ratio of the monosulfonated derivative and the disulfonated derivative {monosulfonated derivative/(monosulfonated derivative + disulfonated derivative)} is 0.10 or more and 0.90 or less, the above dispersant It is a polymer having a structural unit represented by the above general formula (I).
本發明之彩色濾光片係至少具備基板及設置於該基板上之著色層者,其特徵在於:該著色層之至少1層係上述本發明 之彩色濾光片用著色樹脂組成物之硬化物。 The color filter of the present invention has at least a substrate and a coloring layer provided on the substrate, and is characterized in that: at least one layer of the coloring layer is a cured product of the coloring resin composition for a color filter of the present invention .
本發明之顯示裝置之特徵在於:其具有上述本發明之彩色濾光片。 The display device of the present invention is characterized in that it has the above-mentioned color filter of the present invention.
根據本發明,可提供一種可形成對比度提高之著色層之彩色濾光片用色材分散液。又,本發明可提供一種可形成對比度提高之著色層之彩色濾光片用著色樹脂組成物。又,本發明可提供一種具有使用該彩色濾光片用著色樹脂組成物而形成之對比度提高之著色層之彩色濾光片。又,本發明可提供一種使用該彩色濾光片之顯示裝置。 According to the present invention, it is possible to provide a color material dispersion liquid for a color filter that can form a coloring layer with improved contrast. In addition, the present invention can provide a colored resin composition for a color filter that can form a colored layer with improved contrast. In addition, the present invention can provide a color filter having a coloring layer with improved contrast formed by using the colored resin composition for a color filter. In addition, the present invention can provide a display device using the color filter.
1‧‧‧基板 1‧‧‧Substrate
2‧‧‧遮光部 2‧‧‧Shading part
3‧‧‧著色層 3‧‧‧Coloring layer
10‧‧‧彩色濾光片 10‧‧‧Color filter
20‧‧‧對向基板 20‧‧‧Opposite substrate
30‧‧‧液晶層 30‧‧‧Liquid crystal layer
40‧‧‧液晶顯示裝置 40‧‧‧LCD device
50‧‧‧有機保護層 50‧‧‧Organic protective layer
60‧‧‧無機氧化膜 60‧‧‧Inorganic oxide film
71‧‧‧透明陽極 71‧‧‧Transparent anode
72‧‧‧電洞注入層 72‧‧‧hole injection layer
73‧‧‧電洞傳輸層 73‧‧‧Hole Transmission Layer
74‧‧‧發光層 74‧‧‧Light-emitting layer
75‧‧‧電子注入層 75‧‧‧Electron injection layer
76‧‧‧陰極 76‧‧‧Cathode
80‧‧‧有機發光體 80‧‧‧Organic luminous body
100‧‧‧有機發光顯示裝置 100‧‧‧Organic light emitting display device
圖1係表示本發明之彩色濾光片之一例之概略圖。 Fig. 1 is a schematic diagram showing an example of the color filter of the present invention.
圖2係表示本發明之液晶顯示裝置之一例之概略圖。 Fig. 2 is a schematic diagram showing an example of the liquid crystal display device of the present invention.
圖3係表示本發明之有機發光顯示裝置之一例之概略圖。 FIG. 3 is a schematic diagram showing an example of the organic light emitting display device of the present invention.
以下,針對本發明之彩色濾光片用色材分散液、彩色濾光片用著色樹脂組成物、彩色濾光片及顯示裝置,依序詳細地進行說明。再者,於本發明中,光包含可見及非可見區域之波長之電磁波、以及放射線,放射線例如包含微波、電子束。具體而言,係指波長5μm以下之電磁波、及電子束。於本發明中,(甲基)丙烯酸表示丙烯酸及甲基丙烯酸之各者,(甲基)丙烯酸酯表示丙烯酸酯及甲基丙烯酸酯之各者。 Hereinafter, the color material dispersion liquid for color filters, the colored resin composition for color filters, the color filter, and the display device of the present invention will be described in detail in order. Furthermore, in the present invention, light includes electromagnetic waves with wavelengths in the visible and non-visible regions, and radiation, and the radiation includes, for example, microwaves and electron beams. Specifically, it refers to electromagnetic waves and electron beams with a wavelength of 5 μm or less. In the present invention, (meth)acrylic acid means each of acrylic acid and methacrylic acid, and (meth)acrylate means each of acrylate and methacrylate.
本發明之彩色濾光片用色材分散液係含有色材、色素衍生物、分散劑、及溶劑者,其特徵在於:上述色材包含吡咯并吡咯二酮系色材,上述色素衍生物係包含吡咯并吡咯二酮系色材之單磺化衍生物與吡咯并吡咯二酮系色材之二磺化衍生物之混合物,並且上述單磺化衍生物之莫耳相對於上述單磺化衍生物與上述二磺化衍生物之莫耳之合計之比{單磺化衍生物/(單磺化衍生物+二磺化衍生物)}為0.10以上且0.90以下,且上述分散劑係具有下述通式(I)所表示之構成單元之聚合體。 The color material dispersion liquid for color filters of the present invention contains a color material, a pigment derivative, a dispersant, and a solvent, and is characterized in that the color material includes a diketopyrrolopyrrole color material, and the pigment derivative system Contains a mixture of a monosulfonated derivative of a diketopyrrolopyrrole color material and a disulfonated derivative of a diketopyrrolopyrrole color material, and the molar ratio of the above-mentioned monosulfonated derivative is relative to the above-mentioned monosulfonated derivative The ratio {monosulfonated derivative/(monosulfonated derivative+disulfonated derivative)} of the total molar ratio of the substance to the above-mentioned disulfonated derivative is 0.10 or more and 0.90 or less, and the above-mentioned dispersant system has the following The polymer of the structural unit represented by the general formula (I).
(通式(I)中,R1表示氫原子或甲基,A表示2價之連結基,R2及R3分別獨立地表示氫原子、或可具有雜原子之烴基,R2及R3可相互鍵結而形成環結構。) (In the general formula (I), R 1 represents a hydrogen atom or a methyl group, A represents a divalent linking group, R 2 and R 3 each independently represent a hydrogen atom or a hydrocarbon group that may have a heteroatom, R 2 and R 3 Can be bonded to each other to form a ring structure.)
由於本發明之色材分散液將以既定之比例混合吡咯并吡咯二酮系色材之單磺化衍生物與吡咯并吡咯二酮系色材之二磺化衍生物而成之混合物及作為分散劑之具有上述通式(I)所表示之構成單元之聚合體與吡咯并吡咯二酮系色材組合含有,故而使用該色材分散液而製備之著色樹脂組成物可形成抑制加熱時之對比度之降低,提高對比度之著色層。通常,於色材分散液之製備中, 於使用顏料作為色材之情形時,藉由延長溶劑中之顏料之分散時間而使顏料微細化。經微細化而露出之顏料表面之吸附力較強,有顏料彼此會吸附而凝集之情況。此處,認為於使用分散劑之情形時,分散劑吸附於經微細化而露出之顏料表面,可實現溶劑中之顏料之穩定化,而可使顏料均勻地微細化。然而,於將包含經均勻地微細化之吡咯并吡咯二酮系色材(例如,C.I.顏料紅254(PR254))之組成物製成塗膜後,若於彩色濾光片之製造步驟中對塗膜施加例如230℃之高溫,則吡咯并吡咯二酮系色材粒子析出。推測若對塗膜施加230℃之高溫,則因吸附於吡咯并吡咯二酮系色材之分散劑之熱運動,分散劑之吸附減弱,顏料凝集,顏料結晶生長而於塗膜表面等產生吡咯并吡咯二酮系色材粒子之析出。推測因此顏料表面彼此之凝集力增強而產生PR254之顏料析出物。因該顏料析出物之產生而導致塗膜之對比度降低。作為抑制吡咯并吡咯二酮系色材之凝集之嘗試,使用吡咯并吡咯二酮系色材之色素衍生物。色素衍生物係於色材骨架之一部分導入有取代基之化合物,於該取代基與分散劑之間產生相互作用。推測因色素衍生物吸附於色材表面,與色素衍生物相互作用之分散劑產生靜電或者立體排斥作用,其防止色材之凝集而使色材穩定地分散。於吡咯并吡咯二酮系色材之色素衍生物中之吡咯并吡咯二酮系色材之磺化衍生物中,於上述專利文獻2中顯示,與二磺化衍生物相比,單磺化衍生物容易提高分散液之分散性及儲存穩定性。然而,本發明者等人發現,藉由將以既定之比例混合吡咯并吡咯二酮系色材之單磺化衍生物與吡咯并吡咯二酮系色材之二磺化衍生物而成之混合物及具有特定結構之分散劑與吡咯并吡咯二酮系色材組合使用,可較使用單磺化衍生物單體之情形提 高著色層之對比度。作為發揮此種效果之作用,雖未解明,但推測上述單磺化衍生物與顏料分子之親和性更高,上述二磺化衍生物與上述特定分散劑或樹脂等之親和性更高,故而藉由將上述單磺化衍生物與上述二磺化衍生物以既定之比例加以混合,分散液或樹脂組成物中所包含之各成分容易成為更均勻且穩定之分散狀態,且推測即便於對樹脂組成物進行加熱時,亦容易維持均勻且穩定之分散狀態,不易產生昇華、凝集等由熱所導致之形態之變化,藉此抑制對著色層進行加熱時之對比度之降低。 Since the color material dispersion of the present invention will mix the monosulfonated derivative of the diketopyrrolopyrrole color material and the disulfonated derivative of the diketopyrrolopyrrole color material in a predetermined ratio and serve as a dispersion The polymer having the structural unit represented by the above general formula (I) is contained in combination with a diketopyrrolopyrrole color material, so the coloring resin composition prepared by using the color material dispersion liquid can form a contrast that inhibits heating It reduces and improves the contrast of the colored layer. Generally, in the preparation of the color material dispersion liquid, when a pigment is used as the color material, the pigment is made finer by extending the dispersion time of the pigment in the solvent. The surface of the pigment exposed by the miniaturization has a strong adsorption force, and the pigments may adsorb each other and agglomerate. Here, it is considered that when a dispersant is used, the dispersant is adsorbed on the surface of the pigment exposed by the refinement, so that the pigment in the solvent can be stabilized, and the pigment can be uniformly refined. However, after the composition containing the diketopyrrolopyrrole color material (for example, CI Pigment Red 254 (PR254)) that has been uniformly miniaturized is made into a coating film, if the color filter is manufactured in the process When a high temperature of 230°C is applied to the coating film, the diketopyrrolopyrrole color material particles are deposited. It is estimated that if a high temperature of 230℃ is applied to the coating film, the thermal movement of the dispersant adsorbed on the diketopyrrolopyrrole color material will weaken the adsorption of the dispersant, the pigment agglomerates, and the pigment crystal grows to produce pyrrole on the surface of the coating film. Precipitation of diketopyrrole color material particles. It is speculated that the cohesive force between the pigment surfaces is enhanced and the pigment precipitates of PR254 are generated. The contrast of the coating film is reduced due to the generation of the pigment precipitates. As an attempt to inhibit the aggregation of diketopyrrolopyrrole color materials, pigment derivatives of diketopyrrolopyrrole color materials were used. The pigment derivative is a compound in which a substituent is introduced into a part of the color material skeleton, and an interaction occurs between the substituent and the dispersant. It is speculated that because the pigment derivative is adsorbed on the surface of the color material, the dispersant that interacts with the pigment derivative generates static electricity or steric repulsion, which prevents agglomeration of the color material and makes the color material stably dispersed. Among the sulfonated derivatives of diketopyrrolopyrrole color materials among the pigment derivatives of diketopyrrolopyrrole color materials, it is shown in
本發明之色材分散液至少含有色材、色素衍生物、分散劑、及溶劑,亦可於無損本發明之效果之範圍內進而含有其他成分。以下,針對此種本發明之色材分散液之各成分,自本發明之色素衍生物依序詳細地進行說明。 The color material dispersion of the present invention contains at least a color material, a pigment derivative, a dispersant, and a solvent, and may further contain other components within a range that does not impair the effects of the present invention. Hereinafter, each component of the color material dispersion liquid of the present invention will be described in detail in order from the dye derivative of the present invention.
本發明所使用之色素衍生物係包含吡咯并吡咯二酮系色材之單磺化衍生物與吡咯并吡咯二酮系色材之二磺化衍生物之混合物,於該混合物中,相對於上述單磺化衍生物與上述二磺化衍生物之合計的上述單磺化衍生物之含有莫耳比{單磺化衍生物/(單磺化衍生物+二磺化衍生物)}為0.10以上且0.90以下。 The pigment derivative used in the present invention contains a mixture of the monosulfonated derivative of the diketopyrrolopyrrole color material and the disulfonated derivative of the diketopyrrolopyrrole color material. The total molar ratio of the monosulfonated derivative of the monosulfonated derivative and the disulfonated derivative {monosulfonated derivative/(monosulfonated derivative + disulfonated derivative)} is 0.10 or more And below 0.90.
作為吡咯并吡咯二酮系色材之單磺化衍生物,例如可列舉下述通式(1-m)所表示之單磺化衍生物,作為吡咯并吡咯二酮系色材之二磺化衍生物,例如可列舉下述通式(1-d)所表示之二磺化衍生物。 As the monosulfonated derivative of the diketopyrrolopyrrole color material, for example, the monosulfonated derivative represented by the following general formula (1-m) can be cited as the second sulfonation of the diketopyrrolopyrrole color material Examples of derivatives include disulfonated derivatives represented by the following general formula (1-d).
[化3]
(於通式(1-m)及通式(1-d)中,Y1及Y2分別獨立地為選自由鹵素原子、氰基、苄基、可經烷基取代之苯基、及碳數1~10之烷基所構成之群組中之取代基,n及m分別獨立地表示0~5之整數;於n及m為2以上之情形時,數個Y1及Y2可分別相同,亦可不同;Z表示-OH、-OM+p/p、-ON+HR11R12R13、-NH-(CH2)s-NR14R15、-NH-(CH2)t-COOH或-NH-(CH2)u-SO3H,數個Z可分別相同,亦可不同;M表示1價、2價或3價之金屬陽離子,p表示1、2或3;R11、R12、R13、R14及R15分別獨立地表示氫原子、碳數1~20之可經取代之烴基、或與相鄰之氮原子一併形成雜環者;s、t及u分別獨立地表示1~6之整數。) (In general formula (1-m) and general formula (1-d), Y 1 and Y 2 are each independently selected from a halogen atom, a cyano group, a benzyl group, a phenyl group that may be substituted with an alkyl group, and carbon Substituents in a group consisting of an alkyl group of 1-10, n and m each independently represent an integer of 0-5; when n and m are 2 or more, several Y 1 and Y 2 can be respectively The same or different; Z means -OH, -OM +p /p, -ON + HR 11 R 12 R 13 , -NH-(CH 2 ) s -NR 14 R 15 , -NH-(CH 2 ) t -COOH or -NH-(CH 2 ) u -SO 3 H, several Z may be the same or different; M represents a monovalent, divalent or trivalent metal cation, p represents 1, 2 or 3; R 11 , R 12 , R 13 , R 14, and R 15 each independently represent a hydrogen atom, a substituted hydrocarbon group with 1 to 20 carbon atoms, or one that forms a heterocyclic ring together with an adjacent nitrogen atom; s, t, and u independently represents an integer from 1 to 6.)
於上述通式(1-m)及上述通式(1-d)中,Y1及Y2分別獨立地為選自由鹵素原子、氰基、苄基、可經烷基取代之苯基、及碳數1~10之烷基所構成之群組中之取代基,只要根據組合使用之吡咯并吡咯二酮系色材之色調或結構適當選擇即可,其中,就容易提高著色層之對比度之方面而言,較佳為鹵素原子、碳數1~3之烷基。原因在於鹵素原子或碳數1~3之直鏈或支鏈之烷基之位阻較小而不易阻礙對色材之吸附。作為Y1及Y2中之鹵素原子,可列舉 氟原子、氯原子、溴原子、碘原子,其中,較佳為氯原子、溴原子。又,作為苯基之取代基之烷基,亦較佳為碳數1~3之直鏈或支鏈之烷基。作為碳數1~3之直鏈或支鏈之烷基,可列舉甲基、乙基、正丙基、異丙基。 In the above general formula (1-m) and the above general formula (1-d), Y 1 and Y 2 are each independently selected from a halogen atom, a cyano group, a benzyl group, a phenyl group that may be substituted with an alkyl group, and The substituents in the group consisting of alkyl groups with 1 to 10 carbon atoms can be appropriately selected according to the hue or structure of the diketopyrrolopyrrole color material used in combination. Among them, it is easy to increase the contrast of the colored layer. From the point of view, a halogen atom and an alkyl group having 1 to 3 carbon atoms are preferred. The reason is that the steric hindrance of the halogen atom or the linear or branched alkyl group with
於上述通式(1-m)及上述通式(1-d)中,n及m分別獨立地為鍵結於吡咯并吡咯二酮骨架之苯基之取代基之數量,就進一步提高對比度之方面而言,分別較佳為0或1。推測藉由使n及m分別為0或1,作用於吡咯并吡咯二酮系色材之側之位阻較小,而可使更多之氫鍵結或吸附於吡咯并吡咯二酮系色材之一次粒子之表面,從而容易成為更均勻且穩定之分散狀態,而抑制著色層加熱時之對比度降低之效果提高。 In the above general formula (1-m) and the above general formula (1-d), n and m are each independently the number of substituents of the phenyl group bonded to the diketopyrrolopyrrole skeleton, which further improves the contrast From the aspect, it is preferably 0 or 1, respectively. It is speculated that by setting n and m to 0 or 1, the steric hindrance acting on the side of the diketopyrrolopyrrole color material is smaller, and more hydrogen can be bonded or adsorbed on the diketopyrrolopyrrole color material. The surface of the primary particles of the material can easily become a more uniform and stable dispersion state, and the effect of suppressing the decrease in contrast when the colored layer is heated is improved.
於上述通式(1-m)及上述通式(1-d)中,Z係-OH、-OM+p/p、-ON+HR11R12R13、-NH-(CH2)s-NR14R15、-NH-(CH2)t-COOH或-NH-(CH2)u-SO3H,只要根據組合使用之吡咯并吡咯二酮系色材之色調或結構適當選擇即可,其中,就提高著色層之對比度之方面而言,Z較佳為-OH、-OM+p/p、或-NH-(CH2)s-NR14R15,更佳為-OH。 In the above general formula (1-m) and the above general formula (1-d), Z is -OH, -OM +p /p, -ON + HR 11 R 12 R 13 , -NH-(CH 2 ) s -NR 14 R 15 , -NH-(CH 2 ) t -COOH or -NH-(CH 2 ) u -SO 3 H, as long as they are properly selected according to the hue or structure of the diketopyrrolopyrrole color material used in combination However, in terms of improving the contrast of the colored layer, Z is preferably -OH, -OM +p /p, or -NH-(CH 2 ) s -NR 14 R 15 , more preferably -OH.
於-OM+p/p中,M表示1價、2價或3價之金屬陽離子,p表示1、2或3。作為M+p,例如可列舉鹼金屬、鹼土金屬或過渡金屬之金屬陽離子,較佳可列舉Na+、K+、Mg2+、Ca2+、Sr2+、Ba2+、Mn2+、Zn2+、Cu2+、Ni2+、Cd2+、Co2+、Al3+及Cr3+。 In -OM +p /p, M represents a monovalent, divalent or trivalent metal cation, and p represents 1, 2, or 3. Examples of M +p include metal cations of alkali metals, alkaline earth metals or transition metals, preferably Na + , K + , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Mn 2+ , Zn 2+ , Cu 2+ , Ni 2+ , Cd 2+ , Co 2+ , Al 3+ and Cr 3+ .
-ON+HR11R12R13中之R11、R12及R13、及-NH-(CH2)s-NR14R15中之R14及R15分別獨立地表示氫原子、碳數1~20之可經取代之烴基、或與相鄰之氮原子一併形成雜環者。上述烴基可為飽和或者不飽和脂肪族烴基或者芳香族烴基之任一者。 又,上述雜環可進而包含氮、氧、或者硫原子。作為R11、R12、R13、R14及R15,其中,較佳為氫原子、碳數1~20之烷基、碳數1~20之芳烷基、碳數5或6之環烷基、碳數6~10之芳基。就溶劑再溶解性之方面而言,其中,較佳為碳數3~20之烷基、碳數3~20之芳烷基、碳數5或6之環烷基、碳數6~10之芳基,更佳為碳數3~20之直鏈之烷基。此處,所謂溶劑再溶解性,係指已經乾燥過一次之色材分散液或感光性樹脂組成物之固形份再次溶解於溶劑中之性質。若溶劑再溶解性良好,則於製造彩色濾光片時附著之感光性樹脂組成物之乾燥物之去除、清掃變得容易,於製造上成為較大之優勢。 -ON + HR 11 R 12 R 13 in R 11 , R 12 and R 13 , and -NH-(CH 2 ) s -NR 14 R 15 in R 14 and R 15 each independently represent a hydrogen atom and carbon number The hydrocarbon group of 1-20 can be substituted, or the one that forms a heterocyclic ring together with the adjacent nitrogen atom. The above-mentioned hydrocarbon group may be either a saturated or unsaturated aliphatic hydrocarbon group or an aromatic hydrocarbon group. In addition, the heterocyclic ring may further include a nitrogen, oxygen, or sulfur atom. As R 11 , R 12 , R 13 , R 14 and R 15 , among them, a hydrogen atom, an alkyl group with 1 to 20 carbons, an aralkyl group with 1 to 20 carbons, and a ring with 5 or 6 carbons are preferred. Alkyl, aryl with 6-10 carbons. In terms of solvent resolubility, among them, alkyl groups with 3 to 20 carbons, aralkyl groups with 3 to 20 carbons, cycloalkyls with 5 or 6 carbons, and 6 to 10 carbons are preferred. The aryl group is more preferably a straight-chain alkyl group with a carbon number of 3-20. Here, the solvent re-solubility refers to the property that the solid content of the color material dispersion liquid or photosensitive resin composition that has been dried once is re-dissolved in the solvent. If the solvent resolubility is good, the removal and cleaning of the dried matter of the photosensitive resin composition attached during the manufacture of the color filter becomes easier, which becomes a great advantage in the manufacture.
作為-NH-(CH2)s-NR14R15中之胺成分之代表性者,例如可列舉:哌啶基甲基、二甲胺基乙基、二乙胺基乙基、二甲胺基丙基、二乙胺基丙基、二丁胺基丙基、哌啶基乙基、甲基哌啶基乙基、啉基乙基、哌啶基丙基、甲基哌啶基丙基、二乙胺基己基、二乙胺基乙氧基丙基、二乙胺基丁基、二甲胺基戊基、N-N-甲基-月桂基-胺基丙基、2-乙基己胺基乙基、硬脂胺基乙基、油胺基乙基等。 Representative examples of the amine component in -NH-(CH 2 ) s -NR 14 R 15 include piperidinyl methyl, dimethylaminoethyl, diethylaminoethyl, and dimethylamine. Propyl, diethylaminopropyl, dibutylaminopropyl, piperidinylethyl, methylpiperidinylethyl, Alkylethyl, piperidinylpropyl, methylpiperidinylpropyl, diethylaminohexyl, diethylaminoethoxypropyl, diethylaminobutyl, dimethylaminopentyl, NN -Methyl-lauryl-aminopropyl, 2-ethylhexylaminoethyl, stearylaminoethyl, oleylaminoethyl, etc.
就於使用鹽型分散劑之情形時,由於可利用與鹽型分散劑之鹽形成部位或殘存之胺基之相互作用提高分散劑之色材吸附力,故而對比度提高之方面而言,較佳為上述通式(1-m)所表示之單磺化衍生物及上述通式(1-d)所表示之二磺化衍生物具有未形成鹽之磺酸基(-SO3H)。又,上述通式(1-m)所表示之單磺化衍生物及上述通式(1-d)所表示之二磺化衍生物除磺酸基、磺醯胺基、磺酸鹽以外,亦可進而取代有鄰苯二甲醯亞胺甲基等其他官能基。 In the case of using a salt-type dispersant, since the interaction with the salt-forming site or the remaining amine group of the salt-type dispersant can be used to increase the color material adsorption capacity of the dispersant, it is preferable in terms of contrast improvement The monosulfonated derivative represented by the above general formula (1-m) and the disulfonated derivative represented by the above general formula (1-d) have a sulfonic acid group (-SO 3 H) that does not form a salt. In addition, the monosulfonated derivative represented by the above general formula (1-m) and the disulfonated derivative represented by the above general formula (1-d) except for a sulfonic acid group, a sulfonamide group, and a sulfonate, It may be further substituted with other functional groups such as phthaliminomethyl.
又,就溶劑再溶解性變得良好之方面而言,較佳為上述通式(1-m)及上述通式(1-d)之Z之至少1個為-NH-(CH2)s-NR14R15或-ON+HR11R12R13之情況。 In addition, in terms of improved solvent re-solubility, it is preferable that at least one of Z in the general formula (1-m) and the general formula (1-d) is -NH-(CH 2 ) s -NR 14 R 15 or -ON + HR 11 R 12 R 13 .
作為於本發明中適當使用之上述通式(1-m)所表示之單磺化衍生物、上述通式(1-d)所表示之二磺化衍生物,分別可列舉下述通式(i-m)所表示之單磺化衍生物、下述通式(i-d)所表示之二磺化衍生物。 As the monosulfonated derivative represented by the above general formula (1-m) and the disulfonated derivative represented by the above general formula (1-d) suitably used in the present invention, the following general formula ( The monosulfonated derivative represented by im), and the disulfonated derivative represented by the following general formula (id).
(於通式(i-m)及通式(i-d)中,X表示氫原子、氯原子或溴原子,數個X可分別相同,亦可不同;Z'表示-OH、-OM+p/p、或-NH-(CH2)s-NR14R15,數個Z'可分別相同,亦可不同;M表示1價、2價或3價之金屬陽離子,p表示1、2或3;R14及R15分別獨立地表示氫原子、碳數1~20之可經取代之烴基、或與相鄰之氮原子一併形成雜環者;s表示1~6之整數。) (In the general formula (im) and the general formula (id), X represents a hydrogen atom, a chlorine atom or a bromine atom, and several Xs may be the same or different; Z'represents -OH, -OM +p /p, Or -NH-(CH 2 ) s -NR 14 R 15 , several Z's may be the same or different; M represents a monovalent, divalent or trivalent metal cation, and p represents 1, 2 or 3; R 14 and R 15 each independently represent a hydrogen atom, a substituted hydrocarbon group with 1 to 20 carbon atoms, or one that forms a heterocyclic ring together with an adjacent nitrogen atom; s represents an integer of 1 to 6.)
上述吡咯并吡咯二酮系色材之單磺化衍生物之莫耳相對於上述吡咯并吡咯二酮系色材之單磺化衍生物與上述吡咯并吡咯二酮系色材之二磺化衍生物之莫耳之合計之比{單磺化衍生物 /(單磺化衍生物+二磺化衍生物)}只要為0.10以上且0.90以下,則並無特別限定,其中,就抑制加熱所導致之對比度之降低從而提高著色層之對比度之方面及色材分散液之分散穩定性之方面而言,較佳為0.20以上,更佳為0.30以上,進而更佳為0.50以上。又,雖並無特別限定,但就生產性之方面而言,上述比較佳為0.80以下,更佳為0.70以下。 The molar ratio of the monosulfonated derivative of the diketopyrrolopyrrole color material is relative to the monosulfonated derivative of the diketopyrrolopyrrole color material and the disulfonated derivative of the diketopyrrolopyrrole color material The ratio of the total moles of the substance {monosulfonated derivative/(monosulfonated derivative + disulfonated derivative)} is not particularly limited as long as it is 0.10 or more and 0.90 or less. Among them, heating is suppressed In terms of reducing the contrast to improve the contrast of the colored layer and the dispersion stability of the color material dispersion liquid, it is preferably 0.20 or more, more preferably 0.30 or more, and even more preferably 0.50 or more. Furthermore, although it is not particularly limited, in terms of productivity, the above-mentioned ratio is preferably 0.80 or less, and more preferably 0.70 or less.
再者,於本發明中,上述吡咯并吡咯二酮系色材之單磺化衍生物及上述吡咯并吡咯二酮系色材之二磺化衍生物可分別單獨使用1種或將2種以上混合使用。 Furthermore, in the present invention, the monosulfonated derivative of the diketopyrrolopyrrole color material and the disulfonated derivative of the diketopyrrolopyrrole color material may be used alone or in combination of two or more Mixed use.
於本發明之色材分散液中,就抑制加熱所導致之對比度降低之方面而言,上述吡咯并吡咯二酮系色材之單磺化衍生物及上述吡咯并吡咯二酮系色材之二磺化衍生物之合計含量相對於吡咯并吡咯二酮系色材100質量份,較佳為1質量份以上,較佳為1.5質量份以上,更佳為2質量份以上,另一方面,就進一步提高著色層之亮度之方面而言,較佳為20質量份以下,更佳為15質量份以下,更佳為12質量份以下,進而更佳為10質量份以下。 In the color material dispersion of the present invention, in terms of suppressing the decrease in contrast caused by heating, the monosulfonated derivative of the diketopyrrolopyrrole color material and the second of the diketopyrrolopyrrole color material The total content of the sulfonated derivatives relative to 100 parts by mass of the diketopyrrolopyrrole color material is preferably 1 part by mass or more, preferably 1.5 parts by mass or more, more preferably 2 parts by mass or more. In terms of further improving the brightness of the colored layer, it is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, more preferably 12 parts by mass or less, and still more preferably 10 parts by mass or less.
於本發明之色材分散液中,上述吡咯并吡咯二酮系色材之單磺化衍生物及上述吡咯并吡咯二酮系色材之二磺化衍生物之合計含量於色材與色素衍生物之合計含量(100質量%)中,較佳為1質量%以上且20質量%以下,更佳為1.5質量%以上且15質量%以下,進而更佳為2質量%以上且10質量%以下。藉由為上述下限值以上,可進一步抑制加熱所導致之對比度降低,藉由為上述上限值以下,可進一步提高著色層之亮度。 In the color material dispersion of the present invention, the total content of the monosulfonated derivative of the diketopyrrolopyrrole color material and the disulfonated derivative of the diketopyrrolopyrrole color material is derived from the color material and the pigment The total content (100% by mass) of the substance is preferably 1% by mass or more and 20% by mass or less, more preferably 1.5% by mass or more and 15% by mass or less, and still more preferably 2% by mass or more and 10% by mass or less . By being more than the above-mentioned lower limit, it is possible to further suppress the decrease in contrast caused by heating, and by being less than the above-mentioned upper limit, the brightness of the colored layer can be further improved.
本發明中使用之上述吡咯并吡咯二酮系色材之單磺 化衍生物及上述吡咯并吡咯二酮系色材之二磺化衍生物,例如可藉由將吡咯并吡咯二酮系色材投入至濃硫酸、發煙硫酸、氯磺酸或該等之混合液等磺化劑中進行磺化反應,以單磺化衍生物與二磺化衍生物之混合物之形式製造。磺化反應後,較佳為利用大量之水對反應液進行稀釋,或者於包含製造金屬鹽或胺鹽時所需之金屬鹽或胺之水溶液中進行中和,於對所獲得之懸浮液進行過濾後,利用水系之洗淨液進行洗淨並乾燥。藉由適當選擇所使用之水溶液中之金屬鹽或胺,可如設計般適當導入磺酸之鹽。又,於製造磺醯胺時,使亞硫醯氯作用於藉由上述磺化反應而獲得之磺化衍生物,製成磺醯氯後與胺進行混合,藉此可如設計般適當導入磺化醯胺。 The monosulfonated derivative of the diketopyrrolopyrrole color material and the disulfonated derivative of the diketopyrrolopyrrole color material used in the present invention can be used, for example, by adding the diketopyrrolopyrrole color material Put it into a sulfonating agent such as concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, or a mixture of these to perform sulfonation reaction, and manufacture as a mixture of monosulfonated derivatives and disulfonated derivatives. After the sulfonation reaction, it is preferable to use a large amount of water to dilute the reaction solution, or to neutralize the resulting suspension in an aqueous solution containing the metal salt or amine required for the production of the metal salt or amine salt. After filtration, use an aqueous cleaning solution to clean and dry. By appropriately selecting the metal salt or amine in the aqueous solution used, the sulfonic acid salt can be appropriately introduced as designed. In addition, in the production of sulfonamides, the sulfonated derivative obtained by the sulfonation reaction is made to act on sulfite chloride, and the sulfonate chloride is mixed with the amine, so that the sulfonate can be appropriately introduced as designed. Amide.
於利用上述方法進行磺化之情形時,藉由調整反應液濃度、反應溫度、反應時間等,可控制每1個分子之磺酸基或磺醯胺基之導入量、及單磺化衍生物與二磺化衍生物之混合比例。具體而言,藉由提高磺化劑之硫酸濃度、或提高磺化反應之反應溫度、或延長反應時間,可使二磺化衍生物增多。 In the case of sulfonation using the above method, by adjusting the concentration of the reaction solution, reaction temperature, reaction time, etc., the introduction amount of sulfonic acid groups or sulfonamide groups per molecule, and monosulfonated derivatives can be controlled Mixing ratio with disulfonated derivatives. Specifically, by increasing the sulfuric acid concentration of the sulfonating agent, or increasing the reaction temperature of the sulfonation reaction, or prolonging the reaction time, the number of disulfonated derivatives can be increased.
作為用於製造上述吡咯并吡咯二酮系色材之單磺化衍生物及上述吡咯并吡咯二酮系色材之二磺化衍生物之吡咯并吡咯二酮系色材,例如較佳為具有下述通式(2)所表示之結構之吡咯并吡咯二酮系色材。 As the monosulfonated derivative of the diketopyrrolopyrrole color material and the disulfonated derivative of the diketopyrrolopyrrole color material, the diketopyrrolopyrrole color material, for example, preferably has The diketopyrrolopyrrole color material of the structure represented by the following general formula (2).
[化5]
(於通式(2)中,Y1及Y2、以及n及m分別獨立地與通式(1-m)及通式(1-d)相同;於n及m為2以上之情形時,數個Y1及Y2可分別相同,亦可不同。) (In the general formula (2), Y 1 and Y 2 , and n and m are independently the same as the general formula (1-m) and the general formula (1-d); when n and m are 2 or more , Several Y 1 and Y 2 can be the same or different respectively.)
於上述通式(2)中,關於Y1及Y2、以及n及m,可與上述通式(1-m)及上述通式(1-d)相同,因此省略此處之說明。 In the above general formula (2), Y 1 and Y 2 , and n and m may be the same as the above general formula (1-m) and the above general formula (1-d), so the description here is omitted.
作為用於製造包含上述吡咯并吡咯二酮系色材之單磺化衍生物與上述吡咯并吡咯二酮系色材之二磺化衍生物之混合物之吡咯并吡咯二酮系色材,其中,就抑制加熱所導致之對比度之降低之效果較高之方面而言,較佳為C.I.顏料橙71、C.I.顏料紅254、255、264、272,更佳為C.I.顏料紅254、255,尤佳為C.I.顏料紅254。 As a diketopyrrolopyrrole color material for producing a mixture of the monosulfonated derivative of the diketopyrrolopyrrole color material and the disulfonated derivative of the diketopyrrolopyrrole color material, the diketopyrrolopyrrole color material is As far as the effect of suppressing the decrease in contrast caused by heating is high,
本發明所使用之色素衍生物亦可於無損本發明之效果之範圍內,除上述吡咯并吡咯二酮系色材之單磺化衍生物及上述吡咯并吡咯二酮系色材之二磺化衍生物以外,進而含有其他色素衍生物。作為其他色素衍生物,例如就色調之方面而言,可較佳地使用具有黃色色材之色素骨架之色素衍生物,其中,就抑制加熱所導致之對比 度之降低從而提高著色層之對比度之方面而言,可較佳地使用C.I.顏料黃138(PY138)之磺化衍生物。 The pigment derivatives used in the present invention can also be within the range that does not impair the effects of the present invention, except for the monosulfonated derivatives of the diketopyrrolopyrrole color materials and the disulfonation of the diketopyrrolopyrrole color materials. In addition to derivatives, other pigment derivatives are further included. As other pigment derivatives, for example, in terms of hue, a pigment derivative having a pigment skeleton of a yellow color material can be preferably used. Among them, in terms of suppressing the decrease in contrast caused by heating and improving the contrast of the colored layer In general, the sulfonated derivative of CI Pigment Yellow 138 (PY138) can be preferably used.
作為PY138之磺化衍生物,可列舉於PY138鍵結有選自由磺酸基、磺醯胺基、及磺酸鹽所構成之群組中之至少1種之具有以下之通式(S)所表示之結構者。 As the sulfonated derivative of PY138, at least one selected from the group consisting of a sulfonic acid group, a sulfonamide group, and a sulfonate bonded to PY138 has the following general formula (S) Representation of the structure.
(於通式(S)中,Z"係選自由磺酸基、-SO2NH-(CH2)v-NR'R"、-SO2NH-(CH2)v-COOH、-SO2NH-(CH2)v-SO3H、及磺酸鹽所構成之群組中之1種,R'及R"分別獨立地表示氫原子、碳數1~20之可經取代之烴基、或與相鄰之氮原子一併形成雜環者,v分別獨立地為1~6之整數;w表示取代基數,且表示1~4之整數。) (In the general formula (S), Z" is selected from sulfonic acid group, -SO 2 NH-(CH 2 ) v -NR'R", -SO 2 NH-(CH 2 ) v -COOH, -SO 2 One of the group consisting of NH-(CH 2 ) v -SO 3 H and sulfonate, R'and R" each independently represent a hydrogen atom, a substituted hydrocarbon group with 1 to 20 carbon atoms, Or if it forms a heterocyclic ring together with adjacent nitrogen atoms, v is independently an integer from 1 to 6; w represents the number of substituents, and represents an integer from 1 to 4.)
上述通式(S)之R'及R"與上述通式(1-d)及上述通式(1-m)之R14及R15相同。作為以上述-SO2NH-(CH2)v-NR'R"所表示之取代基之形式導入之胺成分之代表性者,例如可列舉與作為上述通式(1-m)及上述通式(1-d)之-NH-(CH2)s-NR14R15中之胺成分之代表性者例示者相同者。就於使用鹽型分散劑之情形時,由於可利用與鹽型分散劑之鹽形成部位或殘存之胺基之相互作用提高分散劑之 色材吸附力,故而對比度提高之方面而言,作為PY138之磺化衍生物,較佳為存在未形成鹽之磺酸基之情況。又,於上述-SO2NH-(CH2)v-NR'R"所表示之磺醯胺基之情況、及與包含碳數為3以上之長鏈烷基之胺基形成鹽之磺酸鹽之情形時,溶劑再溶解性變得良好,就該點而言較佳。 R'and R" of the above general formula (S) are the same as R 14 and R 15 of the above general formula (1-d) and the above general formula (1-m). As the above -SO 2 NH-(CH 2 ) Representative examples of amine components introduced in the form of substituents represented by v -NR'R" include, for example, -NH-(CH 2 ) The representative examples of the amine components in s -NR 14 R 15 are the same. In the case of using a salt-type dispersant, the interaction with the salt-forming site or the remaining amine group of the salt-type dispersant can be used to increase the color material adsorption capacity of the dispersant, so in terms of contrast improvement, it is PY138 The sulfonated derivative of the sulfonate is preferably the case where there is a sulfonic acid group that does not form a salt. In addition, in the case of the sulfonamide group represented by the above -SO 2 NH-(CH 2 ) v -NR'R", and the sulfonic acid that forms a salt with an amine group containing a long-chain alkyl group having 3 or more carbon atoms In the case of a salt, the solvent re-solubility becomes good, which is preferable in this point.
作為適當使用之取代基,可列舉磺酸基、-SO2NHC2H4COOH、-SO3-N(CH3)2(C18H37)2 +、-SO2NHC3H6N(C2H5)2等,其中,較佳為磺酸基。 Examples of suitably used substituents include sulfonic acid groups, -SO 2 NHC 2 H 4 COOH, -SO 3 -N(CH 3 ) 2 (C 18 H 37 ) 2 + , -SO 2 NHC 3 H 6 N( C 2 H 5 ) 2 and the like, among them, a sulfonic acid group is preferred.
又,於通式(S)中,就提高著色層之對比度及耐熱性之方面而言,取代基數w較佳為1~2,其中,較佳為1。 Furthermore, in the general formula (S), the number of substituents w is preferably 1 to 2 in terms of improving the contrast and heat resistance of the colored layer, and among them, 1 is preferred.
PY138之磺化衍生物例如可藉由於製造上述吡咯并吡咯二酮系色材之單磺化衍生物與上述吡咯并吡咯二酮系色材之二磺化衍生物之混合物之方法中,使用PY138代替吡咯并吡咯二酮系色材而製造。 The sulfonated derivative of PY138 can be used, for example, in a method for producing a mixture of the monosulfonated derivative of the diketopyrrolopyrrole color material and the disulfonated derivative of the diketopyrrolopyrrole color material. Manufactured instead of diketopyrrolopyrrole color materials.
作為PY138之磺化衍生物,可單獨使用1種或將2種以上混合使用。例如,亦可將磺酸基及/或磺醯胺基之種類、取代位置或取代數不同之2種以上之磺化衍生物混合使用。 As the sulfonated derivative of PY138, one kind can be used alone or two or more kinds can be used in combination. For example, two or more sulfonated derivatives different in the type, substitution position, or substitution number of the sulfonic acid group and/or the sulfonamide group may be used in combination.
於本發明之色材分散液中,於含有PY138之磺化衍生物之情形時,PY138之磺化衍生物之含量於色材與色素衍生物之合計含量(100質量%)中,較佳為1質量%以上且15質量%以下,更佳為1.5質量%以上且10質量%以下,進而較佳為2質量%以上且7質量%以下。藉由以此種含量使用,不大幅改變色調便可製作達成高亮度且高對比度化之要求之著色層。 In the color material dispersion of the present invention, when the sulfonated derivative of PY138 is contained, the content of the sulfonated derivative of PY138 is based on the total content (100% by mass) of the color material and the pigment derivative, preferably 1% by mass or more and 15% by mass or less, more preferably 1.5% by mass or more and 10% by mass or less, and still more preferably 2% by mass or more and 7% by mass or less. By using this content, a coloring layer that meets the requirements of high brightness and high contrast can be produced without greatly changing the color tone.
又,於本發明之色材分散液中,色素衍生物之含量於 色材與色素衍生物之合計含量(100質量%)中,較佳為1質量%以上且30質量%以下,更佳為2質量%以上且20質量%以下。藉由以此種含量使用,可進一步提高著色層之亮度及對比度。 In addition, in the color material dispersion of the present invention, the content of the pigment derivative in the total content (100% by mass) of the color material and the pigment derivative is preferably 1% by mass or more and 30% by mass or less, more preferably 2% by mass or more and 20% by mass or less. By using this content, the brightness and contrast of the colored layer can be further improved.
本發明所使用之色材包含吡咯并吡咯二酮系色材。於本發明中,藉由將包含上述吡咯并吡咯二酮系色材之單磺化衍生物及上述吡咯并吡咯二酮系色材之二磺化衍生物之混合物與吡咯并吡咯二酮系色材組合使用,可抑制塗膜之對比度降低。作為本發明所使用之吡咯并吡咯二酮系色材,較佳為具有下述通式(2')所表示之結構之吡咯并吡咯二酮系色材。 The color material used in the present invention includes a diketopyrrolopyrrole color material. In the present invention, a mixture of the monosulfonated derivative of the diketopyrrolopyrrole color material and the disulfonated derivative of the diketopyrrolopyrrole color material is combined with the diketopyrrolopyrrole color material. The combination of materials can prevent the decrease of the contrast of the coating film. The diketopyrrolopyrrole color material used in the present invention is preferably a diketopyrrolopyrrole color material having a structure represented by the following general formula (2').
(於通式(2')中,Y1及Y2分別獨立地與通式(1-m)及通式(1-d)相同;n'及m'分別獨立地表示0~5之整數;於n'及m'為2以上之情形時,數個Y1及Y2可分別相同,亦可不同。) (In the general formula (2'), Y 1 and Y 2 are independently the same as the general formula (1-m) and the general formula (1-d); n'and m'each independently represent an integer from 0 to 5 ; When n'and m'are 2 or more, several Y 1 and Y 2 may be the same or different respectively.)
於上述通式(2')中,Y1及Y2可與上述通式(1-m)及上述通式(1-d)相同,因此,省略此處之說明。上述通式(2')中之n'及m'分別獨立地為鍵結於吡咯并吡咯二酮骨架之苯基之取代基之數 量,更佳為分別為0或1。於使用作為色材而非上述色素衍生物之原料之吡咯并吡咯二酮系色材所具有之上述通式(2')所表示之結構中,n'及m'尤其更佳為分別為1。關於通式(2')中之取代基Y1及Y2,只要根據所需顏色適當選擇即可,其中,較佳為鹵素原子、氰基、甲基、苯基,尤其是較佳為氯原子、溴原子。 In the above general formula (2'), Y 1 and Y 2 may be the same as the above general formula (1-m) and the above general formula (1-d), therefore, the description here is omitted. In the above general formula (2'), n'and m'are each independently the number of substituents of the phenyl group bonded to the diketopyrrolopyrrole skeleton, more preferably 0 or 1, respectively. In the structure represented by the general formula (2') of the diketopyrrolopyrrole-based color material used as the color material instead of the raw material of the pigment derivative, n'and m'are particularly preferably 1 respectively . Regarding the substituents Y 1 and Y 2 in the general formula (2'), they can be appropriately selected according to the desired color. Among them, halogen atoms, cyano groups, methyl groups, and phenyl groups are preferred, and chlorine is especially preferred. Atom, bromine atom.
作為本發明所使用之吡咯并吡咯二酮系色材之平均一次粒徑,於製成彩色濾光片之著色層之情形時,只要可實現所需之顯色即可,適當調整即可。其中,較佳為10~100nm之範圍內,更佳為15~60nm。再者,上述色材之平均粒徑可利用根據電子顯微鏡照片直接測量一次粒子之大小之方法求出。具體而言,測量各個一次粒子之短軸徑與長軸徑,並將其平均值設為該粒子之粒徑。繼而,將100個以上之粒子分別與所求出之粒徑之長方體近似而求出粒子之體積(質量),求出體積平均粒徑並將其設為平均粒徑。再者,電子顯微鏡使用穿透型(TEM)或掃描型(SEM)之任一者均可獲得相同結果。 As the average primary particle size of the diketopyrrolopyrrole color material used in the present invention, when the coloring layer of the color filter is formed, the desired color development can be achieved, and it can be adjusted appropriately. Among them, it is preferably in the range of 10 to 100 nm, and more preferably 15 to 60 nm. Furthermore, the average particle size of the above-mentioned color material can be obtained by directly measuring the size of the primary particles from electron micrographs. Specifically, the minor axis diameter and the major axis diameter of each primary particle are measured, and the average value is taken as the particle diameter of the particle. Then, the volume (mass) of the particles is obtained by approximating 100 or more particles to the rectangular parallelepiped of the obtained particle size, and the volume average particle size is obtained and used as the average particle size. Furthermore, the same result can be obtained by using either transmission type (TEM) or scanning type (SEM) for the electron microscope.
本發明所使用之吡咯并吡咯二酮系色材可利用再結晶法、溶劑鹽研磨法等公知之方法製造。亦可使用市售之C.I.顏料紅254、255、264、272、C.I.顏料橙71等。於吡咯并吡咯二酮系色材為C.I.顏料紅254之情形時,例如,可對CLARIANT製造之商品名Hostaperm Red D2B-COFLV3781、BASF JAPAN製造之商品名Irgaphor Red B-CF等市售之C.I.顏料紅254進行研磨後使用。 The diketopyrrolopyrrole color material used in the present invention can be produced by a known method such as a recrystallization method and a solvent salt grinding method. Commercially available C.I. Pigment Red 254, 255, 264, 272, C.I.
於本發明之色材分散液中,色材整體中所包含之吡咯并吡咯二酮系色材之含有比例較佳為20質量%以上,更佳為30質量%以上,進而更佳為35質量%以上。又,於本發明之色材分散液 中,色材及色素衍生物之合計中所包含之吡咯并吡咯二酮系色材之含有比例較佳為20質量%以上,更佳為30質量%以上,進而更佳為35質量%以上。 In the color material dispersion of the present invention, the content of the diketopyrrolopyrrole color material contained in the entire color material is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 35% by mass %above. In addition, in the color material dispersion of the present invention, the content of the diketopyrrolopyrrole color material contained in the total of the color material and the pigment derivative is preferably 20% by mass or more, more preferably 30% by mass or more , And more preferably 35% by mass or more.
於本發明中,為了達成所需色度,作為色材,除吡咯并吡咯二酮系色材以外,亦可於無損本發明之效果之範圍內進而含有其他色材。作為其他色材,並無特別限定,可列舉各種有機顏料、無機顏料及可分散之染料等,其中,有機顏料之顯色性較高且耐熱性亦較高,因此可較佳地使用。例如,藉由將作為其他色材之紅色顏料、或橙色顏料或黃色顏料等與吡咯并吡咯二酮系色材組合,可調整成所需之適合紅色著色層之色度。 In the present invention, in order to achieve the desired chromaticity, as the color material, in addition to the diketopyrrolopyrrole-based color material, other color materials may be further contained within a range that does not impair the effects of the present invention. There are no particular limitations on other color materials, and various organic pigments, inorganic pigments, and dispersible dyes can be cited. Among them, organic pigments have high color rendering properties and high heat resistance, so they can be preferably used. For example, by combining red pigments, orange pigments, or yellow pigments as other color materials with diketopyrrolopyrrole color materials, the desired chromaticity of the red color layer can be adjusted.
作為上述使用作為其他色材之有機顏料,例如可列舉於色指數(C.I.;The Society of Dyers and Colourists公司發行)中分類為顏料(Pigment)之化合物、具體而言標註如下述之色指數(C.I.)編號者。 As the above-mentioned organic pigments used as other color materials, for example, compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colourists), specifically labeled as the following color index (CI ) Numbered person.
C.I.顏料黃1、3、12、13、14、15、16、17、20、24、31、55、60、61、65、71、73、74、81、83、93、95、97、98、100、101、104、106、108、109、110、113、114、116、117、119、120、126、127、128、129、138、139、150、151、152、153、154、155、156、166、168、175;C.I.顏料橙1、5、13、14、16、17、24、34、36、38、40、43、46、49、51、61、63、64、71、73;C.I.顏料紅1、2、3、4、5、6、7、8、9、10、11、12、14、15、16、17、18、19、21、22、23、30、31、32、37、38、40、41、42、48:1、48:2、 48:3、48:4、49:1、49:2、50:1、52:1、53:1、57、57:1、57:2、58:2、58:4、60:1、63:1、63:2、64:1、81:1、83、88、90:1、97、101、102、104、105、106、108、112、113、114、122、123、144、146、149、150、151、166、168、170、171、172、174、175、176、177、178、179、180、185、187、188、190、193、194、202、206、207、208、209、215、216、220、224、226、242、243、245、265。 CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 55, 60, 61, 65, 71, 73, 74, 81, 83, 93, 95, 97, 98 , 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 126, 127, 128, 129, 138, 139, 150, 151, 152, 153, 154, 155 , 156, 166, 168, 175; CI Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73; CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31 , 32, 37, 38, 40, 41, 42, 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 53:1, 57 , 57:1, 57:2, 58:2, 58:4, 60:1, 63:1, 63:2, 64:1, 81:1, 83, 88, 90:1, 97, 101, 102 , 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179 , 180, 185, 187, 188, 190, 193, 194, 202, 206, 207, 208, 209, 215, 216, 220, 224, 226, 242, 243, 245, 265.
作為上述無機顏料之具體例,可列舉氧化鈦、鈦黑、碳黑等。 As specific examples of the above-mentioned inorganic pigments, titanium oxide, titanium black, carbon black, and the like can be cited.
作為上述可分散之染料,可列舉:藉由對染料賦予各種取代基使之不溶於溶劑中而變得可分散之染料,或藉由與溶解度較低之溶劑組合使用而變得可分散之染料,或將可溶性之染料與相對離子形成鹽而對溶劑不溶化(色澱化)之色澱色材。藉由將此種可分散之染料與分散劑組合使用,可提高該染料之分散性或分散穩定性。再者,作為標準,只要相對於10g溶劑(或混合溶劑),染料之溶解量為100mg以下,則可判定該染料可於該溶劑(或混合溶劑)中分散。作為上述可分散之染料,可自習知公知之染料之中適當選擇,並無特別限定,例如可列舉:偶氮染料、金屬錯鹽偶氮染料、蒽醌染料、三苯甲烷染料、染料、花青染料、萘醌染料、醌亞胺染料、次甲基染料、酞菁染料等。 Examples of the above-mentioned dispersible dyes include: dyes that are made dispersible by imparting various substituents to the dyes to make them insoluble in a solvent, or dyes that are made dispersible by being used in combination with a solvent with lower solubility , Or a lake color material that forms a salt with a soluble dye and an opposite ion, but does not dissolve (lake) in the solvent. By using such a dispersible dye in combination with a dispersant, the dispersibility or dispersion stability of the dye can be improved. Furthermore, as a standard, as long as the dissolved amount of the dye is 100 mg or less relative to 10 g of the solvent (or mixed solvent), it can be determined that the dye can be dispersed in the solvent (or mixed solvent). The above-mentioned dispersible dyes can be appropriately selected from conventionally known dyes, and are not particularly limited. For example, azo dyes, metal complex salt azo dyes, anthraquinone dyes, triphenylmethane dyes, Dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, phthalocyanine dyes, etc.
其中,作為可與吡咯并吡咯二酮系色材組合而較佳地使用之其他色材,可列舉選自由C.I.顏料紅177、242、C.I.顏料黃138、139、150所構成之群組中之至少1種。又,於本發明中,就抑制加熱所導致之對比度之降低,提高著色層之對比度之方面而 言,作為上述其他色材,較佳為含有如下黃色色材:其係選自由下述通式(A)所表示之偶氮化合物及其互變異構結構之偶氮化合物之單、二、三及四陰離子所構成之群組中之至少1種陰離子、選自由Cd、Co、Al、Cr、Sn、Pb、Zn、Fe、Ni、Cu及Mn所構成之群組中之至少2種金屬離子、及下述通式(B)所表示之化合物的複合分子。又,若組合該特定之黃色色材使用,則就抑制P/V比((組成物中之色材成分質量)/(組成物中之色材成分以外之固形份質量)比),容易形成紅色著色層,製版性提高之方面而言亦較佳。再者,此處所言之色材成分中包含色材及色素衍生物。 Among them, other color materials that can be preferably used in combination with diketopyrrolopyrrole color materials include those selected from the group consisting of CI Pigment Red 177, 242, CI Pigment Yellow 138, 139, and 150 At least one. Furthermore, in the present invention, in terms of suppressing the decrease in contrast caused by heating and improving the contrast of the colored layer, as the above-mentioned other color material, it is preferable to contain the following yellow color material: which is selected from the following general formulas (A) At least one anion in the group consisting of the mono-, di-, tri-, and tetra-anions of the azo compound and its tautomeric structure of the azo compound, selected from Cd, Co, Al, Cr, A composite molecule of at least two metal ions in the group consisting of Sn, Pb, Zn, Fe, Ni, Cu, and Mn, and a compound represented by the following general formula (B). In addition, if the specific yellow color material is used in combination, the P/V ratio ((the mass of the color material in the composition)/(the mass of the solid content other than the color material in the composition) ratio) can be suppressed, and it is easy to form The red colored layer is also better in terms of improved plate-making properties. Furthermore, the color material components mentioned here include color materials and pigment derivatives.
(於通式(A)中,Ra分別獨立地為-OH、-NH2、-NH-CN、醯基胺基、烷基胺基或芳基胺基,Rb分別獨立地為-OH或-NH2) (In the general formula (A), R a is each independently -OH, -NH 2 , -NH-CN, an acylamino group, an alkylamino group or an arylamino group, and R b is each independently -OH Or -NH 2 )
(通式(B)中,Rc分別獨立地為氫原子或烷基) (In the general formula (B), R c is each independently a hydrogen atom or an alkyl group)
於由上述通式(A)所表示之偶氮化合物及其互變異構結構之偶氮化合物之陰離子與特定之金屬離子構成之金屬錯合 物、及上述通式(B)所表示之化合物之複合分子中,該等分子間之鍵例如可藉由分子間相互作用、或藉由路易斯酸-鹼相互作用、或藉由配位鍵而形成。又,亦可為如客體分子被組入至構成主體分子之格子中之包接化合物般之結構。或者,亦可為2種物質形成共同結晶,且形成第二成分之原子位於第一成分之規則性格子之位置之混合置換結晶。 Among the metal complexes composed of the anion of the azo compound represented by the above general formula (A) and the azo compound of its tautomeric structure and a specific metal ion, and the compound represented by the above general formula (B) In a composite molecule, the intermolecular bonds can be formed, for example, by intermolecular interactions, or by Lewis acid-base interactions, or by coordination bonds. In addition, it may also have a structure like an inclusion compound in which guest molecules are incorporated into the lattice constituting the host molecule. Alternatively, it can also be a mixed replacement crystal in which two substances form a common crystal, and the atoms of the second component are located in the regular lattice of the first component.
作為上述通式(A)中之醯基胺基中之醯基,例如可列舉:烷基羰基、苯基羰基、烷基磺醯基、苯基磺醯基、可經烷基、苯基、或萘基取代之胺甲醯基、可經烷基、苯基、或萘基取代之胺磺醯基、可經烷基、苯基、或萘基取代之甲脒基等。上述烷基之碳數較佳為1以上且6以下。又,上述烷基例如亦可經F、Cl、Br等鹵素、-OH、-CN、-NH2、及/或碳數1以上且6以下之烷氧基取代。又,上述苯基及萘基例如亦可經F、Cl、Br等鹵素、-OH、-CN、-NH2、-NO2、碳數1以上且6以下之烷基、及/或碳數1以上且6以下之烷氧基取代。作為上述通式(A)中之烷基胺基中之烷基,較佳為碳數為1以上且6以下。上述烷基例如亦可經F、Cl、Br等鹵素、-OH、-CN、-NH2、及/或碳數1以上且6以下之烷氧基取代。作為上述通式(A)中之芳基胺基中之芳基,可列舉苯基、萘基,該等芳基例如亦可經F、Cl、Br等鹵素、-OH、碳數1以上且6以下之烷基、碳數1以上且6以下之烷氧基、-NH2、-NO2及-CN等取代。 As the acyl group in the acylamino group in the above general formula (A), for example, an alkylcarbonyl group, a phenylcarbonyl group, an alkylsulfonyl group, a phenylsulfonyl group, an alkyl group, a phenyl group, Or naphthyl substituted aminoformyl, alkyl, phenyl, or naphthyl substituted aminosulfonyl, alkyl, phenyl, or naphthyl substituted formamidino, etc. The carbon number of the above-mentioned alkyl group is preferably 1 or more and 6 or less. In addition, the above-mentioned alkyl group may be substituted with halogens such as F, Cl, and Br, -OH, -CN, -NH 2 , and/or an alkoxy group having 1 to 6 carbon atoms, for example. In addition, the above-mentioned phenyl group and naphthyl group may be subjected to halogens such as F, Cl, Br, -OH, -CN, -NH 2 , -NO 2 , alkyl groups with 1 to 6 carbon atoms, and/or carbon atoms. Alkoxy substituted with 1 or more and 6 or less. The alkyl group in the alkylamino group in the general formula (A) preferably has a carbon number of 1 or more and 6 or less. The above-mentioned alkyl group may be substituted with halogens such as F, Cl, and Br, -OH, -CN, -NH 2 , and/or an alkoxy group having 1 to 6 carbon atoms, for example. Examples of the aryl group in the arylamino group in the above general formula (A) include phenyl and naphthyl. These aryl groups may be substituted with halogens such as F, Cl, and Br, -OH, and carbon number of 1 or more. Substitutions such as alkyl groups of 6 or less, alkoxy groups of 1 to 6 carbon atoms, -NH 2 , -NO 2 and -CN.
於上述通式(A)所表示之偶氮化合物及其互變異構結構之偶氮化合物中,作為Ra,就成為紅色色調之方面而言,較佳為分別獨立地為-OH、-NH2、-NH-CN、或烷基胺基、2個Ra可分別相同,亦可不同。於上述通式(A)中,關於2個Ra,其中,就色調 之方面而言,進而較佳為兩者均為-OH之情況、兩者均為-NH-CN之情況、或一個為-OH且另一個為-NH-CN之情況,進而更佳為兩者均為-OH之情況。 Azo compound and an azo compound of the structural configuration to the tautomers of formula (A) represented by the sum, as R a, in terms of aspect became red hues, preferably are each independently -OH, -NH 2, -NH-CN, or an alkyl group, two R a may be the same, respectively, or different. In the above-mentioned general formula (A), regarding two Ras , among them, in terms of hue, it is more preferable that both are -OH, both are -NH-CN, or one When it is -OH and the other is -NH-CN, it is more preferable that both are -OH.
又,於上述通式(A)所表示之偶氮化合物及其互變異構結構之偶氮化合物中,作為Rb,就色調之方面而言,更佳為兩者均為-OH之情況。 In addition, in the azo compound represented by the general formula (A) and the azo compound of the tautomeric structure, as R b , in terms of color tone, it is more preferable that both are -OH.
作為選自由Cd、Co、Al、Cr、Sn、Pb、Zn、Fe、Ni、Cu及Mn所構成之群組中之至少2種金屬,其中,較佳為至少包含1種成為2價或3價之陽離子之金屬,較佳為包含選自由Ni、Cu、及Zn所構成之群組中之至少1種,進而較佳為至少包含Ni。進而較佳為包含Ni及進而選自由Cd、Co、Al、Cr、Sn、Pb、Zn、Fe、Cu及Mn所構成之群組中之至少1種金屬,進而更佳為包含Ni及進而選自由Zn、Cu、Al及Fe所構成之群組中之至少1種金屬。其中,作為上述至少2種金屬,尤佳為Ni與Zn或Ni與Cu。 As at least two metals selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu, and Mn, it is preferable to include at least one of them to become divalent or 3 The metal of the valence cation preferably contains at least one selected from the group consisting of Ni, Cu, and Zn, and more preferably contains at least Ni. More preferably, it contains Ni and at least one metal selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Cu, and Mn, and more preferably contains Ni and further selected At least one metal from the group consisting of Zn, Cu, Al, and Fe. Among them, as the above-mentioned at least two kinds of metals, Ni and Zn or Ni and Cu are particularly preferred.
於上述黃色色材中,至少2種金屬之含有比例只要適當製備即可。其中,就呈紅色色調之方面而言,於上述黃色色材中,關於Ni與進而選自由Cd、Co、Al、Cr、Sn、Pb、Zn、Fe、Cu及Mn所構成之群組中之至少1種金屬之含有比例,較佳為以Ni:其他上述至少1種金屬為97:3~10:90之莫耳比包含,進而較佳為以95:5~10:90之莫耳比包含。其中,就呈紅色色調之方面而言,較佳為以Ni:Zn為90:10~10:90之莫耳比包含Ni與Zn,進而較佳為以80:20~20:80之莫耳比包含。或者,就呈紅色色調之方面而言,較佳為以Ni:Cu為97:3~10:90之莫耳比包含Ni與Cu,進而較佳為以96:4~20:80之莫耳比包含。於黃色色材 呈紅色色調之情形時,即便抑制P/V比,亦容易製作高色濃度之紅色之色度區域中所包含之紅色像素。 In the above-mentioned yellow color material, the content ratio of at least two kinds of metals may be appropriately prepared. Among them, in terms of the red hue, in the above-mentioned yellow color material, regarding Ni and further selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Cu, and Mn The content ratio of at least one metal is preferably Ni: the other above-mentioned at least one metal is contained in a molar ratio of 97:3-10:90, and more preferably a molar ratio of 95:5-10:90. Include. Among them, in terms of the red hue, it is preferable to include Ni and Zn in a molar ratio of Ni:Zn of 90:10 to 10:90, and more preferably to have a molar ratio of 80:20 to 20:80. Than contains. Or, in terms of the red hue, it is preferable to include Ni and Cu with a molar ratio of Ni:Cu of 97:3 to 10:90, and more preferably a molar ratio of 96:4 to 20:80 Than contains. When the yellow color material has a red hue, even if the P/V ratio is suppressed, it is easy to produce the red pixels contained in the red chromaticity area with high color density.
上述黃色色材亦可進而包含與上述特定之金屬離子不同之金屬離子。上述黃色色材例如亦可包含選自由Li、Cs、Mg、Na、K、Ca、Sr、Ba及La所構成之群組中之至少1種金屬離子。 The yellow color material may further include a metal ion different from the specific metal ion. The yellow color material may include, for example, at least one metal ion selected from the group consisting of Li, Cs, Mg, Na, K, Ca, Sr, Ba, and La.
作為於上述黃色色材中至少包含2種金屬離子之態樣,可列舉於共通之結晶格子中至少包含2種金屬離子之情況、及於分開之結晶格子中分別各包含1種金屬離子之結晶凝集之情況。其中,就對比度進一步提高之方面而言,較佳為於共通之結晶格子中至少包含2種金屬離子之情況。再者,於共通之結晶格子中至少包含2種金屬離子之態樣或於分開之結晶格子中分別各包含1種金屬離子之結晶凝集之態樣,可參照例如日本專利特開2014-12838號公報並使用X射線繞射法適當判斷。 Examples of the aspect in which at least two metal ions are contained in the yellow color material include a case where at least two metal ions are contained in a common crystal lattice, and crystals each containing one metal ion in separate crystal lattices. The situation of agglutination. Among them, in terms of further improvement in contrast, the case where at least two types of metal ions are contained in a common crystal lattice is preferable. Furthermore, for the state where at least two metal ions are contained in a common crystal lattice or the state where crystals each containing one metal ion in separate crystal lattices are aggregated, please refer to, for example, Japanese Patent Laid-Open No. 2014-12838 Communiqué and use the X-ray diffraction method to make appropriate judgments.
作為上述通式(B)中之Rc中之烷基,較佳為碳數1以上且6以下之烷基,進而較佳為碳數1以上且4以下之烷基。該烷基亦可經-OH基取代。其中,Rc較佳為氫原子。 The alkyl group in R c in the general formula (B) is preferably an alkyl group having 1 or more and 6 or less carbon atoms, and more preferably an alkyl group having 1 or more and 4 or less carbon atoms. The alkyl group may also be substituted by -OH group. Among them, R c is preferably a hydrogen atom.
關於上述通式(B)所表示之化合物之含量,以上述通式(A)所表示之偶氮化合物及其互變異構結構之偶氮化合物之1莫耳為基準,通常為5莫耳以上且300莫耳以下,較佳為10莫耳以上且250莫耳以下,進而較佳為100莫耳以上且200莫耳以下。 Regarding the content of the compound represented by the above general formula (B), based on 1 mol of the azo compound represented by the above general formula (A) and the azo compound of its tautomeric structure, it is usually 5 mol or more And 300 mol or less, preferably 10 mol or more and 250 mol or less, and more preferably 100 mol or more and 200 mol or less.
又,於上述黃色色材中,亦可進而包含:脲及取代脲、例如苯基脲、十二烷基脲等、以及其與醛、尤其是甲醛之縮聚物;雜環、例如巴比妥酸、苯并咪唑酮、苯并咪唑酮-5-磺酸、2,3-二羥基喹啉、2,3-二羥基喹啉-6-磺酸、咔唑、咔唑-3,6-二磺酸、2- 羥基喹啉、2,4-二羥基喹啉、己內醯胺、6-苯基-1,3,5-三-2,4-二胺、6-甲基-1,3,5-三-2,4-二胺、三聚氰酸等。又,於上述黃色色材中,亦可進而包含:水溶性聚合物、例如乙烯-環氧丙烷-嵌段聚合物、聚乙烯醇、聚(甲基)丙烯酸;例如如羧甲基纖維素、羥乙基纖維素、羥丙基纖維素、甲基-及乙基羥乙基纖維素般之改質纖維素等。 In addition, the above-mentioned yellow color material may further include: urea and substituted urea, such as phenylurea, dodecyl urea, etc., and its condensation polymer with aldehydes, especially formaldehyde; heterocycles, such as barbiturates Acid, benzimidazolone, benzimidazolone-5-sulfonic acid, 2,3-dihydroxyquine Morpholine, 2,3-dihydroxyquine Lin-6-sulfonic acid, carbazole, carbazole-3,6-disulfonic acid, 2-hydroxyquinoline, 2,4-dihydroxyquinoline, caprolactam, 6-phenyl-1,3, 5-Three -2,4-diamine, 6-methyl-1,3,5-tri -2,4-Diamine, cyanuric acid, etc. In addition, the yellow color material may further include: water-soluble polymers, such as ethylene-propylene oxide-block polymer, polyvinyl alcohol, poly(meth)acrylic acid; such as carboxymethyl cellulose, Modified cellulose like hydroxyethyl cellulose, hydroxypropyl cellulose, methyl- and ethyl hydroxyethyl cellulose, etc.
上述黃色色材例如可藉由參照日本專利特開2014-12838號公報而製備。 The yellow color material can be prepared by referring to Japanese Patent Laid-Open No. 2014-12838, for example.
於本發明之色材分散液含有吡咯并吡咯二酮系色材以外之其他色材之情形時,該其他色材之含量較佳為色材整體之80質量%以下,更佳為70質量%以下,進而更佳為65質量%以下。又,於本發明之色材分散液含有吡咯并吡咯二酮系色材以外之其他色材之情形時,該其他色材之含量較佳為色材及色素衍生物之合計之80質量%以下,更佳為70質量%以下,進而更佳為65質量%以下。 When the color material dispersion of the present invention contains color materials other than diketopyrrolopyrrole color materials, the content of the other color materials is preferably 80% by mass or less of the entire color material, more preferably 70% by mass Hereinafter, it is more preferably 65% by mass or less. In addition, when the color material dispersion of the present invention contains color materials other than diketopyrrolopyrrole color materials, the content of the other color materials is preferably 80% by mass or less of the total of the color materials and pigment derivatives. , More preferably 70% by mass or less, and still more preferably 65% by mass or less.
本發明之彩色濾光片用色材分散液含有具有上述通式(I)所表示之構成單元之聚合體作為分散劑。上述通式(I)所表示之構成單元具有鹼性,且係作為對色材之吸附部位發揮功能。本發明之色材分散液藉由使用具有通式(I)所表示之構成單元之聚合體,對上述特定之色材及色素衍生物之吸附性能提高,色材之分散性及分散穩定性提高,從而可提高著色層之對比度。 The color material dispersion liquid for a color filter of the present invention contains a polymer having a structural unit represented by the above-mentioned general formula (I) as a dispersant. The structural unit represented by the above general formula (I) has basicity and functions as an adsorption site for the color material. The color material dispersion of the present invention uses a polymer having the structural unit represented by the general formula (I) to improve the adsorption performance of the above-mentioned specific color material and pigment derivatives, and the dispersibility and dispersion stability of the color material are improved , Which can improve the contrast of the colored layer.
於通式(I)中,A為2價之連結基。作為A中之2價之連結基,例如可列舉:碳原子數1以上且10以下之伸烷基、伸芳 基、-CONH-基、-COO-基、碳原子數1以上且10以下之醚基(-R'-OR"-:R'及R"分別獨立地為伸烷基)及該等之組合等。其中,就分散性之方面而言,通式(I)中之A較佳為包含-CONH-基、或-COO-基之2價之連結基。 In the general formula (I), A is a divalent linking group. Examples of the divalent linking group in A include: alkylene, arylene, -CONH-, -COO-, and carbon atoms of 1 to 10 and carbon atoms of 1 to 10 Ether group (-R'-OR"-: R'and R" are each independently an alkylene group) and combinations thereof. Among them, in terms of dispersibility, A in the general formula (I) is preferably a divalent linking group including a -CONH- group or a -COO- group.
R2及R3中之可包含雜原子之烴基中之烴基,例如可列舉:烷基、芳烷基、芳基等。作為烷基,例如可列舉:甲基、乙基、丙基、丁基、異丙基、第三丁基、2-乙基己基、環戊基、環己基等,烷基之碳原子數較佳為1以上且18以下,其中,更佳為甲基或乙基。作為芳烷基,例如可列舉:苄基、苯乙基、萘基甲基、聯苯基甲基等。芳烷基之碳原子數較佳為7以上且20以下,進而較佳為7以上且14以下。又,作為芳基,可列舉:苯基、聯苯基、萘基、甲苯基、二甲苯基等。芳基之碳原子數較佳為6以上且24以下,進而較佳為6以上且12以下。再者,上述較佳之碳原子數中不包含取代基之碳原子數。包含雜原子之烴基具有上述烴基中之碳原子經雜原子取代之結構。作為烴基可包含之雜原子,例如可列舉:氧原子、氮原子、硫原子、矽原子等。又,烴基中之氫原子亦可經碳原子數1以上且5以下之烷基、氟原子、氯原子、溴原子等鹵素原子取代。 The hydrocarbon group in the hydrocarbon group that may contain a hetero atom in R 2 and R 3 includes, for example, an alkyl group, an aralkyl group, and an aryl group. Examples of alkyl groups include methyl, ethyl, propyl, butyl, isopropyl, tertiary butyl, 2-ethylhexyl, cyclopentyl, cyclohexyl, etc. The number of carbon atoms in the alkyl group is relatively high. It is preferably 1 or more and 18 or less, and among them, a methyl group or an ethyl group is more preferable. As an aralkyl group, a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group, etc. are mentioned, for example. The number of carbon atoms of the aralkyl group is preferably 7 or more and 20 or less, and more preferably 7 or more and 14 or less. Moreover, as an aryl group, a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, etc. are mentioned. The number of carbon atoms of the aryl group is preferably 6 or more and 24 or less, and more preferably 6 or more and 12 or less. Furthermore, the above-mentioned preferred number of carbon atoms does not include the number of carbon atoms of the substituent. The hydrocarbon group containing heteroatoms has a structure in which the carbon atoms in the above hydrocarbon group are substituted by heteroatoms. Examples of heteroatoms that may be contained in the hydrocarbon group include an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom. In addition, the hydrogen atom in the hydrocarbon group may be substituted with a halogen atom such as an alkyl group having 1 or more and 5 or less carbon atoms, a fluorine atom, a chlorine atom, and a bromine atom.
R2與R3相互鍵結而形成環結構係指R2與R3經由氮原子形成環結構。R2及R3所形成之環結構中亦可包含雜原子。環結構並無特別限定,例如可列舉:吡咯啶環、哌啶環、啉環等。 R 2 and R 3 are bonded to each other to form a ring structure means that R 2 and R 3 form a ring structure via a nitrogen atom. The ring structure formed by R 2 and R 3 may also include heteroatoms. The ring structure is not particularly limited, and examples include: pyrrolidine ring, piperidine ring, Morpholino ring and so on.
於本發明中,其中,R2與R3較佳為分別獨立地為氫原子、碳原子數1以上且5以下之烷基、苯基,或R2與R3鍵結而形成吡咯啶環、哌啶環、啉環,其中,較佳為R2及R3之至少1 個為碳原子數1以上且5以下之烷基、苯基,或R2與R3鍵結而形成吡咯啶環、哌啶環、啉環。 In the present invention, wherein R 2 and R 3 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, or R 2 and R 3 are bonded to form a pyrrolidine ring , Piperidine ring, Among them, it is preferable that at least one of R 2 and R 3 is an alkyl group or a phenyl group having 1 to 5 carbon atoms, or R 2 and R 3 are bonded to form a pyrrolidine ring or a piperidine ring , Morpholino ring.
作為上述通式(I)所表示之構成單元,可列舉:(甲基)丙烯酸二甲胺基乙酯、(甲基)丙烯酸二甲胺基丙酯、(甲基)丙烯酸二乙胺基乙酯、(甲基)丙烯酸二乙胺基丙酯等含烷基取代胺基之(甲基)丙烯酸酯等;二甲胺基乙基(甲基)丙烯醯胺、二甲胺基丙基(甲基)丙烯醯胺等含烷基取代胺基之(甲基)丙烯醯胺等。其中,就提高分散性及分散穩定性之方面而言,可較佳地使用(甲基)丙烯酸二甲胺基乙酯、(甲基)丙烯酸二乙胺基乙酯、二甲胺基丙基(甲基)丙烯醯胺。通式(I)所表示之構成單元可由1種構成,亦可包含2種以上之構成單元。 As the structural unit represented by the above general formula (I), dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, and diethylaminoethyl (meth)acrylate can be cited. (Meth)acrylates containing alkyl substituted amino groups, such as esters, diethylaminopropyl (meth)acrylate, etc.; dimethylaminoethyl (meth)acrylamide, dimethylaminopropyl ( (Meth)acrylamide and other (meth)acrylamides containing alkyl substituted amino groups. Among them, in terms of improving dispersibility and dispersion stability, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and dimethylaminopropyl can be preferably used. (Meth)acrylamide. The structural unit represented by the general formula (I) may be composed of one type, or may include two or more types of structural units.
作為具有通式(I)所表示之構成單元之聚合體,就提高分散性之方面而言,較佳為進而包含具有溶劑親和性之部位。作為溶劑親和性部位,較佳為以具有溶劑親和性之方式根據溶劑自可與誘導通式(I)所表示之構成單元之單體聚合之具有乙烯性不飽和鍵之單體之中適當選擇並使用。作為標準,較佳為以對於組合使用之溶劑而聚合體之23℃下之溶解度成為50(g/100g溶劑)以上之方式導入溶劑親和性部位。作為於本發明中所使用之聚合體,就可提高色材之分散性及分散穩定性以及樹脂組成物之耐熱性,從而形成高亮度且高對比度之著色層之方面而言,其中,較佳為嵌段共聚合體或接枝共聚合體,尤佳為嵌段共聚合體。以下,對尤佳之嵌段共聚合體詳細地進行說明。 As a polymer having a structural unit represented by the general formula (I), it is preferable to further include a portion having solvent affinity in terms of improving dispersibility. As the solvent affinity site, it is preferable to appropriately select the monomer having an ethylenically unsaturated bond from the monomer having an ethylenically unsaturated bond that can be polymerized with the monomer that induces the constituent unit represented by the general formula (I) in a manner having solvent affinity. And use. As a standard, it is preferable to introduce the solvent affinity site so that the solubility of the polymer at 23° C. becomes 50 (g/100g solvent) or more with respect to the solvent used in combination. As the polymer used in the present invention, in terms of improving the dispersibility and dispersion stability of the color material and the heat resistance of the resin composition, thereby forming a high-brightness and high-contrast colored layer, among them, preferred It is a block copolymer or a graft copolymer, and is particularly preferably a block copolymer. Hereinafter, a particularly preferred block copolymer will be described in detail.
若將包含上述通式(I)所表示之構成單元之嵌段設為A嵌段,則該A嵌段之上述通式(I)所表示之構成單元具有鹼性,且係作為對色材之吸附部位發揮功能。另一方面,不包含上述通式(I)所表示之構成單元之B嵌段係作為具有溶劑親和性之嵌段發揮功能。於本發明中,嵌段共聚合體之各嵌段之配置並無特別限定,例如可設為AB嵌段共聚合體、ABA嵌段共聚合體、BAB嵌段共聚合體等。其中,就分散性優異之方面而言,較佳為AB嵌段共聚合體、或ABA嵌段共聚合體。 If the block containing the structural unit represented by the above general formula (I) is referred to as the A block, the structural unit represented by the above general formula (I) of the A block has basicity and serves as a counter color material The adsorption part functions. On the other hand, the B block which does not contain the structural unit represented by the above general formula (I) functions as a block having solvent affinity. In the present invention, the arrangement of each block of the block copolymer is not particularly limited. For example, it can be an AB block copolymer, an ABA block copolymer, a BAB block copolymer, and the like. Among them, in terms of excellent dispersibility, AB block copolymers or ABA block copolymers are preferred.
作為構成B嵌段之構成單元,可列舉可與誘導通式(I)所表示之構成單元之單體共聚合之具有不飽和雙鍵之單體,其中,較佳為下述通式(II)所表示之構成單元。 As the structural unit constituting the B block, a monomer having an unsaturated double bond that can be copolymerized with a monomer that induces the structural unit represented by the general formula (I) is exemplified. Among them, the following general formula (II) is preferred. ) Represents the constituent unit.
(通式(II)中,A'係直接鍵或2價之連結基,R4係氫原子或甲基,R5係烴基、-[CH(R6)-CH(R7)-O]x-R8或-[(CH2)y-O]z-R8所表示之1價之基;R6及R7分別獨立地為氫原子或甲基,R8係氫原子、烴基、-CHO、-CH2CHO、或-CH2COOR9所表示之1價之基,R9係氫原子或碳原子數1以上且5以下之烷基;上述烴基亦可具有取代基;x表示1以上且18以下之整數,y表示1以上且5以下之整數,z表示1以上且18以下之整數。) (In the general formula (II), A'is a direct bond or a divalent linking group, R 4 is a hydrogen atom or a methyl group, and R 5 is a hydrocarbyl group, -[CH(R 6 )-CH(R 7 )-O] x -R 8 or -[(CH 2 ) y -O] z -R 8 represents a monovalent group; R 6 and R 7 are each independently a hydrogen atom or a methyl group, and R 8 is a hydrogen atom, a hydrocarbon group, A monovalent group represented by -CHO, -CH 2 CHO, or -CH 2 COOR 9 , R 9 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; the above-mentioned hydrocarbon group may also have a substituent; x represents An integer of 1 or more and 18 or less, y represents an integer of 1 or more and 5 or less, and z represents an integer of 1 or more and 18 or less.)
作為通式(II)之2價之連結基A',可設為與通式(I)中之A相同者。直接鍵意指A'不具有原子,即通式(II)中之C(碳原子) 與R5未經由其他原子而鍵結。其中,就對有機溶劑之溶解性之方面而言,A'較佳為直接鍵、包含-CONH-基或-COO-基之2價之連結基。就所獲得之聚合物之耐熱性或對可適當使用作為溶劑之丙二醇單甲醚乙酸酯(PGMEA)之溶解性、及為相對廉價之材料之方面而言,A'較佳為-COO-基。 As the divalent linking group A'of the general formula (II), it can be the same as A in the general formula (I). The direct bond means that A'does not have atoms, that is, C (carbon atom) and R 5 in the general formula (II) are bonded without other atoms. Among them, in terms of solubility in organic solvents, A'is preferably a direct bond, a divalent linking group including a -CONH- group or a -COO- group. In terms of the heat resistance of the obtained polymer or the solubility of propylene glycol monomethyl ether acetate (PGMEA), which can be suitably used as a solvent, and the relatively inexpensive material, A'is preferably -COO- base.
作為R5中之烴基,較佳為碳原子數1以上且18以下之烷基、碳原子數2以上且18以下之烯基、芳烷基、或芳基。上述碳原子數1以上且18以下之烷基可為直鏈狀、支鏈狀、環狀之任一者,例如可列舉:甲基、乙基、正丙基、異丙基、正丁基、2-乙基己基、2-乙氧基乙基、環戊基、環己基、基、異基、二環戊基、二環戊烯基、金剛烷基、低級烷基取代金剛烷基等。上述碳原子數2以上且18以下之烯基可為直鏈狀、支鏈狀、環狀之任一者。作為此種烯基,例如可列舉:乙烯基、烯丙基、丙烯基等。烯基之雙鍵之位置並無限定,就所獲得之聚合物之反應性之方面而言,較佳為於烯基之末端存在雙鍵。作為烷基或烯基等脂肪族烴之取代基,可列舉硝基、鹵素原子等。 As the hydrocarbon group in R 5, preferably 1 or more carbon atoms and an alkyl group of 18 or less carbon atoms, 2 or more and 18 or less of the alkenyl group, an aralkyl group, or an aryl group. The above-mentioned alkyl group having 1 or more and 18 or less carbon atoms may be linear, branched, or cyclic. Examples include methyl, ethyl, n-propyl, isopropyl, and n-butyl. , 2-ethylhexyl, 2-ethoxyethyl, cyclopentyl, cyclohexyl, Base, different Group, dicyclopentyl, dicyclopentenyl, adamantyl, lower alkyl substituted adamantyl, etc. The above-mentioned alkenyl group having 2 or more and 18 or less carbon atoms may be linear, branched, or cyclic. As such an alkenyl group, a vinyl group, an allyl group, a propenyl group, etc. are mentioned, for example. The position of the double bond of the alkenyl group is not limited. In terms of the reactivity of the obtained polymer, it is preferable that a double bond exists at the end of the alkenyl group. Examples of the substituent of aliphatic hydrocarbons such as an alkyl group or an alkenyl group include a nitro group and a halogen atom.
作為芳基,可列舉:苯基、聯苯基、萘基、甲苯基、二甲苯基等,進而亦可具有取代基。芳基之碳原子數較佳為6以上且24以下,進而較佳為6以上且12以下。又,作為芳烷基,可列舉:苄基、苯乙基、萘基甲基、聯苯基甲基等,進而亦可具有取代基。芳烷基之碳原子數較佳為7以上且20以下,進而較佳為7以上且14以下。作為芳基或芳烷基等芳香環之取代基,除碳原子數1以上且4以下之直鏈狀、支鏈狀之烷基以外,亦可列舉烯基、硝基、鹵素原子等。再者,上述較佳之碳原子數中不包含取代基之碳原子 數。 As an aryl group, a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, etc. are mentioned, and it may have a substituent further. The number of carbon atoms of the aryl group is preferably 6 or more and 24 or less, and more preferably 6 or more and 12 or less. Moreover, as an aralkyl group, a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group, etc. are mentioned, and it may have a substituent further. The number of carbon atoms of the aralkyl group is preferably 7 or more and 20 or less, and more preferably 7 or more and 14 or less. As the substituent of an aromatic ring such as an aryl group or an aralkyl group, in addition to a linear or branched alkyl group having 1 to 4 carbon atoms, an alkenyl group, a nitro group, a halogen atom, and the like can also be mentioned. Furthermore, the above-mentioned preferred number of carbon atoms does not include the number of carbon atoms of the substituent.
於上述R5中,x為1以上且18以下之整數,較佳為1以上且4以下之整數,更佳為1以上且2以下之整數,y為1以上且5以下之整數,較佳為1以上且4以下之整數,更佳為2或3。z為1以上且18以下之整數,較佳為1以上且4以下之整數,更佳為1以上且2以下之整數。 In the above R 5 , x is an integer of 1 or more and 18 or less, preferably an integer of 1 or more and 4 or less, more preferably an integer of 1 or more and 2 or less, and y is an integer of 1 or more and 5 or less, preferably It is an integer of 1 or more and 4 or less, more preferably 2 or 3. z is an integer of 1 or more and 18 or less, preferably an integer of 1 or more and 4 or less, and more preferably an integer of 1 or more and 2 or less.
上述R8中之烴基可設為與上述R5所示者相同者。R9為氫原子或碳原子數1以上且5以下之烷基,並且可為直鏈狀、支鏈狀、或環狀之任一者。又,上述通式(II)所表示之構成單元中之R5可相互相同,亦可不同。 The hydrocarbon group in the above R 8 can be the same as that shown in the above R 5. R 9 is a hydrogen atom or an alkyl group having 1 or more and 5 or less carbon atoms, and may be linear, branched, or cyclic. In addition, R 5 in the structural unit represented by the general formula (II) may be the same as or different from each other.
作為上述R5,其中,較佳為以與下述溶劑之相溶性變得優異之方式選定,具體而言,例如於上述溶劑使用通常使用作為彩色濾光片用著色樹脂組成物之溶劑之二醇醚乙酸酯系、醚系、酯系等溶劑之情形時,較佳為甲基、乙基、異丁基、正丁基、2-乙基己基、苄基等。 As the above-mentioned R 5 , among them, it is preferable to select so that the compatibility with the following solvent becomes excellent. Specifically, for the above-mentioned solvent, for example, the second solvent that is generally used as a colored resin composition for color filters is used. In the case of solvents such as alcohol ether acetate-based, ether-based, and ester-based solvents, methyl, ethyl, isobutyl, n-butyl, 2-ethylhexyl, benzyl, etc. are preferred.
進而,上述R5可於無損上述嵌段共聚合體之分散性能等之範圍內經烷氧基、羥基、環氧基、異氰酸酯基等取代基取代,又,亦可於上述嵌段共聚合體之合成後,與具有上述取代基之化合物反應而附加上述取代基。 Furthermore, the above-mentioned R 5 may be substituted with substituents such as alkoxy, hydroxyl, epoxy, and isocyanate groups within a range that does not impair the dispersibility of the above-mentioned block copolymer, and it may also be used after the synthesis of the above-mentioned block copolymer. , React with the compound having the above-mentioned substituent to add the above-mentioned substituent.
於本發明中,上述嵌段共聚合體之溶劑親和性之嵌段部之玻璃轉移溫度(Tg)只要適當選擇即可。就耐熱性之方面而言,其中,溶劑親和性之嵌段部之玻璃轉移溫度(Tg)較佳為80℃以上,更佳為100℃以上。本發明中之溶劑親和性之嵌段部之玻璃轉移溫度(Tg)可利用下述式進行計算。又,色材親和性嵌段部及嵌段共聚 合體之玻璃轉移溫度亦可同樣地計算。 In the present invention, the glass transition temperature (Tg) of the solvent-affinity block portion of the above-mentioned block copolymer may be appropriately selected. In terms of heat resistance, the glass transition temperature (Tg) of the solvent-compatible block portion is preferably 80°C or higher, more preferably 100°C or higher. The glass transition temperature (Tg) of the solvent affinity block part in the present invention can be calculated by the following formula. In addition, the glass transition temperature of the color material affinity block portion and the block copolymer can also be calculated in the same way.
1/Tg=Σ(Xi/Tgi) 1/Tg=Σ(Xi/Tgi)
此處,溶劑親和性之嵌段部設為i=1至n之n個單體成分共聚合而成。Xi係第i個單體之重量分率(ΣXi=1),Tgi係第i個單體之均聚物之玻璃轉移溫度(絕對溫度)。其中,Σ取i=1至n之和。再者,各單體之均聚物玻璃轉移溫度之值(Tgi)可採用Polymer Handbook(3rd Edition)(J.Brandrup,E.H.Immergut著(Wiley-Interscience、1989))之值。 Here, the solvent affinity block part is made by copolymerizing n monomer components of i=1 to n. Xi is the weight fraction of the i-th monomer (ΣXi=1), and Tgi is the glass transition temperature (absolute temperature) of the homopolymer of the i-th monomer. Among them, Σ takes the sum of i=1 to n. Furthermore, the value of the homopolymer glass transition temperature (Tgi) of each monomer can be the value of the Polymer Handbook (3rd Edition) (by J. Brandrup, E.H. Immergut (Wiley-Interscience, 1989)).
構成溶劑親和性之嵌段部之構成單元之數量只要於提高色材分散性之範圍內適當調整即可。其中,就使溶劑親和性部位與色材親和性部位有效地作用而提高色材之分散性之方面而言,構成溶劑親和性之嵌段部之構成單元之數量較佳為10以上且200以下,更佳為10以上且100以下,進而較佳為10以上且70以下。 The number of structural units constituting the solvent-affinity block portion may be appropriately adjusted within the range of improving the dispersibility of the color material. Among them, in terms of allowing the solvent affinity site and the color material affinity site to effectively act to improve the dispersibility of the color material, the number of structural units constituting the solvent affinity block portion is preferably 10 or more and 200 or less , More preferably 10 or more and 100 or less, and still more preferably 10 or more and 70 or less.
溶劑親和性之嵌段部只要以作為溶劑親和性部位發揮功能之方式選擇即可,構成溶劑親和性之嵌段部之重複單元可由1種構成,亦可包含2種以上之重複單元。 The solvent-affinity block portion may be selected so as to function as a solvent-affinity portion, and the repeating unit constituting the solvent-affinity block portion may be composed of one type, or may include two or more types of repeating units.
又,其中,於本發明中,就分散性良好且於塗膜形成時不會析出異物而提高亮度及對比度之方面而言,分散劑較佳為包含上述通式(II)所表示之結構,且鹽形成前之胺值為40mgKOH/g以上且120mgKOH/g以下之聚合體。藉由使胺值為上述範圍內,黏度之經時穩定性或耐熱性優異,並且鹼顯影性或溶劑再溶解性亦優異。於本發明中,關於分散劑之胺值,就分散性及分散穩定性之方面而言,其中,鹽形成前之胺值較佳為80mgKOH/g以上,更佳 為90mgKOH/g以上。另一方面,就溶劑再溶解性之方面而言,分散劑之鹽形成前之胺值較佳為110mgKOH/g以下,更佳為105mgKOH/g以下。胺值係指與中和試樣1g中所包含之胺成分所需之過氯酸相當量之氫氧化鉀之mg數,可藉由JIS-K7237所定義之方法測定。於藉由該方法測定之情形時,即便為與分散劑中之有機酸化合物形成鹽之胺基,通常由於該有機酸化合物會解離,故而亦可測定使用作為分散劑之嵌段共聚合體本身之胺值。 Furthermore, in the present invention, it is preferable that the dispersing agent includes the structure represented by the above general formula (II) in terms of good dispersibility and no precipitation of foreign matter during coating film formation to improve brightness and contrast. And the amine value before salt formation is a polymer of 40 mgKOH/g or more and 120 mgKOH/g or less. By setting the amine value within the above range, the viscosity with time stability or heat resistance is excellent, and the alkali developability or solvent resolubility is also excellent. In the present invention, regarding the amine value of the dispersant, in terms of dispersibility and dispersion stability, the amine value before salt formation is preferably 80 mgKOH/g or more, more preferably 90 mgKOH/g or more. On the other hand, in terms of solvent resolubility, the amine value of the dispersant before salt formation is preferably 110 mgKOH/g or less, more preferably 105 mgKOH/g or less. The amine value refers to the mg number of potassium hydroxide equivalent to the amount of perchloric acid required to neutralize the amine component contained in 1 g of the sample, and can be measured by the method defined in JIS-K7237. In the case of measurement by this method, even if it is an amine group that forms a salt with the organic acid compound in the dispersant, usually because the organic acid compound is dissociated, it is also possible to measure the amount of the block copolymer itself used as the dispersant. Amine value.
關於本發明所使用之分散劑之酸值,就顯影殘渣之抑制效果之方面而言,作為下限,較佳為1mgKOH/g以上。其中,就顯影殘渣之抑制效果更優異之方面而言,分散劑之酸值更佳為2mgKOH/g以上。另一方面,就分散性及分散穩定性之方面而言,本發明所使用之分散劑之酸值較佳為0mgKOH/g。又,關於本發明所使用之分散劑之酸值,就可防止顯影密接性之惡化或溶劑再溶解性之惡化之方面而言,作為分散劑之酸值之上限,較佳為18mgKOH/g以下。其中,就顯影密接性、及溶劑再溶解性變得良好之方面而言,分散劑之酸值更佳為12mgKOH/g以下,進而更佳為8mgKOH/g以下。於本發明所使用之分散劑中,鹽形成前之嵌段共聚合體之酸值較佳為1mgKOH/g以上,進而較佳為2mgKOH/g以上。原因在於顯影殘渣之抑制效果提高。另一方面,就分散性及分散穩定性之方面而言,鹽形成前之嵌段共聚合體之酸值較佳為0mgKOH/g。又,作為鹽形成前之嵌段共聚合體之酸值之上限,較佳為18mgKOH/g以下,更佳為12mgKOH/g以下,進而更佳為8mgKOH/g以下。原因在於顯影密接性、及溶劑再溶解性變得良好。 Regarding the acid value of the dispersant used in the present invention, the lower limit is preferably 1 mgKOH/g or more in terms of the effect of suppressing development residue. Among them, the acid value of the dispersant is more preferably 2 mgKOH/g or more in terms of the more excellent effect of suppressing the development residue. On the other hand, in terms of dispersibility and dispersion stability, the acid value of the dispersant used in the present invention is preferably 0 mgKOH/g. Also, regarding the acid value of the dispersant used in the present invention, in terms of preventing deterioration of development adhesion or deterioration of solvent resolubility, the upper limit of the acid value of the dispersant is preferably 18 mgKOH/g or less . Among them, the acid value of the dispersant is more preferably 12 mgKOH/g or less, and even more preferably 8 mgKOH/g or less, in terms of good development adhesion and solvent resolubility. In the dispersant used in the present invention, the acid value of the block copolymer before salt formation is preferably 1 mgKOH/g or more, and more preferably 2 mgKOH/g or more. The reason is that the effect of suppressing development residue is improved. On the other hand, in terms of dispersibility and dispersion stability, the acid value of the block copolymer before salt formation is preferably 0 mgKOH/g. In addition, the upper limit of the acid value of the block copolymer before salt formation is preferably 18 mgKOH/g or less, more preferably 12 mgKOH/g or less, and still more preferably 8 mgKOH/g or less. The reason is that the development adhesiveness and solvent resolubility become better.
又,於本發明中,就顯影密接性提高之方面而言,分 散劑之玻璃轉移溫度較佳為30℃以上。即,分散劑為鹽形成前嵌段共聚合體或鹽型嵌段共聚合體,其玻璃轉移溫度均較佳為30℃以上。若分散劑之玻璃轉移溫度較低,則尤其接近顯影液溫度(通常23℃左右)而有顯影密接性降低之虞。推測其原因在於若該玻璃轉移溫度接近顯影液溫度,則於顯影時分散劑之運動變大,其結果為顯影密接性惡化。推測藉由使玻璃轉移溫度為30℃以上,可抑制顯影時之分散劑之分子運動,因此顯影密接性之降低得以抑制。就顯影密接性之方面而言,其中,分散劑之玻璃轉移溫度較佳為32℃以上,更佳為35℃以上。另一方面,就準確稱量容易等使用時之操作性之觀點而言,較佳為200℃以下。本發明中之分散劑之玻璃轉移溫度可藉由依據JIS K7121並藉由示差掃描熱量測定(DSC)進行測定而求出。 Furthermore, in the present invention, the glass transition temperature of the dispersant is preferably 30°C or higher in terms of improvement in development adhesion. That is, the dispersant is a pre-salt-formed block copolymer or a salt-type block copolymer, and its glass transition temperature is preferably 30°C or higher. If the glass transition temperature of the dispersant is relatively low, it will be particularly close to the temperature of the developer (usually around 23°C), and the development adhesion may decrease. It is presumed that the reason is that if the glass transition temperature is close to the temperature of the developer, the movement of the dispersant during development becomes larger, and as a result, the development adhesion deteriorates. It is estimated that by setting the glass transition temperature to 30°C or higher, the molecular movement of the dispersant during development can be suppressed, and therefore the decrease in development adhesion can be suppressed. In terms of developing adhesiveness, the glass transition temperature of the dispersant is preferably 32°C or higher, and more preferably 35°C or higher. On the other hand, from the viewpoint of operability during use such as easy accurate weighing, it is preferably 200°C or lower. The glass transition temperature of the dispersant in the present invention can be determined by measuring by differential scanning calorimetry (DSC) in accordance with JIS K7121.
若提高色材濃度而增加分散劑含量,則黏合劑量會相對減少,因此,著色樹脂層於顯影時容易自基底基板剝離。分散劑包含含有源自含羧基單體之構成單元之B嵌段,且具有上述特定之酸值及玻璃轉移溫度,藉此顯影密接性提高。推測若酸值過高,則顯影性優異,但極性過高,反而於顯影時容易產生剝離。 If the concentration of the color material is increased and the content of the dispersant is increased, the amount of binder will be relatively reduced. Therefore, the colored resin layer is likely to peel off from the base substrate during development. The dispersant contains a B block containing a structural unit derived from a carboxyl group-containing monomer, and has the above-mentioned specific acid value and glass transition temperature, thereby improving the development adhesion. It is estimated that if the acid value is too high, the developability is excellent, but if the polarity is too high, peeling easily occurs during development.
根據以上情況,於本發明中,就色材分散穩定性優異而提高對比度,於製成著色樹脂組成物時溶劑再溶解性優異,進而具有較高之顯影密接性之方面而言,上述分散劑較佳為包含上述通式(I)所表示之結構且上述胺值為40mgKOH/g以上且120mgKOH/g以下之聚合體,且上述酸值為1mgKOH/g以上且18mgKOH/g以下或0mgKOH/g,玻璃轉移溫度為30℃以上。 Based on the above, in the present invention, the dispersant is excellent in dispersion stability of the color material to improve contrast, excellent in solvent re-solubility when it is made into a colored resin composition, and higher developing adhesiveness. Preferably, it is a polymer comprising the structure represented by the general formula (I) and the amine value is 40 mgKOH/g or more and 120 mgKOH/g or less, and the acid value is 1 mgKOH/g or more and 18 mgKOH/g or less or 0 mgKOH/g , The glass transition temperature is above 30°C.
作為上述含羧基單體,可使用可與具有通式(I)所表示 之構成單元之單體共聚合且含有不飽和雙鍵與羧基之單體。作為此種單體,例如可列舉:(甲基)丙烯酸、乙烯基苯甲酸、順丁烯二酸、順丁烯二酸單烷基酯、反丁烯二酸、衣康酸、丁烯酸、桂皮酸、丙烯酸二聚物等。又,亦可利用(甲基)丙烯酸2-羥基乙酯等具有羥基之單體與順丁烯二酸酐或鄰苯二甲酸酐、環己烷二羧酸酐般之環狀酸酐之加成反應物、ω-羧基-聚己內酯單(甲基)丙烯酸酯等。又,作為羧基之前驅物,亦可使用順丁烯二酸酐、衣康酸酐、檸康酸酐等含酸酐基單體。其中,就共聚合性或成本、溶解性、玻璃轉移溫度等之方面而言,尤佳為(甲基)丙烯酸。 As the above-mentioned carboxyl group-containing monomer, a monomer which can be copolymerized with a monomer having a structural unit represented by the general formula (I) and which contains an unsaturated double bond and a carboxyl group can be used. Examples of such monomers include (meth)acrylic acid, vinyl benzoic acid, maleic acid, monoalkyl maleate, fumaric acid, itaconic acid, and crotonic acid. , Cinnamic acid, acrylic acid dimer, etc. In addition, the addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride can also be used , Ω-carboxy-polycaprolactone mono(meth)acrylate, etc. In addition, as the precursor of the carboxyl group, an acid anhydride group-containing monomer such as maleic anhydride, itaconic anhydride, and citraconic anhydride may also be used. Among them, (meth)acrylic acid is particularly preferred in terms of copolymerization, cost, solubility, glass transition temperature, and the like.
於鹽形成前之嵌段共聚合體中,源自含羧基單體之構成單元之含有比例,只要以嵌段共聚合體之酸值成為上述特定酸值之範圍內之方式適當設定即可,並無特別限定,相對於嵌段共聚合體之總構成單元之合計質量,較佳為0.05質量%以上且4.5質量%以下,更佳為0.07質量%以上且3.7質量%以下。藉由使源自含羧基單體之構成單元之含有比例為上述下限值以上,而表現出顯影殘渣之抑制效果,藉由使其為上述上限值以下,可防止顯影密接性之惡化或溶劑再溶解性之惡化。再者,源自含羧基單體之構成單元只要成為上述特定之酸值即可,可由1種構成,亦可包含2種以上之構成單元。 In the block copolymer before salt formation, the content ratio of the constituent units derived from the carboxyl group-containing monomer can be appropriately set so that the acid value of the block copolymer falls within the range of the above-mentioned specific acid value. Particularly limited, with respect to the total mass of the total structural units of the block copolymer, it is preferably 0.05% by mass or more and 4.5% by mass or less, and more preferably 0.07% by mass or more and 3.7% by mass or less. By making the content ratio of the constitutional unit derived from the carboxyl group-containing monomer more than the above lower limit, the effect of suppressing development residues is exhibited, and by making it below the above upper limit, it is possible to prevent deterioration of development adhesion or Deterioration of solvent re-solubility. Furthermore, the structural unit derived from a carboxyl group-containing monomer should just have the said specific acid value, and it may be comprised by 1 type, and may contain 2 or more types of structural units.
又,就將本發明所使用之分散劑之玻璃轉移溫度設為特定值以上而提高顯影密接性之方面而言,較佳為將單體之均聚物之玻璃轉移溫度之值(Tgi)為10℃以上之單體於B嵌段中合計設為75質量%以上,進而較佳為設為85質量%以上。 In addition, in terms of setting the glass transition temperature of the dispersant used in the present invention to a specific value or higher to improve development adhesion, it is preferable to set the value of the glass transition temperature (Tgi) of the homopolymer of the monomer to The total amount of monomers at 10° C. or higher in the B block is 75% by mass or more, and more preferably 85% by mass or more.
於上述嵌段共聚合體中,作為上述A嵌段之構成單元 之單元數m與上述B嵌段之構成單元之單元數n之比率m/n,較佳為0.05以上且1.5以下之範圍內,就色材之分散性、分散穩定性之方面而言,更佳為0.1以上且1.0以下之範圍內。 In the block copolymer, the ratio m/n of the unit number m of the structural unit of the A block to the unit number n of the structural unit of the B block is preferably in the range of 0.05 or more and 1.5 or less, In terms of the dispersibility and dispersion stability of the color material, it is more preferably in the range of 0.1 or more and 1.0 or less.
上述嵌段共聚合體之重量平均分子量Mw並無特別限定,就使色材分散性及分散穩定性良好之方面而言,較佳為1000以上且20000以下,更佳為2000以上且15000以下,進而較佳為3000以上且12000以下。此處,重量平均分子量(Mw)係藉由凝膠滲透層析法(GPC)並以標準聚苯乙烯換算值的形式求出。再者,針對成為嵌段共聚合體之原料之巨單體或鹽型嵌段共聚合體、接枝共聚合體,亦以上述條件進行。 The weight average molecular weight Mw of the above-mentioned block copolymer is not particularly limited. In terms of improving the dispersibility and dispersion stability of the color material, it is preferably 1,000 or more and 20,000 or less, more preferably 2,000 or more and 15,000 or less, and further Preferably it is 3000 or more and 12000 or less. Here, the weight average molecular weight (Mw) is calculated as a standard polystyrene conversion value by gel permeation chromatography (GPC). Furthermore, the macromonomers, salt-type block copolymers, and graft copolymers used as raw materials for the block copolymers are also carried out under the above-mentioned conditions.
上述嵌段共聚合體之製造方法並無特別限定。可藉由公知之方法製造嵌段共聚合體,其中,較佳為利用活性聚合法製造。原因在於其可製造不易產生鏈轉移或失活而分子量一致之共聚合體,從而可提高分散性等。作為活性聚合法,可列舉:活性自由基聚合法、群組轉移聚合法等活性陰離子聚合法、活性陽離子聚合法等。藉由利用該等方法將單體依序聚合,可製造共聚合體。例如,首先製造A嵌段,並將構成B嵌段之構成單元聚合於A嵌段,藉此可製造嵌段共聚合體。又,於上述製造方法中,亦可使A嵌段與B嵌段之聚合順序顛倒。又,亦可分別製造A嵌段與B嵌段,其後,將A嵌段與B嵌段偶合。 The manufacturing method of the said block copolymer is not specifically limited. The block copolymer can be produced by a known method, and among them, it is preferably produced by a living polymerization method. The reason is that it can produce copolymers that are not prone to chain transfer or deactivation and have a uniform molecular weight, thereby improving dispersibility and the like. Examples of the living polymerization method include living anionic polymerization methods such as living radical polymerization methods and group transfer polymerization methods, living cationic polymerization methods, and the like. By using these methods to sequentially polymerize monomers, copolymers can be produced. For example, the A block is first produced, and the constituent units constituting the B block are polymerized into the A block, thereby producing a block copolymer. In addition, in the above-mentioned production method, the order of polymerization of the A block and the B block may be reversed. In addition, the A block and the B block may be produced separately, and thereafter, the A block and the B block may be coupled.
作為此種具有包含上述通式(I)所表示之構成單元之嵌段部與具有溶劑親和性之嵌段部之嵌段共聚合體之具體例,例如可列舉日本專利第4911253號公報所記載之嵌段共聚合體作為較佳者。 As a specific example of such a block copolymer having a block portion containing the structural unit represented by the above general formula (I) and a block portion having solvent affinity, for example, the one described in Japanese Patent No. 4911253 can be cited Block copolymers are preferred.
於本發明中,就色材之分散性或分散穩定性之方面而言,即便將如包含上述通式(I)所表示之構成單元之聚合體中之胺基般之通式(I)所表示之構成單元所具有之末端之氮部位中之至少一部分與有機酸化合物或鹵化烴形成鹽而成者使用作為分散劑亦較佳(以下,有時將此種聚合體稱為鹽型聚合體)。其中,就顯影性變得優異之方面而言,較佳為將通式(I)所表示之構成單元所具有之末端之氮部位中之至少一部分與有機酸化合物形成鹽而成者使用作為分散劑。其中,就色材之分散性及分散穩定性優異而對比度提高之方面而言,較佳為包含具有三級胺之重複單元之聚合體為嵌段共聚合體,並且上述有機酸化合物為苯基膦酸或苯基次膦酸等酸性有機磷化合物。作為此種分散劑所使用之有機酸化合物之具體例,例如可列舉日本專利特開2012-236882號公報等所記載之有機酸化合物作為較佳者。又,作為上述鹵化烴,就色材之分散性及分散穩定性優異之方面而言,較佳為溴化烯丙基、氯化苄基等鹵化烯丙基及鹵化芳烷基之至少1種。 In the present invention, in terms of the dispersibility or dispersion stability of the color material, even if the general formula (I) is the same as the amine group in the polymer containing the structural unit represented by the general formula (I) It is also preferable to use as a dispersant as a dispersing agent at least a part of the nitrogen part of the terminal of the structural unit possessed by the organic acid compound or halogenated hydrocarbon. ). Among them, in terms of excellent developability, it is preferred that at least a part of the terminal nitrogen site of the structural unit represented by the general formula (I) forms a salt with an organic acid compound as a dispersion Agent. Among them, in terms of excellent dispersibility and dispersion stability of the color material and improved contrast, it is preferable that the polymer containing the repeating unit having a tertiary amine is a block copolymer, and the organic acid compound is a phenylphosphine Acidic organic phosphorus compounds such as acid or phenylphosphinic acid. As a specific example of the organic acid compound used for such a dispersing agent, the organic acid compound described in Unexamined-Japanese-Patent No. 2012-236882 etc. is mentioned as a preferable thing, for example. In addition, as the above-mentioned halogenated hydrocarbon, at least one of halogenated allyl groups such as brominated allyl group and chloride benzyl group and halogenated aralkyl group is preferable in terms of excellent dispersibility and dispersion stability of the color material. .
又,作為本發明所使用之分散劑,就分散性與分散穩定性之方面、及抑制加熱所導致之對比度之降低之方面而言,較佳為具有上述通式(I)所表示之構成單元之聚合體中之通式(I)所表示之構成單元所具有之末端之氮部位中之一部分形成鹽,而未形成鹽之氮部位殘存。認為吡咯并吡咯二酮色材之磺化衍生物容易與殘存之氮部位吸附,因此分散性更優異而對比度提高。其中,就容易吸附吡咯并吡咯二酮系色材之磺化衍生物之方面而言,較佳為以相對於具有上述通式(I)所表示之構成單元之聚合體中之通式(I)所表示之構成單元所具有之末端之氮部位1莫耳而有機酸化合物為0.2莫 耳當量以上且0.8莫耳當量以下形成鹽,更佳為以0.3莫耳當量以上且0.7莫耳當量以下形成鹽。 In addition, as the dispersant used in the present invention, it is preferable to have a structural unit represented by the general formula (I) in terms of dispersibility and dispersion stability, and in terms of suppressing the decrease in contrast caused by heating A part of the terminal nitrogen portion of the structural unit represented by the general formula (I) in the polymer forms a salt, and the nitrogen portion that does not form a salt remains. It is believed that the sulfonated derivative of the diketopyrrolopyrrole color material is easily adsorbed to the remaining nitrogen site, so that the dispersibility is more excellent and the contrast is improved. Among them, in terms of easily adsorbing the sulfonated derivative of the diketopyrrolopyrrole color material, it is preferable to compare the general formula (I) in the polymer having the structural unit represented by the general formula (I). The nitrogen part of the terminal of the structural unit represented by) is 1 mol and the organic acid compound is 0.2 mol equivalent or more and 0.8 mol equivalent or less to form a salt, more preferably 0.3 mol equivalent or more and 0.7 mol equivalent or less Form salt.
於本發明之色材分散液中,使用具有上述通式(I)所表示之構成單元之聚合體之至少1種作為分散劑,其含量根據所使用之色材之種類、進而下述彩色濾光片用著色樹脂組成物中之固形份濃度等而適當選定。就分散性及分散穩定性之方面而言,分散劑之含量相對於色材分散液中之總固形份100質量份,較佳為以3質量份以上且45質量份以下、更佳為以5質量份以上且35質量份以下之比例調配。尤其是於形成色材濃度較高之塗膜或著色層之情形時,分散劑之含量相對於色材分散液中之總固形份100質量份,較佳為以3質量份以上且25質量份以下、更佳為以5質量份以上且20質量份以下之比例調配。再者,於本發明中,固形份係除上述溶劑以外之全部物質,亦包含溶解於溶劑中之單體等。 In the color material dispersion of the present invention, at least one polymer having the structural unit represented by the general formula (I) is used as a dispersant, and its content depends on the type of color material used, and the following color filter The solid content concentration in the colored resin composition for optical sheets, etc. is appropriately selected. In terms of dispersibility and dispersion stability, the content of the dispersant relative to 100 parts by mass of the total solid content in the color material dispersion is preferably 3 parts by mass or more and 45 parts by mass or less, more preferably 5 parts by mass. It is blended in a ratio of more than part by mass and less than 35 parts by mass. Especially in the case of forming a coating film or colored layer with a high color material concentration, the content of the dispersant is preferably 3 parts by mass or more and 25 parts by mass relative to 100 parts by mass of the total solid content in the color material dispersion. Hereinafter, it is more preferable to blend in a ratio of 5 parts by mass or more and 20 parts by mass or less. Furthermore, in the present invention, the solid content refers to all substances other than the above-mentioned solvents, and also includes monomers dissolved in the solvents and the like.
溶劑只要為不會與色材分散液中之各成分反應且可使該等溶解或者分散之溶劑即可,並無特別限定。作為溶劑之具體例,例如可列舉:甲醇、乙醇、N-丙醇、異丙醇、甲氧基醇、乙氧基醇等醇系溶劑;甲氧基乙氧基乙醇、乙氧基乙氧基乙醇等卡必醇系溶劑;乙酸乙酯、乙酸丁酯、甲氧基丙酸甲酯、甲氧基丙酸乙酯、乙氧基丙酸乙酯、乳酸乙酯、羥基丙酸甲酯、羥基丙酸乙酯、乙酸正丁酯、乙酸異丁酯、丁酸異丁酯、丁酸正丁酯、環己醇乙酸酯等酯系溶劑;丙酮、甲基乙基酮、甲基異丁基酮、環己酮、2-庚酮等酮系溶劑;乙酸甲氧基乙酯、丙二醇單甲醚乙酸酯、乙酸3-甲氧基-3-甲基-1- 丁酯、乙酸3-甲氧基丁酯、乙酸乙氧基乙酯等二醇醚乙酸酯系溶劑;乙酸甲氧基乙氧基乙酯、乙酸乙氧基乙氧基乙酯、丁基卡必醇乙酸酯(BCA)等卡必醇乙酸酯系溶劑;丙二醇二乙酸酯、1,3-丁二醇二乙酸酯等二乙酸酯類;乙二醇單甲醚、乙二醇單乙醚、乙二醇二甲醚、二乙二醇二甲醚、二乙二醇單乙醚、二乙二醇二乙醚、丙二醇單甲醚、二丙二醇二甲醚等二醇醚系溶劑;N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基吡咯烷酮等非質子性醯胺溶劑;γ-丁內酯等內酯系溶劑;四氫呋喃等環狀醚系溶劑;苯、甲苯、二甲苯、萘等不飽和烴系溶劑;N-庚烷、N-己烷、N-辛烷等飽和烴系溶劑;甲苯、二甲苯等芳香族烴類等有機溶劑。該等溶劑之中,就其他成分之溶解性之方面而言,可適當使用二醇醚乙酸酯系溶劑、卡必醇乙酸酯系溶劑、二醇醚系溶劑、酯系溶劑。其中,作為本發明所使用之溶劑,就其他成分之溶解性或塗佈適合性之方面而言,較佳為選自由丙二醇單甲醚乙酸酯、丙二醇單甲醚、丁基卡必醇乙酸酯(BCA)、乙酸3-甲氧基-3-甲基-1-丁酯、乙氧基丙酸乙酯、乳酸乙酯、及乙酸3-甲氧基丁酯所構成之群組中之1種以上。 The solvent is not particularly limited as long as it does not react with each component in the color material dispersion liquid and can dissolve or disperse these components. Specific examples of solvents include, for example, alcoholic solvents such as methanol, ethanol, N-propanol, isopropanol, methoxy alcohol, and ethoxy alcohol; methoxyethoxyethanol, ethoxyethoxy Carbitol solvents such as ethyl alcohol; ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate , Ethyl hydroxypropionate, n-butyl acetate, isobutyl acetate, isobutyl butyrate, n-butyl butyrate, cyclohexanol acetate and other ester solvents; acetone, methyl ethyl ketone, methyl Ketone solvents such as isobutyl ketone, cyclohexanone and 2-heptanone; methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, Glycol ether acetate solvents such as 3-methoxybutyl acetate and ethoxyethyl acetate; methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, butyl carbitol Carbitol acetate solvents such as acetate (BCA); diacetate esters such as propylene glycol diacetate and 1,3-butanediol diacetate; ethylene glycol monomethyl ether, ethylene glycol mono Glycol ether solvents such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, and dipropylene glycol dimethyl ether; N, Aprotic amide solvents such as N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; lactone-based solvents such as γ-butyrolactone; cyclic ether-based solvents such as tetrahydrofuran Solvents; unsaturated hydrocarbon solvents such as benzene, toluene, xylene, and naphthalene; saturated hydrocarbon solvents such as N-heptane, N-hexane, and N-octane; organic solvents such as aromatic hydrocarbons such as toluene and xylene. Among these solvents, in terms of solubility of other components, glycol ether acetate-based solvents, carbitol acetate-based solvents, glycol ether-based solvents, and ester-based solvents can be suitably used. Among them, the solvent used in the present invention is preferably selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and butyl carbitol ethyl in terms of solubility of other components or coating suitability. Acid ester (BCA), 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, ethyl lactate, and 3-methoxybutyl acetate One or more of them.
關於含有溶劑之色材分散液中之固形份之含有比例,於將包含溶劑之色材分散液整體設為100質量份時,固形份較佳為0.1質量份以上且70質量份以下,更佳為1.0質量份以上且50質量份以下。 Regarding the content ratio of the solid content in the solvent-containing color material dispersion liquid, when the entire color material dispersion liquid containing the solvent is 100 parts by mass, the solid content is preferably 0.1 parts by mass or more and 70 parts by mass or less, more preferably It is 1.0 part by mass or more and 50 parts by mass or less.
只要無損本發明之效果,則亦可視需要於本發明之色材分散液中進而調配分散輔助樹脂、其他成分。作為分散輔助樹脂,例如可 列舉下述彩色濾光片用著色樹脂組成物中所例示之鹼可溶性樹脂。存在如下情況:藉由鹼可溶性樹脂之位阻而色材粒子彼此不易接觸,從而分散穩定化或藉由該分散穩定化效果而具有減少分散劑之效果。又,作為其他成分,例如可列舉用以提高潤濕性之界面活性劑、用以提高密接性之矽烷偶合劑、消泡劑、防收縮劑、抗氧化劑、防凝集劑、紫外線吸收劑等。 As long as the effect of the present invention is not impaired, the dispersion auxiliary resin and other components may be further formulated in the color material dispersion liquid of the present invention as needed. Examples of the dispersion auxiliary resin include alkali-soluble resins exemplified in the following colored resin composition for color filters. There are cases where the color material particles are not easily contacted with each other due to the steric hindrance of the alkali-soluble resin, thereby stabilizing the dispersion or having the effect of reducing the dispersant due to the dispersion stabilizing effect. In addition, as other components, for example, surfactants for improving wettability, silane coupling agents for improving adhesion, defoaming agents, anti-shrinking agents, antioxidants, anti-aggregating agents, ultraviolet absorbers, etc. can be cited.
本發明之色材分散液可使用作為用以製備下述彩色濾光片用著色樹脂組成物之備用製備物。即,所謂色材分散液,係於製備下述彩色濾光片用著色樹脂組成物之前階段中預先製備之(組成物中之色材成分質量)/(組成物中之色材成分以外之固形份質量)比較高之色材分散液。具體而言,(組成物中之色材成分質量)/(組成物中之色材成分以外之固形份質量)比通常為1.0以上。色材分散液可藉由與下述各成分加以混合而製備分散性優異之彩色濾光片用著色樹脂組成物。 The color material dispersion of the present invention can be used as a ready-to-use preparation for preparing the following colored resin composition for color filters. In other words, the so-called color material dispersion liquid is prepared in advance in the stage of preparing the following colored resin composition for color filters (the quality of the color material in the composition)/(the solid form other than the color material in the composition) Parts mass) relatively high color material dispersion. Specifically, the ratio of (mass of color material components in the composition)/(mass of solid content other than the color material components in the composition) is usually 1.0 or more. The color material dispersion liquid can be mixed with the following components to prepare a colored resin composition for color filters with excellent dispersibility.
本發明之彩色濾光片用色材分散液可藉由於上述溶劑中至少添加包含吡咯并吡咯二酮系色材之色材、上述色素衍生物、及上述分散劑,並進行習知公知之分散處理而獲得。作為用以進行分散處理之分散機,例如可列舉:雙輥、三輥等輥磨機、球磨機、振動球磨機等球磨機、塗料調節器、連續圓盤型珠磨機、連續環型珠磨機等珠磨機。作為珠磨機之較佳之分散條件,所使用之珠徑較佳為0.03~2.00mm,更佳為0.05~1.0mm。 The color material dispersion liquid for the color filter of the present invention can be prepared by adding at least a color material containing a diketopyrrolopyrrole color material, the above-mentioned pigment derivative, and the above-mentioned dispersing agent to the above-mentioned solvent, and performing a conventionally known dispersion. Obtained by processing. Examples of the dispersing machine for performing the dispersion treatment include: two-roll, three-roll, etc. roll mills, ball mills, vibrating ball mills, and other ball mills, paint conditioners, continuous disc type bead mills, continuous ring type bead mills, etc. Bead mill. As a preferable dispersion condition of the bead mill, the diameter of the beads used is preferably 0.03~2.00mm, more preferably 0.05~1.0mm.
色材分散液中之色材之平均分散粒徑因所使用之色 材之種類而有所不同,較佳為10~100nm之範圍內,更佳為15~60nm之範圍內。色材分散液中之色材之平均分散粒徑係分散於至少含有溶劑之色材分散液中之色材粒子之分散粒徑,並且係藉由雷射光散射粒度分佈計而測定。作為藉由雷射光散射粒度分佈計而進行之粒徑之測定,可利用色材分散液所使用之溶劑將色材分散液適當稀釋成可利用雷射光散射粒度分佈計進行測定之濃度(例如,1000倍等),使用雷射光散射粒度分佈計(例如,日機裝公司製造之Nanotrac粒度分佈測定裝置UPA-EX150)並藉由動態光散射法於23℃下進行測定。此處之平均分散粒徑係體積平均粒徑。 The average dispersed particle size of the color material in the color material dispersion depends on the type of color material used, and is preferably in the range of 10 to 100 nm, and more preferably in the range of 15 to 60 nm. The average dispersed particle size of the color material in the color material dispersion liquid is the dispersed particle diameter of the color material particles dispersed in the color material dispersion liquid containing at least a solvent, and is measured by a laser light scattering particle size distribution meter. As for the measurement of the particle size by the laser light scattering particle size distribution meter, the color material dispersion liquid can be appropriately diluted with the solvent used in the color material dispersion liquid to a concentration that can be measured by the laser light scattering particle size distribution meter (for example, 1000 times etc.), using a laser light scattering particle size distribution meter (for example, Nanotrac particle size distribution measuring device UPA-EX150 manufactured by Nikkiso Co., Ltd.) and measuring by dynamic light scattering method at 23°C. The average dispersed particle diameter here is the volume average particle diameter.
本發明之彩色濾光片用著色樹脂組成物係含有色材、色素衍生物、分散劑、黏合劑成分、及溶劑者,其特徵在於:上述色材包含吡咯并吡咯二酮系色材,上述色素衍生物係包含吡咯并吡咯二酮系色材之單磺化衍生物與吡咯并吡咯二酮系色材之二磺化衍生物之混合物,並且上述單磺化衍生物之莫耳相對於上述單磺化衍生物與上述二磺化衍生物之莫耳之合計之比{單磺化衍生物/(單磺化衍生物+二磺化衍生物)}為0.10以上且0.90以下,上述分散劑係具有上述通式(I)所表示之構成單元之聚合體。 The colored resin composition for a color filter of the present invention contains a color material, a pigment derivative, a dispersant, a binder component, and a solvent, and is characterized in that the color material includes a diketopyrrolopyrrole color material. The pigment derivative is a mixture of the monosulfonated derivative of the diketopyrrolopyrrole color material and the disulfonated derivative of the diketopyrrolopyrrole color material, and the mole of the monosulfonated derivative is relative to the above The ratio of the total molar ratio of the monosulfonated derivative and the disulfonated derivative {monosulfonated derivative/(monosulfonated derivative + disulfonated derivative)} is 0.10 or more and 0.90 or less, the above dispersant It is a polymer having a structural unit represented by the above general formula (I).
本發明之彩色濾光片用著色樹脂組成物,藉由將包含上述吡咯并吡咯二酮系色材之單磺化衍生物與上述吡咯并吡咯二酮系色材之二磺化衍生物之混合物及上述分散劑與包含吡咯并吡咯二酮系色材之色材組合使用,可抑制著色層形成時之加熱所導致 之對比度之降低,故而可形成高對比度之著色層。 The colored resin composition for color filters of the present invention comprises a mixture of the monosulfonated derivative of the diketopyrrolopyrrole color material and the disulfonated derivative of the diketopyrrolopyrrole color material The combination of the above-mentioned dispersant and the color material containing the diketopyrrolopyrrole color material can suppress the decrease in contrast caused by heating during the formation of the coloring layer, so that a high-contrast coloring layer can be formed.
本發明之彩色濾光片用著色樹脂組成物至少含有色材、色素衍生物、分散劑、黏合劑成分、溶劑,亦可於無損本發明之效果之範圍內進而含有其他成分。以下,對本發明之彩色濾光片用著色樹脂組成物中所包含之各成分進行說明,色材、色素衍生物、分散劑、及溶劑與上述本發明之色材分散液中所說明者相同,因此省略此處之說明。 The colored resin composition for a color filter of the present invention contains at least a color material, a pigment derivative, a dispersant, a binder component, and a solvent, and may further contain other components within a range that does not impair the effects of the present invention. Hereinafter, each component contained in the colored resin composition for a color filter of the present invention will be described. The color material, pigment derivative, dispersant, and solvent are the same as those described in the above-mentioned color material dispersion of the present invention. Therefore, the description here is omitted.
本發明之彩色濾光片用著色樹脂組成物含有用以賦予成膜性或對被塗佈面之密接性之黏合劑成分。為了對塗膜賦予充分之硬度,較佳為含有硬化性黏合劑成分。作為硬化性黏合劑成分,並無特別限定,可適當使用習知公知之用於形成彩色濾光片之著色層之硬化性黏合劑成分。作為硬化性黏合劑成分,例如可使用包含包括可藉由可見光線、紫外線、電子束等進行聚合硬化之光硬化性樹脂之光硬化性黏合劑成分,或包括可藉由加熱進行聚合硬化之熱硬化性樹脂之熱硬化性黏合劑成分者。 The colored resin composition for a color filter of the present invention contains a binder component for imparting film-forming properties or adhesion to the coated surface. In order to provide sufficient hardness to the coating film, it is preferable to contain a curable adhesive component. The curable adhesive component is not particularly limited, and conventionally known curable adhesive components for forming the colored layer of a color filter can be suitably used. As the curable adhesive component, for example, a photocurable adhesive component including a photocurable resin that can be polymerized and cured by visible light, ultraviolet rays, electron beams, etc., or a heat-curable resin that can be polymerized and cured by heating can be used. It is a thermosetting adhesive component of curable resin.
於形成著色層時使用光微影步驟之情形時,可適當使用具有鹼顯影性之感光性黏合劑成分。再者,感光性黏合劑成分中亦可進而使用熱硬化性黏合劑成分。作為感光性黏合劑成分,可列舉正型感光性黏合劑成分與負型感光性黏合劑成分。作為正型感光性黏合劑成分,例如可列舉包含鹼可溶性樹脂與作為感光性賦予成分之含鄰二疊氮醌基之化合物之系統等。 In the case of using the photolithography step when forming the coloring layer, a photosensitive adhesive component with alkali developability can be appropriately used. In addition, a thermosetting adhesive component may be further used in the photosensitive adhesive component. As the photosensitive binder component, a positive photosensitive binder component and a negative photosensitive binder component can be cited. Examples of the positive photosensitive binder component include a system containing an alkali-soluble resin and an o-quinonediazide group-containing compound as a photosensitive imparting component.
另一方面,作為負型感光性黏合劑成分,可適當使用 至少含有鹼可溶性樹脂、多官能單體、及光起始劑之系統。於本發明之彩色濾光片用著色樹脂組成物中,就可藉由光微影法並使用現有之步驟簡便地形成圖案之方面而言,較佳為負型感光性黏合劑成分。以下,對構成負型感光性黏合劑成分之鹼可溶性樹脂、多官能單體、及光起始劑具體地進行說明。 On the other hand, as a negative photosensitive adhesive component, a system containing at least an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator can be suitably used. In the colored resin composition for a color filter of the present invention, a negative photosensitive adhesive component is preferable in terms of a light lithography method and a simple pattern formation using an existing process. Hereinafter, the alkali-soluble resin, the polyfunctional monomer, and the photoinitiator constituting the negative photosensitive adhesive component will be specifically described.
本發明中之鹼可溶性樹脂具有酸性基,作為黏合劑樹脂發揮作用,且可自對於形成圖案時所使用之鹼性顯影液而言為可溶性者中適當選擇並使用。於本發明中,所謂鹼可溶性樹脂,可將酸值為40mgKOH/g以上作為標準。本發明中之較佳之鹼可溶性樹脂係具有酸性基、通常羧基之樹脂,具體而言,可列舉:具有羧基之丙烯酸系共聚合體及具有羧基之苯乙烯-丙烯酸系共聚合體等丙烯酸系樹脂、具有羧基之環氧(甲基)丙烯酸酯樹脂等。該等之中,尤佳為側鏈具有羧基並且側鏈進而具有乙烯性不飽和基等光聚合性官能基者。原因在於藉由含有光聚合性官能基,所形成之硬化膜之膜強度提高。又,該等丙烯酸系共聚合體及苯乙烯-丙烯酸系共聚合體等丙烯酸系樹脂、以及環氧丙烯酸酯樹脂亦可將2種以上混合使用。 The alkali-soluble resin in the present invention has an acidic group, functions as a binder resin, and can be appropriately selected and used from those that are soluble in the alkaline developer used for pattern formation. In the present invention, the so-called alkali-soluble resin may have an acid value of 40 mgKOH/g or more as a standard. Preferred alkali-soluble resins in the present invention are resins having acidic groups and usually carboxyl groups. Specifically, they include acrylic resins such as acrylic copolymers having carboxyl groups and styrene-acrylic copolymers having carboxyl groups. Carboxyl epoxy (meth)acrylate resin, etc. Among these, those having a carboxyl group in the side chain and further having a photopolymerizable functional group such as an ethylenically unsaturated group in the side chain are particularly preferable. The reason is that by containing a photopolymerizable functional group, the film strength of the formed cured film is improved. In addition, acrylic resins such as these acrylic copolymers and styrene-acrylic copolymers, and epoxy acrylate resins may be used in combination of two or more types.
具有含有羧基之構成單元之丙烯酸系共聚合體、及具有羧基之苯乙烯-丙烯酸系共聚合體等丙烯酸系樹脂,例如係藉由公知之方法使含羧基之乙烯性不飽和單體、及視需要之可共聚合之其他單體(共)聚合而獲得之(共)聚合體。作為含羧基之乙烯性不飽和單體,例如可列舉:(甲基)丙烯酸、乙烯基苯甲酸、順丁烯二酸、順丁烯二酸單烷基酯、反丁烯二酸、衣康酸、丁烯酸、桂皮酸、丙烯酸二聚物等。又,亦可利用(甲基)丙烯酸2-羥基乙酯等具有羥基 之單體與順丁烯二酸酐或鄰苯二甲酸酐、環己烷二羧酸酐般之環狀酸酐之加成反應物、ω-羧基-聚己內酯單(甲基)丙烯酸酯等。又,作為羧基之前驅物,亦可使用順丁烯二酸酐、衣康酸酐、檸康酸酐等含酸酐之單體。其中,就共聚性或成本、溶解性、玻璃轉移溫度等之方面而言,尤佳為(甲基)丙烯酸。 Acrylic resins such as acrylic copolymers having structural units containing carboxyl groups, and styrene-acrylic copolymers having carboxyl groups, for example, by known methods to make carboxyl-containing ethylenically unsaturated monomers, and if necessary A (co)polymer obtained by the (co)polymerization of other copolymerizable monomers. Examples of carboxyl group-containing ethylenically unsaturated monomers include (meth)acrylic acid, vinyl benzoic acid, maleic acid, monoalkyl maleate, fumaric acid, and itaconic acid. Acid, crotonic acid, cinnamic acid, acrylic acid dimer, etc. In addition, the addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride can also be used , Ω-carboxy-polycaprolactone mono(meth)acrylate, etc. In addition, as the precursor of the carboxyl group, an acid anhydride-containing monomer such as maleic anhydride, itaconic anhydride, and citraconic anhydride can also be used. Among them, (meth)acrylic acid is particularly preferred in terms of copolymerization, cost, solubility, glass transition temperature, and the like.
就著色層之密接性優異之方面而言,鹼可溶性樹脂較佳為進而具有烴環。藉由於鹼可溶性樹脂中具有作為體積大之基之烴環,硬化時之收縮被抑制,基板之間之剝離緩和而基板密接性提高。又,本發明者等人獲得如下見解:藉由使用具有烴環之鹼可溶性樹脂,所獲得之著色層之耐溶劑性、尤其是著色層之膨潤被抑制。作用雖未明確,但推測藉由於著色層內包含體積大之烴環,著色層內之分子之運動被抑制,結果,塗膜之強度增高,因溶劑而產生之膨潤被抑制。作為此種烴環,可列舉可具有取代基之脂肪族烴環、可具有取代基之芳香族烴環、及該等之組合,烴環可具有烷基、羰基、羧基、氧羰基、醯胺基、羥基、硝基、胺基、鹵素原子等取代基。烴環可以1價之基之形式被包含,亦可以2價以上之基之形式被包含。 In terms of excellent adhesion of the colored layer, the alkali-soluble resin preferably further has a hydrocarbon ring. Since the alkali-soluble resin has a hydrocarbon ring as a bulky group, shrinkage during curing is suppressed, peeling between the substrates is relaxed, and the adhesion of the substrates is improved. In addition, the inventors of the present invention have obtained the knowledge that by using an alkali-soluble resin having a hydrocarbon ring, the solvent resistance of the obtained colored layer, especially the swelling of the colored layer, is suppressed. Although the effect is not clear, it is speculated that the movement of molecules in the colored layer is suppressed due to the large hydrocarbon ring contained in the colored layer. As a result, the strength of the coating film increases and the swelling caused by the solvent is suppressed. Examples of such a hydrocarbon ring include an aliphatic hydrocarbon ring that may have a substituent, an aromatic hydrocarbon ring that may have a substituent, and combinations of these. The hydrocarbon ring may have an alkyl group, a carbonyl group, a carboxyl group, an oxycarbonyl group, and an amide group. Substituents such as hydroxy group, hydroxy group, nitro group, amine group, halogen atom, etc. The hydrocarbon ring may be contained in the form of a monovalent group, or may be contained in the form of a group having a valence of two or more.
作為烴環之具體例,可列舉:環丙烷、環丁烷、環戊烷、環己烷、降烷、三環[5.2.1.0(2,6)]癸烷(二環戊烷)、金剛烷等脂肪族烴環;苯、萘、蒽、菲、茀等芳香族烴環;聯苯、三苯、二苯甲烷、三苯甲烷、茋等鏈狀多環或卡多(Cardo)結構(9,9-二芳基茀)等。 Specific examples of the hydrocarbon ring include: cyclopropane, cyclobutane, cyclopentane, cyclohexane, Alkane, tricyclic [5.2.1.0(2,6)] decane (dicyclopentane), adamantane and other aliphatic hydrocarbon rings; benzene, naphthalene, anthracene, phenanthrene, sulphur and other aromatic hydrocarbon rings; biphenyl, tricyclic Benzene, diphenylmethane, triphenylmethane, stilbene and other chain polycyclic or Cardo structures (9,9-diaryl stilbene) etc.
於包含脂肪族烴環作為烴環之情形時,著色層之耐熱性或密接性提高,並且所獲得之著色層之亮度提高,就該方面而言 較佳。又,於包含上述卡多結構之情形時,著色層之硬化性提高且耐溶劑性(NMP膨潤抑制)提高,就該方面而言尤佳。 In the case where an aliphatic hydrocarbon ring is included as the hydrocarbon ring, the heat resistance or adhesion of the colored layer is improved, and the brightness of the obtained colored layer is improved, which is preferable in this respect. In addition, when the above-mentioned Cardo structure is included, the curability of the colored layer is improved and the solvent resistance (NMP swelling suppression) is improved, which is particularly preferable in this respect.
鹼可溶性樹脂較佳為具有作為具有2個以上之環共有2以上之原子之結構之脂肪族烴環之交聯環式烴環。作為交聯環式烴環之具體例,可列舉:降烷、異烷、金剛烷、三環[5.2.1.0(2,6)]癸烷、三環[5.2.1.0(2,6)]癸烯、三環戊烯、三環戊烷、三環戊二烯、二環戊二烯;該等基之一部分經取代基取代之基。作為上述取代基,可列舉:烷基、環烷基、烷基環烷基、羥基、羰基、硝基、胺基、鹵素原子等。 The alkali-soluble resin is preferably a cross-linked cyclic hydrocarbon ring having an aliphatic hydrocarbon ring having a structure having two or more rings sharing 2 or more atoms. As specific examples of cross-linked cyclic hydrocarbon rings, include: Alkane, iso Alkane, adamantane, tricyclo[5.2.1.0(2,6)]decane, tricyclo[5.2.1.0(2,6)]decene, tricyclopentene, tricyclopentane, tricyclopentadiene , Dicyclopentadiene; a part of these groups substituted by substituents. As said substituent, an alkyl group, a cycloalkyl group, an alkylcycloalkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, a halogen atom, etc. are mentioned.
就與其他材料之相溶性或對鹼性顯影液之溶解性之觀點而言,交聯環式烴環之碳數之下限較佳為5以上,尤佳為7以上。上限較佳為12以下,尤佳為10以下。 From the viewpoint of compatibility with other materials or solubility in an alkaline developer, the lower limit of the carbon number of the crosslinked cyclic hydrocarbon ring is preferably 5 or more, and particularly preferably 7 or more. The upper limit is preferably 12 or less, and particularly preferably 10 or less.
又,鹼可溶性樹脂較佳為具有下述通式(III)所表示之順丁烯二醯亞胺結構。 In addition, the alkali-soluble resin preferably has a maleimide structure represented by the following general formula (III).
(於通式(III)中,RM係可經取代之烴環。) (In the general formula (III), R M is a substituted hydrocarbon ring.)
於鹼可溶性樹脂具有通式(III)所表示之順丁烯二醯亞胺結構之情形時,由於烴環具有氮原子,故而與作為具有上述通式(I)所表示之構成單元之聚合體之鹼性分散劑之相溶性非常好,顯影速度較快,顯影殘渣之抑制效果提高。 When the alkali-soluble resin has the maleimide structure represented by the general formula (III), since the hydrocarbon ring has a nitrogen atom, it is a polymer having the structural unit represented by the general formula (I) The compatibility of the alkaline dispersant is very good, the development speed is faster, and the suppression effect of the development residue is improved.
作為通式(III)之RM中之可經取代之烴環之具體例,可列舉與上述烴環之具體例相同者。例如,可列舉:環戊基、環己基、環辛基等脂肪族烴環、或苯基、甲基苯基、乙基苯基、二甲基苯基、二乙基苯基、甲氧基苯基、苄基、羥基苯基、萘基等芳香族烴環、該等基之一部分經取代基取代之基。 As specific examples of the substituted hydrocarbon ring in R M of the general formula (III), the same as the specific examples of the above-mentioned hydrocarbon ring can be cited. Examples include: aliphatic hydrocarbon rings such as cyclopentyl, cyclohexyl, and cyclooctyl, or phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, and methoxy Aromatic hydrocarbon rings such as phenyl, benzyl, hydroxyphenyl, and naphthyl, and groups in which a part of these groups is substituted with a substituent.
於本發明所使用之鹼可溶性樹脂中,就容易調整各構成單元量,容易增加具有上述烴環之構成單元量而使該構成單元所具有之功能提高之方面而言,較佳為使用獨立具備具有羧基之構成單元及具有上述烴環之構成單元之丙烯酸系共聚合體。具備具有羧基之構成單元及上述烴環之丙烯酸系共聚合體可藉由使用作為上述「可共聚合之其他單體」之具有烴環之乙烯性不飽和單體而製備。 In the alkali-soluble resin used in the present invention, it is easy to adjust the amount of each structural unit, and it is easy to increase the amount of the structural unit having the above-mentioned hydrocarbon ring to improve the function of the structural unit. An acrylic copolymer having a structural unit having a carboxyl group and a structural unit having the above-mentioned hydrocarbon ring. The acrylic copolymer having a structural unit having a carboxyl group and the above-mentioned hydrocarbon ring can be prepared by using an ethylenically unsaturated monomer having a hydrocarbon ring as the above-mentioned "other copolymerizable monomer".
作為具有烴環之乙烯性不飽和單體,例如可列舉:(甲基)丙烯酸環己酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸金剛烷基酯、(甲基)丙烯酸異基酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸苯氧基乙酯、苯乙烯等,就於加熱處理中亦可維持顯影後之著色層之截面形狀之效果較大之方面而言,較佳為使用選自(甲基)丙烯酸環己酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸金剛烷基酯、(甲基)丙烯酸苄酯、及苯乙烯中之至少1種。 Examples of ethylenically unsaturated monomers having a hydrocarbon ring include cyclohexyl (meth)acrylate, dicyclopentyl (meth)acrylate, adamantyl (meth)acrylate, and (meth)acrylic acid. different Base ester, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, styrene, etc., in terms of the effect of maintaining the cross-sectional shape of the colored layer after development during heat treatment , Preferably at least selected from cyclohexyl (meth)acrylate, dicyclopentyl (meth)acrylate, adamantyl (meth)acrylate, benzyl (meth)acrylate, and
又,本發明中所使用之鹼可溶性樹脂較佳為於側鏈具有乙烯性雙鍵。於具有乙烯性雙鍵之情形時,於彩色濾光片製造時之樹脂組成物之硬化步驟中,該鹼可溶性樹脂彼此、或該鹼可溶性樹脂與多官能單體等可形成交聯鍵。硬化膜之膜強度進一步提高而顯影耐受性提高,又,硬化膜之熱收縮被抑制而與基板之密接性變得優異。於鹼可溶性樹脂中導入乙烯性雙鍵之方法,只要自習知公 知之方法中適當選擇即可。例如可列舉:使分子內一併具有環氧基與乙烯性雙鍵之化合物、例如(甲基)丙烯酸縮水甘油酯等與鹼可溶性樹脂所具有之羧基加成而於側鏈導入乙烯性雙鍵之方法,或預先將具有羥基之構成單元導入至共聚合體中,使分子內具備異氰酸酯基與乙烯性雙鍵之化合物加成而於側鏈導入乙烯性雙鍵之方法等。 In addition, the alkali-soluble resin used in the present invention preferably has an ethylenic double bond in the side chain. In the case of having an ethylenic double bond, the alkali-soluble resin or the alkali-soluble resin and the polyfunctional monomer may form a crosslinked bond during the curing step of the resin composition during the color filter manufacturing. The film strength of the cured film is further improved, and the development resistance is improved. In addition, the thermal shrinkage of the cured film is suppressed, and the adhesion to the substrate becomes excellent. The method of introducing an ethylenic double bond into the alkali-soluble resin may be appropriately selected from conventionally known methods. For example, a compound having an epoxy group and an ethylenic double bond in the molecule, such as glycidyl (meth)acrylate and the like, is added to a carboxyl group of an alkali-soluble resin to introduce an ethylenic double bond into the side chain. The method, or a method in which a structural unit having a hydroxyl group is introduced into the copolymer in advance, a compound having an isocyanate group and an ethylenic double bond in the molecule is added, and an ethylenic double bond is introduced into the side chain.
本發明之鹼可溶性樹脂亦可進而含有(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯等具有酯基之構成單元等其他構成單元。具有酯基之構成單元不僅作為抑制著色樹脂組成物之鹼可溶性之成分發揮功能,亦作為提高對溶劑之溶解性、進而溶劑再溶解性之成分發揮功能。 The alkali-soluble resin of the present invention may further contain other structural units such as structural units having ester groups such as methyl (meth)acrylate and ethyl (meth)acrylate. The structural unit having an ester group not only functions as a component that inhibits the alkali solubility of the colored resin composition, but also functions as a component that improves the solubility to the solvent and further the solvent re-solubility.
本發明中之鹼可溶性樹脂較佳為具備具有羧基之構成單元與具有烴環之構成單元之丙烯酸系共聚合體及苯乙烯-丙烯酸系共聚合體等丙烯酸系樹脂,更佳為具備具有羧基之構成單元、具有烴環之構成單元、及具有乙烯性雙鍵之構成單元之丙烯酸系共聚合體及苯乙烯-丙烯酸系共聚合體等丙烯酸系樹脂。 The alkali-soluble resin in the present invention is preferably an acrylic resin having a structural unit having a carboxyl group and a structural unit having a hydrocarbon ring, or an acrylic resin such as a styrene-acrylic copolymer, and more preferably has a structural unit having a carboxyl group , Acrylic resins such as acrylic copolymers and styrene-acrylic copolymers having structural units with hydrocarbon rings and structural units with ethylenic double bonds.
鹼可溶性樹脂可藉由適當調整各構成單元之添加量,而製成具有所需性能之鹼可溶性樹脂。 Alkali-soluble resins can be made into alkali-soluble resins with required properties by appropriately adjusting the addition amount of each constituent unit.
就獲得良好之圖案之方面而言,含羧基之乙烯性不飽和單體之添加量相對於單體總量,較佳為5質量%以上,更佳為10質量%以上。另一方面,就抑制顯影後之圖案表面之膜粗糙等之方面而言,含羧基之乙烯性不飽和單體之添加量相對於單體總量,較佳為50質量%以下,更佳為40質量%以下。若含羧基之乙烯性不飽和單體之比例為上述下限值以上,則所獲得之塗膜對鹼性顯影液之溶解性充分,又,若含羧基之乙烯性不飽和單體之比例為上述上 限值以下,則於利用鹼性顯影液進行顯影時,有所形成之圖案不易自基板脫落或不易產生圖案表面之膜粗糙之傾向。 In terms of obtaining a good pattern, the addition amount of the carboxyl group-containing ethylenically unsaturated monomer is preferably 5% by mass or more, and more preferably 10% by mass or more with respect to the total amount of monomers. On the other hand, in terms of suppressing film roughness on the pattern surface after development, the addition amount of the carboxyl group-containing ethylenically unsaturated monomer relative to the total amount of monomers is preferably 50% by mass or less, more preferably 40% by mass or less. If the ratio of the carboxyl group-containing ethylenically unsaturated monomer is more than the above lower limit, the obtained coating film has sufficient solubility in the alkaline developer, and if the ratio of the carboxyl group-containing ethylenically unsaturated monomer is Below the above upper limit, when developing with an alkaline developer, the formed pattern tends to be less likely to fall off from the substrate or to produce film roughness on the surface of the pattern.
又,於可更佳地使用作為鹼可溶性樹脂之具備具有乙烯性雙鍵之構成單元之丙烯酸系共聚合體及苯乙烯-丙烯酸系共聚合體等丙烯酸系樹脂中,一併具有環氧基與乙烯性雙鍵之化合物相對於含羧基之乙烯性不飽和單體之添加量,較佳為10質量%以上且95質量%以下,更佳為15質量%以上且90質量%以下。 In addition, in acrylic resins such as acrylic copolymers and styrene-acrylic copolymers with structural units having ethylenic double bonds, which can be more preferably used as alkali-soluble resins, they have both epoxy and ethylenic properties. The addition amount of the double bond compound relative to the carboxyl group-containing ethylenically unsaturated monomer is preferably 10% by mass or more and 95% by mass or less, more preferably 15% by mass or more and 90% by mass or less.
含羧基之共聚合體之較佳之重量平均分子量(Mw)較佳為1,000~50,000之範圍,進而較佳為3,000~20,000。若未滿1,000,則存在硬化後之黏合劑功能顯著降低之情況,若超過50,000,則存在於利用鹼性顯影液進行顯影時難以形成圖案之情況。再者,含羧基之共聚合體之上述重量平均分子量(Mw)可將聚苯乙烯作為標準物質,將四氫呋喃(THF,Tetrahydrofuran)作為洗提液並藉由Shodex GPC System-21H進行測定。 The preferred weight average molecular weight (Mw) of the carboxyl group-containing copolymer is preferably in the range of 1,000 to 50,000, and more preferably 3,000 to 20,000. If it is less than 1,000, the adhesive function after curing may be significantly reduced, and if it exceeds 50,000, it may be difficult to form a pattern during development with an alkaline developer. Furthermore, the above-mentioned weight average molecular weight (Mw) of the carboxyl group-containing copolymer can be measured by using polystyrene as a standard substance and tetrahydrofuran (THF, Tetrahydrofuran) as an eluent by Shodex GPC System-21H.
作為具有羧基之環氧(甲基)丙烯酸酯樹脂,並無特別限定,使環氧化合物與含不飽和基之單羧酸之反應物與酸酐反應而獲得之環氧(甲基)丙烯酸酯化合物較適合。環氧化合物、含不飽和基之單羧酸、及酸酐可自公知者中適當選擇並使用。具有羧基之環氧(甲基)丙烯酸酯樹脂可分別單獨使用1種,亦可將兩種以上併用。 The epoxy (meth)acrylate resin having a carboxyl group is not particularly limited. The epoxy (meth)acrylate compound is obtained by reacting the reactant of an epoxy compound and an unsaturated group-containing monocarboxylic acid with an acid anhydride More suitable. Epoxy compounds, unsaturated group-containing monocarboxylic acids, and acid anhydrides can be appropriately selected from known ones and used. The epoxy (meth)acrylate resin which has a carboxyl group may be used individually by 1 type, respectively, and may use 2 or more types together.
就對顯影液所使用之鹼性水溶液之顯影性(溶解性)之方面而言,鹼可溶性樹脂較佳為選擇並使用酸值為50mgKOH/g以上者。就對顯影液所使用之鹼性水溶液之顯影性(溶解性)之方面、及對基板之密接性之方面而言,鹼可溶性樹脂之酸值較佳為70mgKOH/g以上且300mgKOH/g以下,其中,較佳為80mgKOH/g 以上且280mgKOH/g以下。再者,於本發明中,酸值可依據JIS K 0070進行測定。 In terms of the developability (solubility) of the alkaline aqueous solution used in the developer, it is preferable to select and use an alkali-soluble resin having an acid value of 50 mgKOH/g or more. In terms of the developability (solubility) of the alkaline aqueous solution used in the developer and the adhesiveness to the substrate, the acid value of the alkali-soluble resin is preferably 70 mgKOH/g or more and 300 mgKOH/g or less, Among them, it is preferably 80 mgKOH/g or more and 280 mgKOH/g or less. Furthermore, in the present invention, the acid value can be measured in accordance with JIS K 0070.
就獲得硬化膜之膜強度提高且顯影耐受性提高、與基板之密接性優異等效果之方面而言,於鹼可溶性樹脂之側鏈具有乙烯性不飽和基之情形時之乙烯性不飽和鍵當量較佳為100~2000之範圍,尤佳為140~1500之範圍。若該乙烯性不飽和鍵當量為2000以下,則顯影耐受性或密接性優異。又,若為100以上,則可相對增加上述具有羧基之構成單元、或具有烴環之構成單元等其他構成單元之比例,故而顯影性或耐熱性優異。此處,所謂乙烯性不飽和鍵當量,係上述鹼可溶性樹脂中之乙烯性不飽和鍵每1莫耳之重量平均分子量,且由下述數式(1)表示。 In terms of obtaining the effects of improved film strength of the cured film, improved development resistance, and excellent adhesion to the substrate, the ethylenic unsaturated bond when the side chain of the alkali-soluble resin has an ethylenic unsaturated group The equivalent is preferably in the range of 100 to 2000, and particularly preferably in the range of 140 to 1500. If the ethylenically unsaturated bond equivalent is 2000 or less, the development resistance or adhesiveness is excellent. Moreover, if it is 100 or more, the ratio of other structural units, such as the structural unit which has a carboxyl group, or the structural unit which has a hydrocarbon ring, can be relatively increased, and it is excellent in developability and heat resistance. Here, the ethylenically unsaturated bond equivalent is the weight average molecular weight of the ethylenically unsaturated bond in the alkali-soluble resin per 1 mole, and is represented by the following formula (1).
數式(1)乙烯性不飽和鍵當量(g/mol)=W(g)/M(mol) Formula (1) Ethylene unsaturated bond equivalent (g/mol)=W(g)/M(mol)
(數式(1)中,W表示鹼可溶性樹脂之質量(g),M表示鹼可溶性樹脂W(g)中所包含之乙烯性雙鍵之莫耳數(mol)) (In the formula (1), W represents the mass (g) of the alkali-soluble resin, and M represents the number of moles (mol) of the ethylenic double bond contained in the alkali-soluble resin W(g))
上述乙烯性不飽和鍵當量,例如亦可藉由依據JIS K 0070:1992所記載之碘值之試驗方法,測定鹼可溶性樹脂每1g中所包含之乙烯性雙鍵之數量來算出。 The above-mentioned ethylenically unsaturated bond equivalent can also be calculated, for example, by measuring the number of ethylenic double bonds contained in 1 g of the alkali-soluble resin in accordance with the iodine value test method described in JIS K 0070:1992.
彩色濾光片用著色樹脂組成物中使用之鹼可溶性樹脂可單獨使用1種,亦可將2種以上組合使用,其含量並無特別限制,相對於彩色濾光片用著色樹脂組成物之固形份總量,鹼可溶性樹脂較佳為5質量%以上且60質量%以下、進而較佳為10質量%以上且40質量%以下之範圍內。若鹼可溶性樹脂之含量為上述下限 值以上,則容易獲得充分之鹼顯影性,又,若鹼可溶性樹脂之含量為上述上限值以下,則於顯影時容易抑制膜粗糙或圖案之缺損。 The alkali-soluble resin used in the colored resin composition for color filters can be used singly or in combination of two or more. The content is not particularly limited, and is relative to the solid form of the colored resin composition for color filters. As for the total amount, the alkali-soluble resin is preferably in the range of 5% by mass or more and 60% by mass or less, and more preferably in the range of 10% by mass or more and 40% by mass or less. If the content of the alkali-soluble resin is more than the above lower limit value, sufficient alkali developability is easily obtained, and if the content of the alkali-soluble resin is less than the above upper limit value, it is easy to suppress film roughness or pattern defects during development.
彩色濾光片用著色樹脂組成物中使用之多官能單體只要可藉由上述光起始劑聚合即可,並無特別限定,通常可適當使用具有2個以上之乙烯性不飽和雙鍵之化合物,尤佳為具有2個以上之丙烯醯基或甲基丙烯醯基之多官能(甲基)丙烯酸酯。作為此種多官能(甲基)丙烯酸酯,只要自習知公知者中適當選擇並使用即可。作為具體例,例如可列舉日本專利特開2013-029832號公報所記載者等。 The polyfunctional monomer used in the colored resin composition for color filters is not particularly limited as long as it can be polymerized by the above-mentioned photoinitiator. Generally, those having two or more ethylenically unsaturated double bonds can be suitably used. The compound is particularly preferably a multifunctional (meth)acrylate having two or more acryloyl groups or methacryloyl groups. As such a polyfunctional (meth)acrylate, what is necessary is just to select it suitably from a well-known well-known thing, and to use it. As a specific example, for example, those described in JP 2013-029832 A, etc. can be cited.
該等多官能(甲基)丙烯酸酯可單獨使用1種,亦可將2種以上組合使用。又,於對本發明之彩色濾光片用著色樹脂組成物要求優異之光硬化性(高感度)之情形時,多官能單體較佳為具有3個(三官能)以上之可聚合之雙鍵者,較佳為3元以上之多元醇之聚(甲基)丙烯酸酯類或該等之二羧酸改質物,具體而言,較佳為三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯之琥珀酸改質物、季戊四醇四(甲基)丙烯酸酯、二季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯之琥珀酸改質物、二季戊四醇六(甲基)丙烯酸酯等。 These polyfunctional (meth)acrylates may be used individually by 1 type, and may be used in combination of 2 or more types. In addition, when excellent photocurability (high sensitivity) is required for the colored resin composition for color filters of the present invention, the multifunctional monomer preferably has 3 (trifunctional) or more polymerizable double bonds Preferably, poly(meth)acrylates of polyhydric alcohols with three or more valences or these dicarboxylic acid modifiers are preferred. Specifically, trimethylolpropane tri(meth)acrylate, Pentaerythritol tri(meth)acrylate, succinic acid modification product of pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylic acid Ester, dipentaerythritol penta(meth)acrylate modified by succinic acid, dipentaerythritol hexa(meth)acrylate, etc.
彩色濾光片用著色樹脂組成物中使用之上述多官能單體之含量並無特別限制,相對於彩色濾光片用著色樹脂組成物之固形份總量,多官能單體較佳為5質量%以上且60質量%以下,進而較佳為10質量%以上且40質量%以下之範圍內。若多官能單體 之含量為上述下限值以上,則可充分地進行光硬化而抑制曝光部分於顯影時溶出,又,若多官能單體之含量為上述上限值以下,則鹼顯影性充分。 The content of the above-mentioned multifunctional monomer used in the colored resin composition for color filters is not particularly limited, and the multifunctional monomer is preferably 5 mass relative to the total solid content of the colored resin composition for color filters % Or more and 60% by mass or less, more preferably within the range of 10% by mass or more and 40% by mass or less. If the content of the multifunctional monomer is more than the above lower limit, the photocuring can be carried out sufficiently to suppress the elution of the exposed part during development, and if the content of the multifunctional monomer is less than the above upper limit, the alkali developability full.
作為本發明之彩色濾光片用著色樹脂組成物中使用之起始劑,並無特別限制,可自習知已知之各種起始劑之中使用1種或將2種以上組合使用。作為起始劑,可列舉:芳香族酮類、安息香醚類、鹵甲基二唑化合物、α-胺基酮、聯咪唑類、N,N-二甲胺基二苯甲酮、鹵甲基-S-三系化合物、9-氧硫等。作為起始劑之具體例,可列舉:二苯甲酮、4,4'-雙二乙胺基二苯甲酮、4-甲氧基-4'-二甲胺基二苯甲酮等芳香族酮類;安息香甲醚等安息香醚類;乙基安息香等安息香;2-(鄰氯苯基)-4,5-苯基咪唑二聚物等聯咪唑類;2-三氯甲基-5-(對甲氧基苯乙烯基)-1,3,4-二唑等鹵甲基二唑化合物;2-(4-丁氧基-萘并-1-基)-4,6-雙-三氯甲基-S-三等鹵甲基-S-三系化合物;2,2-二甲氧基-1,2-二苯乙烷-1-酮、2-甲基-1-[4-(甲硫基)苯基]-2-啉基丙酮、1,2-苄基-2-二甲胺基-1-(4-啉基苯基)-丁酮-1,1-羥基-環己基-苯基酮、二苯基乙二酮、苯甲醯苯甲酸、苯甲醯苯甲酸甲酯、4-苯甲醯基-4'-甲基二苯硫醚、苄基甲基縮酮、二甲胺基酯苯甲酸、對二甲胺基苯甲酸異戊酯、2-正丁氧基乙基-4-二甲胺基苯甲酸酯、2-氯9-氧硫、2,4-二乙基9-氧硫、2,4-二甲基9-氧硫、異丙基9-氧硫、4-苯甲醯基-甲基二苯硫醚、1-羥基-環己基-苯基酮、2-苄基-2-(二甲胺基)-1-[4-(4-啉基)苯基]-1-丁酮、2-(二甲胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-啉基)苯 基]-1-丁酮、α-二甲氧基-α-苯基苯乙酮、苯基雙(2,4,6-三甲基苯甲醯基)氧化膦、2-甲基-1-[4-(甲硫基)苯基]-2-(4-啉基)-1-丙酮等。其中,可較佳地使用2-甲基-1-[4-(甲硫基)苯基]-2-啉基丙烷-1-酮、2-苄基-2-(二甲胺基)-1-(4-啉基苯基)-1-丁酮、4,4'-雙(二乙胺基)二苯甲酮、二乙基9-氧硫。就調整感度、抑制滲水,從而提高顯影耐受性之方面而言,進而較佳為將如2-甲基-1-[4-(甲硫基)苯基]-2-啉基丙烷-1-酮般之α-胺基苯乙酮系起始劑與如二乙基9-氧硫般之9-氧硫系起始劑組合。使用α-胺基苯乙酮系起始劑與9-氧硫系起始劑之情形時之該等之合計含量相對於著色樹脂組成物之固形份總量,較佳為5質量%以上且15質量%以下。若起始劑量為15質量%以下,則製造步驟中之昇華物減少,故而較佳。若起始劑量為5質量%以上,則滲水等顯影耐受性提高。 The initiator used in the colored resin composition for the color filter of the present invention is not particularly limited, and one kind or a combination of two or more kinds can be used from various known initiators. Examples of the initiator include: aromatic ketones, benzoin ethers, and halomethyl Diazole compounds, α-amino ketones, biimidazoles, N,N-dimethylamino benzophenone, halomethyl-S-tri Series compounds, 9-oxysulfur Wait. Specific examples of the initiator include aromatics such as benzophenone, 4,4'-bisdiethylaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, etc. Ketones; benzoin ethers such as methyl benzoin; benzoin such as ethyl benzoin; biimidazoles such as 2-(o-chlorophenyl)-4,5-phenylimidazole dimer; 2-trichloromethyl-5 -(P-methoxystyryl)-1,3,4- Halomethyl Diazole compound; 2-(4-butoxy-naphth-1-yl)-4,6-bis-trichloromethyl-S-tri Isohalomethyl-S-tri Series compound; 2,2-Dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2- Alkylacetone, 1,2-benzyl-2-dimethylamino-1-(4- (Hydroxyphenyl)-butanone-1,1-hydroxy-cyclohexyl-phenyl ketone, diphenyl ethylenedione, benzyl benzoic acid, benzyl benzoic acid, methyl benzyl benzoate, 4-benzyl- 4'-Methyl diphenyl sulfide, benzyl methyl ketal, dimethylamino ester benzoic acid, isoamyl p-dimethylamino benzoate, 2-n-butoxyethyl-4-dimethylamine Base benzoate, 2-chloro-9-oxysulfur , 2,4-Diethyl 9-oxysulfur , 2,4-Dimethyl 9-oxysulfur , Isopropyl 9-oxysulfur , 4-Benzyl-methyl diphenyl sulfide, 1-hydroxy-cyclohexyl-phenyl ketone, 2-benzyl-2-(dimethylamino)-1-[4-(4- Linyl)phenyl]-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4- (Hydroxy)phenyl)-1-butanone, α-dimethoxy-α-phenylacetophenone, phenylbis(2,4,6-trimethylbenzyl) phosphine oxide, 2- Methyl-1-[4-(methylthio)phenyl]-2-(4- (Alpinyl)-1-acetone and the like. Among them, 2-methyl-1-[4-(methylthio)phenyl]-2- Linylpropan-1-one, 2-benzyl-2-(dimethylamino)-1-(4- (Hydroxyphenyl)-1-butanone, 4,4'-bis(diethylamino)benzophenone, diethyl 9-oxysulfur . In terms of adjusting sensitivity, suppressing water seepage, and improving development tolerance, it is more preferable to add 2-methyl-1-[4-(methylthio)phenyl]-2- Alpha-aminoacetophenone-based starter and diethyl 9-oxysulfide like hydroxypropane-1-one General 9-oxysulfur Department of initiator combination. Using α-aminoacetophenone-based initiator and 9-oxysulfur In the case of a starter, the total content of these is preferably 5% by mass or more and 15% by mass or less with respect to the total solid content of the colored resin composition. If the starting dose is 15% by mass or less, the sublimate in the manufacturing step is reduced, which is preferable. If the starting dose is 5% by mass or more, the development tolerance such as water seepage is improved.
於本發明中,就提高感度之觀點而言,其中,起始劑較佳為包含肟酯系光起始劑。藉由使用肟酯系光起始劑,於形成細線圖案時,容易抑制面內之線寬之差異。進而,藉由使用肟酯系光起始劑,有顯影耐受性提高而滲水產生抑制效果提高之傾向。再者,所謂滲水,係指若使用提高鹼性顯影性之成分,則於鹼性顯影後利用純水進行沖洗後,產生水滲透之痕跡之情況。此種滲水於後烘烤後會消失,因此作為製品不存在問題,但於顯影後進行圖案化面之外觀檢查中,會作為不均異常而被檢測出,從而存在無法將正常品與異常品加以區別之問題。因此,若於外觀檢查中降低檢查裝置之檢查感度,結果會引起最終之彩色濾光片製品之良率降低而成為問題。作為該肟酯系光起始劑,就減少分解物所導致之彩色濾光片用著色樹脂組成物之污染或裝置之污染之方面而言,其中,較佳 為具有芳香環者,更佳為具有包含芳香環之縮合環者,進而較佳為具有包含苯環與雜環之縮合環。作為肟酯系光起始劑,可自1,2-辛二酮-1-[4-(苯硫基)-、2-(鄰苯甲醯基肟)]、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)、日本專利特開2000-80068號公報、特開2001-233842號公報、特表2010-527339、特表2010-527338、特開2013-041153等所記載之肟酯系光起始劑之中適當選擇。作為市售品,亦可使用具有咔唑骨架之Irgacure OXE-01(BASF製造)、Adeka ARKLS NCI-831(ADEKA公司製造)、TR-PBG-304(常州強力電子新材料公司製造)、具有二苯硫醚骨架之Adeka ARKLS NCI-930(ADEKA公司製造)、TR-PBG-345、TR-PBG-3057(以上由常州強力電子新材料公司製造)、具有茀骨架之TR-PBG-365(常州強力電子新材料公司製造)等。就亮度之方面而言,尤佳為使用具有二苯硫醚骨架或茀骨架之肟酯系光起始劑。又,就感度較高之方面而言,較佳為使用具有咔唑骨架之肟酯系光起始劑。又,就容易提高亮度、顯影耐受性,且滲水產生抑制效果較高之方面而言,較佳為將2種以上之肟酯系光起始劑併用。就亮度較高且耐熱性較高之方面而言,尤佳為具有二苯硫醚骨架之肟酯系光起始劑2種之併用,或將具有二苯硫醚骨架之肟酯系光起始劑與具有茀骨架之肟酯系光起始劑併用。又,就感度、亮度優異之方面而言,較佳為將具有咔唑骨架之肟酯系光起始劑與具有茀骨架之肟酯系光起始劑或具有二苯硫醚之肟酯系光起始劑併用。 In the present invention, from the viewpoint of improving sensitivity, among them, the initiator preferably includes an oxime ester-based photoinitiator. By using the oxime ester-based photoinitiator, it is easy to suppress the difference in the line width in the plane when the thin line pattern is formed. Furthermore, by using an oxime ester-based photoinitiator, there is a tendency that the development tolerance is improved and the effect of suppressing the occurrence of water seepage is improved. Furthermore, the term "water seepage" refers to a situation where water seepage marks are produced after alkaline development after washing with pure water if a component that improves alkaline developability is used. This kind of water seepage disappears after post-baking, so there is no problem as a product, but in the appearance inspection of the patterned surface after development, it will be detected as an uneven abnormality, so that it is impossible to distinguish between normal and abnormal products. The issue of distinction. Therefore, if the inspection sensitivity of the inspection device is lowered during the appearance inspection, it will result in a decrease in the yield of the final color filter product, which becomes a problem. As the oxime ester-based photoinitiator, in terms of reducing contamination of the colored resin composition for color filters or device contamination caused by decomposition products, among them, those having an aromatic ring are preferred, and those having an aromatic ring are more preferred. Those having a condensed ring containing an aromatic ring further preferably have a condensed ring containing a benzene ring and a heterocyclic ring. As the oxime ester-based photoinitiator, it can be selected from 1,2-octanedione-1-[4-(phenylthio)-, 2-(o-benzyl oxime)], ethyl ketone, 1-[9 -Ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl)-,1-(O-acetyloxime), Japanese Patent Laid-Open No. 2000-80068, Special The oxime ester-based photoinitiators described in Japanese Patent Publication No. 2001-233842, JP 2010-527339, JP 2010-527338, JP 2013-041153, etc. are appropriately selected. As a commercially available product, Irgacure OXE-01 (manufactured by BASF) with a carbazole skeleton, Adeka ARKLS NCI-831 (manufactured by ADEKA), TR-PBG-304 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), Adeka ARKLS NCI-930 (manufactured by ADEKA), TR-PBG-345, TR-PBG-3057 (the above are manufactured by Changzhou Qiangli Electronic New Materials Co.), TR-PBG-365 (Changzhou) Manufactured by Qiangli Electronic New Materials Co., Ltd.) and so on. In terms of brightness, it is particularly preferable to use an oxime ester-based photoinitiator having a diphenyl sulfide skeleton or a sulphur skeleton. Moreover, in terms of high sensitivity, it is preferable to use an oxime ester-based photoinitiator having a carbazole skeleton. In addition, it is preferable to use two or more types of oxime ester-based photoinitiators in combination in terms of easy improvement in brightness and development tolerance, and a high water-bleeding generation suppression effect. In terms of higher brightness and higher heat resistance, it is particularly preferable to use a combination of two oxime ester photoinitiators with a diphenyl sulfide skeleton, or to use an oxime ester photoinitiator with a diphenyl sulfide skeleton. The starter is used in combination with the oxime ester-based photoinitiator with a citron skeleton. In addition, in terms of excellent sensitivity and brightness, it is preferable to combine an oxime ester-based photoinitiator having a carbazole skeleton and an oxime ester-based photoinitiator having a pyridine skeleton or an oxime ester-based photoinitiator having a diphenyl sulfide. The photoinitiator is used together.
又,就抑制滲水且提高感度之方面而言,較佳為將具有三級胺結構之光起始劑與肟酯系光起始劑組合使用。原因在於由於具有三級胺結構之光起始劑於分子內具有作為氧猝滅劑之三級 胺結構,故而由起始劑產生之自由基不易因氧而失活,從而可提高感度。作為上述具有三級胺結構之光起始劑之市售品,例如可列舉:2-甲基-1-(4-甲硫基苯基)-2-啉基丙烷-1-酮(例如Irgacure 907,BASF公司製造)、2-苄基-2-(二甲胺基)-1-(4-啉基苯基)-1-丁酮(例如Irgacure 369,BASF公司製造)、4,4'-雙(二乙胺基)二苯甲酮(例如Hicure ABP,川口藥品製造)等。又,就調整感度、抑制滲水而提高顯影耐受性之方面而言,較佳為將9-氧硫系起始劑與肟酯系光起始劑進行組合,就亮度、顯影耐受性提高,容易調整感度、滲水產生抑制效果較高、顯影耐受性提高之方面而言,較佳為將2種以上之肟酯系光起始劑與9-氧硫系起始劑進行組合。 Moreover, it is preferable to use a photoinitiator having a tertiary amine structure in combination with an oxime ester-based photoinitiator in terms of suppressing water seepage and improving sensitivity. The reason is that since the photoinitiator with a tertiary amine structure has a tertiary amine structure as an oxygen quencher in the molecule, the free radicals generated by the initiator are not easily deactivated by oxygen, so that the sensitivity can be improved. As a commercially available product of the photoinitiator having the tertiary amine structure, for example, 2-methyl-1-(4-methylthiophenyl)-2- Alkylpropan-1-one (for example, Irgacure 907, manufactured by BASF Corporation), 2-benzyl-2-(dimethylamino)-1-(4- (Alolinylphenyl)-1-butanone (for example, Irgacure 369, manufactured by BASF Corporation), 4,4'-bis(diethylamino)benzophenone (for example, Hicure ABP, manufactured by Kawaguchi Pharmaceutical), and the like. In addition, in terms of adjusting sensitivity, suppressing water seepage and improving development tolerance, it is preferable to add 9-oxysulfur The combination of an oxime ester-based photoinitiator and an oxime ester-based photoinitiator is preferable in terms of improved brightness and development tolerance, easy adjustment of sensitivity, high water seepage suppression effect, and improved development tolerance. More than one kind of oxime ester photoinitiator and 9-oxysulfur Department of initiators for combination.
本發明之彩色濾光片用著色樹脂組成物中所使用之光起始劑之含量相對於上述多官能單體100質量份,通常為0.01質量份以上且100質量份以下左右,較佳為5質量份以上且60質量份以下。若該含量為上述下限值以上,則充分地進行光硬化而抑制曝光部分於顯影時溶出,另一方面,若為上述上限值以下,則所獲得之著色層之黃變性減弱而可抑制亮度降低。又,作為本發明之彩色濾光片用著色樹脂組成物中所使用之光起始劑,就充分地發揮該等光起始劑之併用效果之方面而言,肟酯系光起始劑2種以上之合計含量相對於彩色濾光片用著色樹脂組成物之固形份總量,較佳為0.1質量%以上且12.0質量%以下、進而較佳為1.0質量%以上且8.0質量%以下之範圍內。 The content of the photoinitiator used in the colored resin composition for color filters of the present invention is usually 0.01 parts by mass or more and 100 parts by mass or less, preferably 5 parts by mass, relative to 100 parts by mass of the above-mentioned polyfunctional monomer. Parts by mass or more and 60 parts by mass or less. If the content is more than the above lower limit, the photohardening is sufficiently performed to suppress the elution of the exposed part during development. On the other hand, if the content is less than the above upper limit, the yellowing of the obtained colored layer is weakened and can be suppressed The brightness decreases. In addition, as the photoinitiator used in the colored resin composition for the color filter of the present invention, in terms of fully exhibiting the effect of the combined use of the photoinitiators, the oxime ester-based
又,本發明之彩色濾光片用著色樹脂組成物於上述黏合劑成分包含熱硬化性樹脂之情形時,亦可視需要進而含有熱聚合起始劑。作為熱聚合起始劑,並無特別限制,可自習知已知之熱自 由基聚合起始劑及熱陽離子聚合起始劑等各種熱聚合起始劑之中使用1種或將2種以上組合使用。作為熱自由基聚合起始劑,例如可列舉:2,2'-偶氮二異丁腈(AIBN)等偶氮化合物、過氧化苯甲醯(BPO)等過氧化物等。作為熱陽離子聚合起始劑,例如可列舉:苯磺酸酯、烷基鋶鹽等。於本發明之彩色濾光片用著色樹脂組成物含有熱聚合起始劑之情形時,相對於彩色濾光片用著色樹脂組成物之固形份總量之各種起始劑之合計含量較佳為0.1質量%以上且15.0質量%以下,更佳為1.0質量%以上且10.0質量%以下。 In addition, the colored resin composition for a color filter of the present invention may further contain a thermal polymerization initiator as necessary when the binder component contains a thermosetting resin. The thermal polymerization initiator is not particularly limited, and one type or a combination of two or more types can be used from various thermal polymerization initiators such as conventionally known thermal free radical polymerization initiators and thermal cationic polymerization initiators. Examples of the thermal radical polymerization initiator include azo compounds such as 2,2'-azobisisobutyronitrile (AIBN), and peroxides such as benzyl peroxide (BPO). Examples of the thermal cationic polymerization initiator include benzene sulfonate, alkyl sulfonate, and the like. When the colored resin composition for color filters of the present invention contains a thermal polymerization initiator, the total content of the various initiators relative to the total solid content of the colored resin composition for color filters is preferably 0.1% by mass or more and 15.0% by mass or less, more preferably 1.0% by mass or more and 10.0% by mass or less.
關於本發明之彩色濾光片用著色樹脂組成物中所使用之黏合劑成分,該等之合計含量相對於彩色濾光片用著色樹脂組成物之固形份總量,較佳為以35質量%以上且97質量%以下,更佳為以40質量%以上且96質量%以下之比例調配。若為上述下限值以上,則可獲得硬度或與基板之密接性優異之著色層。又,若為上述上限值以下,則顯影性優異,亦可抑制因熱收縮而導致產生微小之褶皺。 Regarding the binder components used in the colored resin composition for color filters of the present invention, the total content of these components relative to the total solid content of the colored resin composition for color filters is preferably 35% by mass Above and 97% by mass or less, more preferably 40% by mass or more and 96% by mass or less. If it is more than the above lower limit, a colored layer having excellent hardness and adhesion to the substrate can be obtained. Moreover, if it is the said upper limit or less, developability will be excellent, and it can also suppress that a micro wrinkle arises by thermal shrinkage.
彩色濾光片用著色樹脂組成物中亦可視需要包含各種添加劑。作為添加劑,例如除抗氧化劑以外,亦可列舉:巰基化合物、聚合停止劑、鏈轉移劑、調平劑、可塑劑、界面活性劑、消泡劑、矽烷偶合劑、紫外線吸收劑、密接促進劑等。 The colored resin composition for color filters may also contain various additives as needed. Examples of additives include, in addition to antioxidants, mercapto compounds, polymerization stoppers, chain transfer agents, leveling agents, plasticizers, surfactants, defoamers, silane coupling agents, ultraviolet absorbers, and adhesion promoters. Wait.
就提高耐熱性、抑制色材之退色而提高亮度之方面而言,本發明之彩色濾光片用著色樹脂組成物較佳為進而含有抗氧化劑。抗氧化劑只要自習知公知者中適當選擇即可。作為抗氧化劑之 具體例,例如可列舉:受阻酚系抗氧化劑、胺系抗氧化劑、磷系抗氧化劑、硫系抗氧化劑、肼系抗氧化劑等;就耐熱性之方面而言,較佳為使用受阻酚系抗氧化劑。亦可為如國際公開第2014/021023號所記載般之潛在性抗氧化劑。 It is preferable that the colored resin composition for color filters of the present invention further contains an antioxidant in terms of improving heat resistance, suppressing the fading of the color material, and improving brightness. What is necessary is just to select an antioxidant suitably from a well-known thing. Specific examples of antioxidants include, for example, hindered phenol antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, hydrazine antioxidants, etc.; in terms of heat resistance, it is preferable to use Hindered phenolic antioxidants. It can also be a potential antioxidant as described in International Publication No. 2014/021023.
作為受阻酚系抗氧化劑,例如可列舉:季戊四醇肆[3-(3,5-二-第三丁基-4-羥基苯基)丙酸酯](商品名:IRGANOX1010,BASF公司製造)、1,3,5-叁(3,5-二-第三丁基-4-羥基苄基)異氰尿酸酯(商品名:Irganox 3114,BASF製造)、2,4,6-叁(4-羥基-3,5-二-第三丁基苄基)均三甲苯(商品名:Irganox 1330,BASF製造)、2,2'-亞甲基雙(6-第三丁基-4-甲基苯酚)(商品名:Sumilizer MDP-S,住友化學製造)、6,6'-硫代雙(2-第三丁基-4-甲基苯酚)(商品名:Irganox 1081,BASF製造)、3,5-二-第三丁基-4-羥基苄基膦酸二乙酯(商品名:Irgamod 195,BASF製造)等。其中,就耐熱性及耐光性之方面而言,較佳為季戊四醇肆[3-(3,5-二-第三丁基-4-羥基苯基)丙酸酯](商品名:IRGANOX 1010,BASF公司製造)。 Examples of hindered phenol-based antioxidants include: pentaerythritol four [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX 1010, manufactured by BASF Corporation), 1 ,3,5-Tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate (trade name: Irganox 3114, manufactured by BASF), 2,4,6-Tris (4- Hydroxy-3,5-di-tert-butylbenzyl) mesitylene (trade name: Irganox 1330, manufactured by BASF), 2,2'-methylenebis(6-tert-butyl-4-methyl Phenol) (trade name: Sumilizer MDP-S, manufactured by Sumitomo Chemical), 6,6'-thiobis(2-tert-butyl-4-methylphenol) (trade name: Irganox 1081, manufactured by BASF), 3 , Diethyl 5-di-tert-butyl-4-hydroxybenzylphosphonate (trade name: Irgamod 195, manufactured by BASF) and the like. Among them, in terms of heat resistance and light resistance, pentaerythritol four [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX 1010, Made by BASF Corporation).
若本發明之彩色濾光片用著色樹脂組成物組合含有上述肟酯系光起始劑與抗氧化劑,則因協同效應而亮度提高,就該方面而言較佳。 If the colored resin composition combination for a color filter of the present invention contains the above-mentioned oxime ester-based photoinitiator and an antioxidant, the brightness is improved due to a synergistic effect, which is preferable in this respect.
作為抗氧化劑之含量,相對於著色樹脂組成物中之總固形份100質量份,抗氧化劑較佳為0.1質量份以上且10.0質量份以下,更佳為0.5質量份以上且5.0質量份以下。若為上述下限值以上,則耐熱性及耐光性優異。另一方面,若為上述上限值以下,則可將本發明之著色樹脂組成物製成高感度之感光性樹脂組成物。 As the content of the antioxidant, relative to 100 parts by mass of the total solid content in the colored resin composition, the antioxidant is preferably 0.1 parts by mass or more and 10.0 parts by mass or less, more preferably 0.5 parts by mass or more and 5.0 parts by mass or less. If it is more than the said lower limit, it will be excellent in heat resistance and light resistance. On the other hand, if it is not more than the above upper limit, the colored resin composition of the present invention can be made into a highly sensitive photosensitive resin composition.
於將抗氧化劑與上述肟酯系光起始劑組合使用之情 形時,作為抗氧化劑之含量,相對於上述肟酯系光起始劑之合計量100質量份,抗氧化劑較佳為1質量份以上且250質量份以下,更佳為3質量份以上且80質量份以下,進而更佳為5質量份以上且45質量份以下。若為上述範圍內,則上述組合之效果優異。 When an antioxidant is used in combination with the above-mentioned oxime ester-based photoinitiator, the content of the antioxidant is preferably 1 part by mass relative to 100 parts by mass of the total amount of the above-mentioned oxime-ester-based photoinitiator Above and 250 parts by mass or less, more preferably 3 parts by mass or more and 80 parts by mass or less, and still more preferably 5 parts by mass or more and 45 parts by mass or less. If it is in the above range, the effect of the above combination is excellent.
就滲水產生抑制效果提高之方面而言,本發明之彩色濾光片用著色樹脂組成物較佳為進而含有巰基化合物。又,若本發明之彩色濾光片用著色樹脂組成物組合含有上述肟酯系光起始劑與巰基化合物,則顯影耐受性提高,滲水產生抑制效果進而提高,及於形成細線圖案時,直線性進一步提高,或如遮罩線寬之設計般形成細線圖案之能力提高,就該等方面而言較佳。再者,所謂「直線性提高」,係指於塗佈著色組成物後之顯影步驟中形成之著色層之端部之凹凸較少而形成為直線狀或略直線狀。 In terms of improving the effect of suppressing water seepage generation, the colored resin composition for a color filter of the present invention preferably further contains a mercapto compound. In addition, if the colored resin composition combination for a color filter of the present invention contains the above-mentioned oxime ester-based photoinitiator and a mercapto compound, the development resistance is improved, the effect of inhibiting the occurrence of water penetration is further improved, and when a fine line pattern is formed, The linearity is further improved, or the ability to form a thin line pattern like the design of the mask line width is improved, which is better in these respects. Furthermore, the term "improved linearity" means that the end of the colored layer formed in the development step after the application of the colored composition has less unevenness and is formed into a linear or slightly linear shape.
巰基化合物可作為鏈轉移劑發揮功能,具有自反應較慢之自由基獲取自由基而加速反應,從而提高硬化性之性質。作為巰基化合物,例如可列舉:2-巰基苯并噻唑、2-巰基苯并唑、2-巰基苯并咪唑、2-巰基-5-甲氧基苯并噻唑、2-巰基-5-甲氧基苯并咪唑、3-巰基丙酸、3-巰基丙酸甲酯、3-巰基丙酸乙酯、3-巰基丙酸辛酯、1,4-雙(3-巰基丁醯氧基)丁烷、1,3,5-叁(3-巰基丁基氧基乙基)-1,3,5-三-2,4,6(1H,3H,5H)-三酮、三羥甲基丙烷叁(3-巰基丙酸酯)、季戊四醇肆(3-巰基丁酸酯)、季戊四醇肆(3-巰基丙酸酯)、二季戊四醇陸(3-巰基丙酸酯)、及四乙二醇雙(3-巰基丙酸酯)等。作為巰基化合物,可單獨使用或將2種以上組合使用,其中,就交聯密度增高、滲水抑制效果提高之方面而言,較佳為使用選自由1分子中具有2個以上之巰基之多官能巰基化合物所構成之群組中之1種 以上。又,就於長期保存之情形時亦容易維持良好之滲水抑制效果之方面而言,較佳為巰基所鍵結之碳原子為二級碳原子之具有二級巰基之二級巰基化合物,進而更佳為1分子中具有2個以上之該二級巰基之多官能二級巰基化合物。 The sulfhydryl compound can function as a chain transfer agent, and has the property of taking free radicals from the slow-reacting free radicals to accelerate the reaction, thereby improving the hardenability. As the mercapto compound, for example, 2-mercaptobenzothiazole, 2-mercaptobenzo Azole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-methoxybenzimidazole, 3-mercaptopropionic acid, 3-mercaptopropionic acid methyl ester, 3 -Ethyl mercaptopropionate, octyl 3-mercaptopropionate, 1,4-bis(3-mercaptobutoxy)butane, 1,3,5-tris(3-mercaptobutyloxyethyl)- 1,3,5-Three -2,4,6(1H,3H,5H)-triketone, trimethylolpropane three (3-mercaptopropionate), pentaerythritol four (3-mercaptobutyrate), pentaerythritol four (3-mercaptopropane) Acid ester), dipentaerythritol (3-mercaptopropionate), and tetraethylene glycol bis(3-mercaptopropionate). As the mercapto compound, it can be used alone or in combination of two or more. Among them, in terms of increased crosslinking density and improved water penetration inhibitory effect, it is preferable to use a polyfunctional compound selected from the group having two or more mercapto groups in one molecule. One or more of the group consisting of mercapto compounds. In addition, in terms of maintaining a good water permeation inhibitory effect even during long-term storage, it is preferable that the carbon atom to which the sulfhydryl group is bonded is a secondary carbon atom with a secondary sulfhydryl group, and furthermore Preferably, it is a multifunctional secondary mercapto compound having two or more such secondary mercapto groups in one molecule.
彩色濾光片用著色樹脂組成物中所使用之巰基化合物之含量並無特別限制,就充分地發揮上述效果之方面而言,相對於彩色濾光片用著色樹脂組成物之固形份總量,巰基化合物較佳為0.2質量%以上且7質量%以下、進而較佳為0.5質量%以上且5質量%以下之範圍內。 The content of the mercapto compound used in the colored resin composition for color filters is not particularly limited. In terms of fully exerting the above effects, relative to the total solid content of the colored resin composition for color filters, The mercapto compound is preferably within a range of 0.2% by mass or more and 7% by mass or less, and more preferably 0.5% by mass or more and 5% by mass or less.
又,作為界面活性劑及可塑劑之具體例,例如可列舉日本專利特開2013-029832號公報所記載者。 Moreover, as a specific example of a surfactant and a plasticizer, what is described in Unexamined-Japanese-Patent No. 2013-029832 can be mentioned, for example.
色材及色素衍生物之合計含量相對於彩色濾光片用著色樹脂組成物之固形份總量,較佳為以3質量%以上且65質量%以下、更佳為以4質量%以上且60質量%以下之比例調配。若為上述下限值以上,則將彩色濾光片用著色樹脂組成物塗佈成既定之膜厚(通常為1.0~5.0μm)時之著色層具有充分之色濃度。又,若為上述上限值以下,則可獲得保存穩定性優異,並且具有充分之硬度、或與基板之密接性之著色層。尤其是於形成色材濃度較高之著色層之情形時,色材及色素衍生物之合計含量相對於彩色濾光片用著色樹脂組成物之固形份總量,較佳為以15質量%以上且65質量%以下、更佳為以25質量%以上且60質量%以下之比例調配。於本發明之彩色濾光片用著色樹脂組成物中,就抑制加熱所導致之對比度降低之 方面而言,上述吡咯并吡咯二酮系色材之單磺化衍生物及上述吡咯并吡咯二酮系色材之二磺化衍生物之合計含量,相對於吡咯并吡咯二酮系色材100質量份,較佳為1質量份以上,更佳為1.5質量份以上,更佳為2質量份以上,另一方面,就進一步提高著色層之亮度之方面而言,較佳為20質量份以下,更佳為15質量份以下,更佳為12質量份以下,進而更佳為10質量份以下。於本發明之彩色濾光片用著色樹脂組成物中,上述吡咯并吡咯二酮系色材單磺化衍生物及上述吡咯并吡咯二酮系色材二磺化衍生物之合計含量,於色材與色素衍生物之合計含量(100質量%)中,較佳為1質量%以上且20質量%以下,更佳為1.5質量%以上且15質量%以下,進而更佳為2質量%以上且10質量%以下。藉由為上述下限值以上,可進一步抑制加熱所導致之對比度降低,藉由為上述上限值以下,可進一步提高著色層之亮度。又,於本發明之彩色濾光片用著色樹脂組成物進而含有PY138之磺化衍生物之情形時,PY138之磺化衍生物之含量於色材與色素衍生物之合計含量(100質量%)中,較佳為1質量%以上且15質量%以下,更佳為1.5質量%以上且10質量%以下,進而較佳為2質量%以上且7質量%以下。藉由以此種含量使用,可製作不大幅改變色調便達成高亮度且高對比度化之要求之著色層。又,作為分散劑之含量,只要可使色材均勻地分散,則並無特別限定,例如相對於彩色濾光片用著色樹脂組成物之固形份總量,可使用1質量%以上且40質量%以下。進而,相對於彩色濾光片用著色樹脂組成物之固形份總量,較佳為以2質量%以上且30質量%以下之比例調配,尤佳為以3質量%以上且25質量%以下之比例調配。若為上述下限值以上,則色材之分散性及分散穩定性優異,彩 色濾光片用著色樹脂組成物之保存穩定性更優異。又,若為上述上限值以下,則顯影性變得良好。尤其是於形成色材濃度較高之著色層之情形時,分散劑之含量相對於彩色濾光片用著色樹脂組成物之固形份總量,較佳為以2質量%以上且25質量%以下、更佳為以3質量%以上且20質量%以下之比例調配。再者,於鹽型嵌段共聚合體之情形時,分散劑之質量係鹽形成前之上述嵌段共聚合體與有機酸化合物等之合計質量。又,溶劑之含量只要於可高精度地形成著色層之範圍內適當設定即可。相對於包含該溶劑之彩色濾光片用著色樹脂組成物之總量,通常較佳為55質量%以上且95質量%以下之範圍內,其中,更佳為65質量%以上且88質量%以下之範圍內。藉由使上述溶劑之含量為上述範圍內,可製成塗佈性優異者。 The total content of the color material and the pigment derivative relative to the total solid content of the colored resin composition for color filters is preferably 3% by mass or more and 65% by mass or less, more preferably 4% by mass or more and 60% by mass. Proportion of less than mass% is deployed. If it is more than the above lower limit, the coloring layer has sufficient color density when the colored resin composition for color filters is applied to a predetermined film thickness (usually 1.0 to 5.0 μm). Moreover, if it is less than the said upper limit, the coloring layer which is excellent in storage stability, and has sufficient hardness, or adhesiveness with a board|substrate can be obtained. Especially in the case of forming a colored layer with a high color material concentration, the total content of the color material and the pigment derivative relative to the total solid content of the colored resin composition for color filters is preferably 15% by mass or more And 65% by mass or less, and more preferably 25% by mass or more and 60% by mass or less are blended. In the colored resin composition for a color filter of the present invention, the monosulfonated derivative of the diketopyrrolopyrrole color material and the diketopyrrolopyrrole in terms of suppressing the decrease in contrast caused by heating The total content of the two sulfonated derivatives of the color material, relative to 100 parts by mass of the diketopyrrolopyrrole color material, is preferably 1 part by mass or more, more preferably 1.5 parts by mass or more, more preferably 2 parts by mass or more On the other hand, in terms of further improving the brightness of the colored layer, it is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, more preferably 12 parts by mass or less, and still more preferably 10 parts by mass or less. In the colored resin composition for color filters of the present invention, the total content of the above-mentioned diketopyrrolopyrrole-based color material monosulfonated derivative and the above-mentioned diketopyrrolopyrrole-based color material disulfonated derivative is determined in terms of color The total content (100% by mass) of the material and the pigment derivative is preferably 1% by mass or more and 20% by mass or less, more preferably 1.5% by mass or more and 15% by mass or less, still more preferably 2% by mass or more, and 10% by mass or less. By being more than the above-mentioned lower limit, it is possible to further suppress the decrease in contrast caused by heating, and by being less than the above-mentioned upper limit, the brightness of the colored layer can be further improved. In addition, when the colored resin composition for color filters of the present invention further contains the sulfonated derivative of PY138, the content of the sulfonated derivative of PY138 is equal to the total content of the color material and the pigment derivative (100% by mass) Among them, it is preferably 1% by mass or more and 15% by mass or less, more preferably 1.5% by mass or more and 10% by mass or less, and still more preferably 2% by mass or more and 7% by mass or less. By using this content, it is possible to produce a colored layer that meets the requirements of high brightness and high contrast without greatly changing the color tone. In addition, the content of the dispersant is not particularly limited as long as the color material can be uniformly dispersed. For example, it can be 1% by mass or more and 40% by mass relative to the total solid content of the colored resin composition for color filters. %the following. Furthermore, relative to the total solid content of the colored resin composition for color filters, it is preferably blended at a ratio of 2% by mass to 30% by mass, and particularly preferably 3% by mass to 25% by mass. Proportional deployment. If it is more than the above lower limit, the dispersibility and dispersion stability of the color material will be excellent, and the storage stability of the colored resin composition for color filters will be more excellent. Moreover, if it is below the said upper limit, developability will become favorable. Especially in the case of forming a colored layer with a high color material concentration, the content of the dispersant relative to the total solid content of the colored resin composition for color filters is preferably 2% by mass or more and 25% by mass or less , More preferably, it is blended in a ratio of 3% by mass or more and 20% by mass or less. Furthermore, in the case of the salt-type block copolymer, the mass of the dispersant is the total mass of the block copolymer and the organic acid compound, etc. before the salt is formed. In addition, the content of the solvent may be appropriately set within the range where the coloring layer can be formed with high accuracy. With respect to the total amount of the colored resin composition for color filters containing the solvent, it is usually preferably in the range of 55% by mass or more and 95% by mass or less, and more preferably 65% by mass or more and 88% by mass or less Within the range. By setting the content of the above-mentioned solvent within the above-mentioned range, it is possible to obtain an excellent coating property.
本發明之彩色濾光片用著色樹脂組成物之製造方法並無特別限定,例如可列舉:(1)向上述本發明之色材分散液中添加鹼可溶性樹脂、多官能單體、光起始劑、視需要之其他成分,並使用公知之混合手段加以混合之方法;(2)向上述溶劑中同時投入上述色材、上述色素衍生物、上述分散劑、上述鹼可溶性樹脂、上述多官能單體、上述光起始劑、視需要之其他成分,並使用公知之混合手段加以混合之方法;(3)向上述溶劑中添加上述鹼可溶性樹脂、上述多官能單體、上述光起始劑、視需要之其他成分並加以混合後,向其中添加上述本發明之色材分散液並加以混合之方法等。 The method for producing the colored resin composition for color filters of the present invention is not particularly limited, and examples include: (1) Adding alkali-soluble resin, polyfunctional monomer, and photoinitiator to the color material dispersion of the present invention. (2) Put the color material, the pigment derivative, the dispersant, the alkali-soluble resin, and the polyfunctional monofunctional resin into the solvent at the same time. (3) Add the alkali-soluble resin, the polyfunctional monomer, the photoinitiator, the photoinitiator, After mixing other components as needed, the method of adding and mixing the above-mentioned color material dispersion of the present invention.
本發明之彩色濾光片係至少具備基板、及設置於該基板上之著色層者,其特徵在於:該著色層之至少1層係上述本發明之彩色濾光片用著色樹脂組成物之硬化物。 The color filter of the present invention has at least a substrate and a coloring layer provided on the substrate, and is characterized in that at least one layer of the coloring layer is the curing of the coloring resin composition for the color filter of the present invention Things.
一面參照圖,一面對此種本發明之彩色濾光片進行說明。圖1係表示本發明之彩色濾光片之一例之概略截面圖。根據圖1,本發明之彩色濾光片10具有基板1、遮光部2、及著色層3。 With reference to the drawings, the color filter of the present invention will be described. Fig. 1 is a schematic cross-sectional view showing an example of the color filter of the present invention. According to FIG. 1, the
<著色層> <Colored layer>
本發明之彩色濾光片所使用之著色層係至少1層為上述本發明之彩色濾光片用著色樹脂組成物之硬化物之著色層。著色層通常形成於下述基板上之遮光部之開口部,且通常由3色以上之著色圖案構成。又,作為該著色層之排列,並無特別限定,例如可設為條紋型、馬賽克型、三角型、4像素配置型等一般之排列。又,著色層之寬度、面積等可任意地設定。該著色層之厚度係藉由調整塗佈方法、彩色濾光片用著色樹脂組成物之固形份濃度或黏度等而適當控制,通常較佳為1~5μm之範圍。 At least one of the colored layers used in the color filter of the present invention is the colored layer of the cured product of the colored resin composition for the color filter of the present invention. The colored layer is usually formed in the opening of the light-shielding portion on the following substrate, and is usually composed of a colored pattern of more than three colors. In addition, the arrangement of the colored layers is not particularly limited, and it can be, for example, a general arrangement such as a stripe type, a mosaic type, a triangle type, and a 4-pixel arrangement type. In addition, the width, area, etc. of the colored layer can be arbitrarily set. The thickness of the colored layer is appropriately controlled by adjusting the coating method, the solid content concentration or viscosity of the colored resin composition for color filters, etc., and is usually preferably in the range of 1 to 5 μm.
該著色層例如可藉由下述方法形成。首先,使用噴塗法、浸漬塗佈法、棒式塗佈法、輥式塗佈法、旋轉塗佈法、模具塗佈法等塗佈手段將上述本發明之彩色濾光片用著色樹脂組成物塗佈於下述基板上,形成濕式塗膜。其中,可較佳地使用旋轉塗佈法、模具塗佈法。繼而,使用加熱板或烘箱等使該濕式塗膜乾燥後,隔著既定圖案之遮罩對其進行曝光,使鹼可溶性樹脂及多官能單體等進行光聚合反應而製成硬化塗膜。作為曝光所使用之光源,例如可列舉:低壓水銀燈、高壓水銀燈、金屬鹵化物燈等紫外線、電子束 等。曝光量係根據所使用之光源或塗膜之厚度等適當調整。又,曝光後為了促進聚合反應,亦可進行加熱處理。加熱條件根據所使用之彩色濾光片用著色樹脂組成物中之各成分之調配比例、或塗膜之厚度等適當選擇。 This colored layer can be formed by the following method, for example. First, the above-mentioned colored resin composition for color filter of the present invention is applied by coating means such as spray coating method, dip coating method, bar coating method, roll coating method, spin coating method, and die coating method. Coated on the following substrates to form a wet coating film. Among them, the spin coating method and the die coating method can be preferably used. Then, after the wet coating film is dried using a hot plate, an oven, etc., it is exposed through a mask of a predetermined pattern, and an alkali-soluble resin, a polyfunctional monomer, etc. are subjected to photopolymerization to form a cured coating film. As a light source used for exposure, ultraviolet rays, electron beams, etc., such as a low-pressure mercury lamp, a high-pressure mercury lamp, and a metal halide lamp, are mentioned, for example. The amount of exposure is appropriately adjusted according to the light source used or the thickness of the coating film. In addition, in order to promote the polymerization reaction after exposure, heat treatment may be performed. The heating conditions are appropriately selected according to the blending ratio of the components in the colored resin composition for color filters used, the thickness of the coating film, and the like.
繼而,使用顯影液進行顯影處理,將未曝光部分溶解、去除,藉此以所需圖案形成塗膜。作為顯影液,通常使用使鹼溶解於水或水溶性溶劑中而成之溶液。亦可於該鹼性溶液中適量添加界面活性劑等。又,顯影方法可採用一般之方法。顯影處理後,通常進行顯影液之洗淨、彩色濾光片用著色樹脂組成物之硬化塗膜之乾燥而形成著色層。再者,顯影處理後,為了使塗膜充分地硬化,亦可進行加熱處理。作為加熱條件,並無特別限定,根據塗膜之用途適當選擇。 Then, a developing solution is used to perform a development process to dissolve and remove the unexposed part, thereby forming a coating film in a desired pattern. As the developer, a solution obtained by dissolving an alkali in water or a water-soluble solvent is usually used. It is also possible to add an appropriate amount of surfactants and the like to the alkaline solution. In addition, general methods can be used for the development method. After the development treatment, the developer is usually washed, and the cured coating film of the colored resin composition for color filters is dried to form a colored layer. In addition, after the development process, in order to fully harden the coating film, you may perform a heating process. The heating conditions are not particularly limited, and are appropriately selected according to the application of the coating film.
<遮光部> <Shading part>
本發明之彩色濾光片中之遮光部係於下述基板上以圖案狀形成者,並且可設為與於一般之彩色濾光片使用作為遮光部者相同。作為該遮光部之圖案形狀,並無特別限定,例如可列舉條紋狀、矩陣狀等形狀。遮光部亦可為藉由濺鍍法、真空蒸鍍法等而形成之鉻等之金屬薄膜。或者,遮光部亦可為使樹脂黏合劑中含有碳微粒子、金屬氧化物、無機顏料、有機顏料等遮光性粒子而成之樹脂層。於含有遮光性粒子之樹脂層之情形時,有使用感光性抗蝕劑並藉由顯影進行圖案化之方法、使用含有遮光性粒子之噴墨油墨進行圖案化之方法、對感光性抗蝕劑進行熱轉印之方法等。 The light-shielding part in the color filter of the present invention is formed in a pattern on the following substrate, and can be the same as that used as the light-shielding part in a general color filter. The pattern shape of the light-shielding portion is not particularly limited, and examples include shapes such as a stripe shape and a matrix shape. The light-shielding part may also be a metal thin film such as chromium formed by a sputtering method, a vacuum vapor deposition method, or the like. Alternatively, the light-shielding portion may be a resin layer in which light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments are contained in a resin binder. In the case of a resin layer containing light-shielding particles, there are a method of using a photosensitive resist and patterning by development, a method of using inkjet ink containing light-shielding particles, and a method of patterning the photosensitive resist Methods of thermal transfer, etc.
作為遮光部之膜厚,於金屬薄膜之情形時以0.2~0.4 μm左右設定,於使黑色顏料分散或溶解於黏合劑樹脂中而成者之情形時,以0.5~2μm左右設定。 The film thickness of the light-shielding part is set at about 0.2~0.4 μm in the case of a metal thin film, and set at about 0.5~2 μm in the case of a black pigment dispersed or dissolved in a binder resin.
作為基板,使用下述透明基板、矽基板、及於透明基板或矽基板上形成有鋁、銀、銀/銅/鈀合金薄膜等者。亦可於該等基板上形成其他彩色濾光片層、樹脂層、薄膜電晶體(TFT,Thin Film Transistor)等電晶體、電路等。作為本發明之彩色濾光片中之透明基板,只要為對可見光透明之基材即可,並無特別限定,可使用一般之彩色濾光片所使用之透明基板。具體而言,可列舉:石英玻璃、無鹼玻璃、合成石英板等無可撓性之透明之剛性材、或者透明樹脂薄膜、光學用樹脂板、可撓性玻璃等具有可撓性之透明之可撓性材。該透明基板之厚度並無特別限定,可根據本發明之彩色濾光片之用途使用例如100μm~1mm左右者。再者,本發明之彩色濾光片除上述基板、遮光部及著色層以外,例如亦可形成外塗層或透明電極層、以及配向膜或柱狀間隔件等。 As the substrate, the following transparent substrates, silicon substrates, and those having aluminum, silver, silver/copper/palladium alloy thin films, etc. formed on the transparent substrate or silicon substrate are used. Other color filter layers, resin layers, thin film transistors (TFT, Thin Film Transistor) and other transistors, circuits, etc. can also be formed on the substrates. The transparent substrate in the color filter of the present invention is not particularly limited as long as it is a substrate transparent to visible light, and the transparent substrate used in general color filters can be used. Specifically, examples include: non-flexible and transparent rigid materials such as quartz glass, alkali-free glass, synthetic quartz plates, or transparent resin films, optical resin plates, flexible glass, and other flexible and transparent materials. Flexible material. The thickness of the transparent substrate is not particularly limited. According to the application of the color filter of the present invention, for example, a thickness of about 100 μm to 1 mm can be used. Furthermore, in addition to the above-mentioned substrate, light-shielding portion, and coloring layer, the color filter of the present invention may also be formed with, for example, an overcoat layer, a transparent electrode layer, an alignment film, or a columnar spacer.
本發明之顯示裝置之特徵在於具有上述本發明之彩色濾光片。於本發明中,顯示裝置之構成並無特別限定,可自習知公知之顯示裝置之中適當選擇,例如可列舉液晶顯示裝置或有機發光顯示裝置等。 The display device of the present invention is characterized by having the above-mentioned color filter of the present invention. In the present invention, the structure of the display device is not particularly limited, and it can be appropriately selected from conventionally known display devices. For example, a liquid crystal display device or an organic light-emitting display device can be cited.
作為本發明之液晶顯示裝置,例如可列舉具有上述本發明之彩色濾光片、對向基板、及形成於上述彩色濾光片與上述對向基板之間之液晶層的液晶顯示裝置。一面參照圖,一面對此種本發明之液晶顯示裝置進行說明。圖2係表示本發明之液晶顯示裝置之一例之概略圖。如圖2所例示,本發明之液晶顯示裝置40具有彩色濾光片10、具有TFT陣列基板等之對向基板20、及形成於上述彩色濾光片10與上述對向基板20之間之液晶層30。再者,本發明之液晶顯示裝置並不限定於該圖2所示之構成,可設為通常作為使用彩色濾光片之液晶顯示裝置而公知之構成。 Examples of the liquid crystal display device of the present invention include a liquid crystal display device having the color filter of the present invention, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate. With reference to the drawings, the liquid crystal display device of the present invention will be described on the other. Fig. 2 is a schematic diagram showing an example of the liquid crystal display device of the present invention. As shown in FIG. 2, the liquid
作為本發明之液晶顯示裝置之驅動方式,並無特別限定,可採用液晶顯示裝置通常使用之驅動方式。作為此種驅動方式,例如可列舉:扭轉向列(TN,Twisted Nematic)方式、平面內切換(IPS,In plane switching)方式、光學補償彎曲(OCB,Optically Compensated Bend)方式、及多域垂直配向(MVA,Multi-Domain Vertical Alignment)方式等。於本發明中,該等任一方式均可較佳地使用。又,作為對向基板,可根據本發明之液晶顯示裝置之驅動方式等適當選擇並使用。進而,作為構成液晶層之液晶,可根據本發明之液晶顯示裝置之驅動方式等使用介電異向性不同之各種液晶、及該等之混合物。 The driving method of the liquid crystal display device of the present invention is not particularly limited, and a driving method commonly used in liquid crystal display devices can be adopted. As such a driving method, for example, a twisted nematic (TN, Twisted Nematic) method, an in-plane switching (IPS) method, an optically compensated bend (OCB, Optically Compensated Bend) method, and a multi-domain vertical alignment may be mentioned. (MVA, Multi-Domain Vertical Alignment) method, etc. In the present invention, any of these methods can be preferably used. In addition, as the counter substrate, it can be appropriately selected and used according to the driving method of the liquid crystal display device of the present invention and the like. Furthermore, as the liquid crystal constituting the liquid crystal layer, various liquid crystals having different dielectric anisotropies and mixtures thereof can be used according to the driving method of the liquid crystal display device of the present invention.
作為液晶層之形成方法,可使用通常使用作為液晶單元之製作方法之方法,例如可列舉真空注入方式或液晶滴加方式等。於藉由上述方法形成液晶層後,使液晶單元緩冷至常溫,藉此使封入之液晶配向。 As a method of forming the liquid crystal layer, a method generally used as a method of producing a liquid crystal cell can be used, for example, a vacuum injection method or a liquid crystal dropping method can be cited. After the liquid crystal layer is formed by the above method, the liquid crystal cell is slowly cooled to normal temperature, thereby aligning the enclosed liquid crystal.
作為本發明之有機發光顯示裝置,例如可列舉具有上述本發明之彩色濾光片及有機發光體之有機發光顯示裝置。一面參照圖,一面對此種本發明之有機發光顯示裝置進行說明。圖3係表示本發明之有機發光顯示裝置之一例之概略圖。如圖3所例示,本發明之有機發光顯示裝置100具有彩色濾光片10及有機發光體80。亦可於彩色濾光片10與有機發光體80之間具有有機保護層50或無機氧化膜60。 As the organic light-emitting display device of the present invention, for example, an organic light-emitting display device having the above-mentioned color filter and organic light-emitting body of the present invention can be cited. With reference to the drawings, the organic light emitting display device of the present invention will be described on the other. FIG. 3 is a schematic diagram showing an example of the organic light emitting display device of the present invention. As shown in FIG. 3, the organic light-emitting
作為有機發光體80之積層方法,例如可列舉:向彩色濾光片上表面逐次形成透明陽極71、電洞注入層72、電洞傳輸層73、發光層74、電子注入層75、及陰極76之方法,或將形成於另一基板上之有機發光體80貼合於無機氧化膜60上之方法等。有機發光體80中之透明陽極71、電洞注入層72、電洞傳輸層73、發光層74、電子注入層75、及陰極76、其他構成可適當使用公知者。以如上方式製作之有機發光顯示裝置100亦可應用於例如被動驅動方式之有機電致發光(EL,Electroluminescence)顯示器或主動驅動方式之有機EL顯示器。再者,本發明之有機發光顯示裝置並不限定於該圖3所示之構成,可設為作為通常使用彩色濾光片之有機發光顯示裝置公知之構成。 Examples of the method of stacking the organic light-emitting
以下,示出實施例對本發明具體地進行說明。並不藉由該等記載限制本發明。再者,所獲得之色素衍生物之結構、磺酸基之導入個數、及單磺化衍生物與二磺化衍生物之混合比例可藉由使用核磁共振裝置(Bruker BioSpin公司,AVANCEIII HD500MHz) 所測得之1H-及13C-NMR圖譜、使用MALDI-TOF-MS裝置(日本電子股份有限公司製造,型號JMS-S3000)所測得之質譜(MS,mass spectrometry)圖譜確認。 Hereinafter, examples will be shown to specifically describe the present invention. The invention is not limited by these descriptions. Furthermore, the structure of the obtained pigment derivative, the number of introduced sulfonic acid groups, and the mixing ratio of the monosulfonated derivative and the disulfonated derivative can be achieved by using a nuclear magnetic resonance device (Bruker BioSpin, AVANCEIII HD500MHz) The measured 1H- and 13C-NMR spectra were confirmed by mass spectrometry (MS, mass spectrometry) spectra measured using a MALDI-TOF-MS device (manufactured by JEOL Ltd., model JMS-S3000).
將吡咯并吡咯二酮系色材(C.I.顏料紅254,商品名Hostaperm Red D2B-COFLV3781,CLARIANT製造)30質量份添加至20%發煙硫酸300質量份中,其後,以下述表1所示之反應溫度(A℃)、反應時間(B小時)分別進行反應。冷卻後,使反應混合物於3,000質量份之冰水中析出,並進行過濾及水洗而獲得水漿。使該水漿乾燥,藉此獲得下述表1所示之產量(C質量份)之R254磺化物A~E。分別利用NMR對所獲得之R254磺化物A~E進行解析,結果為包含下述化學式(1-m)所表示之單磺化物與下述化學式(1-d)所表示之二磺化物之混合物或下述化學式(1-m)所表示之單磺化物單體。將R254磺化物A~E中之單磺化物(單體)與二磺化物(二聚物)之比率(莫耳%)示於表1。 30 parts by mass of diketopyrrolopyrrole color material (CI Pigment Red 254, trade name Hostaperm Red D2B-COFLV3781, manufactured by CLARIANT) was added to 300 parts by mass of 20% oleum, and thereafter, as shown in Table 1 below The reaction temperature (A°C) and reaction time (B hours) were used for the reaction. After cooling, the reaction mixture was precipitated in 3,000 parts by mass of ice water, and filtered and washed with water to obtain a water slurry. The water slurry was dried to obtain R254 sulfonates A to E in the yield (C parts by mass) shown in Table 1 below. The obtained R254 sulfonates A to E were analyzed by NMR, and the results were a mixture of the monosulfonate represented by the following chemical formula (1-m) and the disulfonate represented by the following chemical formula (1-d) Or the monosulfonate monomer represented by the following chemical formula (1-m). Table 1 shows the ratio (mol %) of monosulfonate (monomer) and disulfonate (dimer) in R254 sulfonates A to E.
於550g之蒸餾水之中導入23.1g之重氮巴比妥酸及19.2g之巴比妥酸。繼而,使用氫氧化鉀水溶液以成為偶氮巴比妥酸(0.3莫耳)之方式進行調整,並與750g之蒸餾水加以混合。藉由滴加而添加5g之30%之鹽酸。其後,導入38.7g之三聚氰胺。繼而,混合添加0.57莫耳之氯化鎳溶液與0.03莫耳之氯化銅溶液,並於80℃之溫度下攪拌8小時。藉由過濾將顏料單離、洗淨,於120℃下使之乾燥,利用乳缽進行磨碎,獲得Azo顏料1(Ni:Cu=95:5(莫耳比)之azo顏料)。 Into 550g of distilled water, 23.1g of diazobarbituric acid and 19.2g of barbituric acid were introduced. Then, the potassium hydroxide aqueous solution was used to adjust so as to become azobarbituric acid (0.3 mol), and it was mixed with 750 g of distilled water. Add 5g of 30% hydrochloric acid by dripping. After that, 38.7 g of melamine was introduced. Then, 0.57 mol of nickel chloride solution and 0.03 mol of copper chloride solution were mixed and added, and the mixture was stirred at a temperature of 80° C. for 8 hours. The pigment was separated by filtration, washed, dried at 120°C, and ground with a mortar to obtain Azo pigment 1 (Ni:Cu=95:5 (mole ratio) azo pigment).
於製造例6中,使用0.39莫耳之氯化鎳溶液與0.21莫耳之氯化鋅溶液代替0.57莫耳之氯化鎳溶液與0.03莫耳之氯化銅溶液,除此以外,以與製造例4相同之方式獲得Azo顏料2(Ni:Zn=65:35(莫耳比)之azo顏料)。 In manufacturing example 6, 0.39 mol of nickel chloride solution and 0.21 mol of zinc chloride solution were used instead of 0.57 mol of nickel chloride solution and 0.03 mol of copper chloride solution. Azo pigment 2 (Ni:Zn=65:35 (mole ratio) azo pigment) was obtained in the same manner as in Example 4.
將500ml之四口可分離式燒瓶減壓並乾燥後,進行Ar(氬氣)置換。一面使Ar流動,一面添加脫水THF100g、甲基三甲基矽烷基二甲基乙烯酮縮醛2.0g、四丁基銨-3-氯苯甲酸酯(TBACB)之1M乙腈溶液0.15ml、均三甲苯0.2g。使用滴加漏斗歷時45分鐘向其中滴加甲基丙烯酸2-乙基己酯(EHMA)13.4質量份、甲基丙烯酸正丁酯(BMA)14.3質量份、甲基丙烯酸苄酯(BzMA)9.9質量份、甲基丙烯酸甲酯(MMA)35.7質量份。當反應進行時會發熱,故而藉由冰冷將溫度保持為未滿40℃。1小時後,歷時15分鐘滴加甲基丙烯酸二甲胺基乙酯(DMMA)26.7質量份。反應1小時後,添加甲醇5質量份而使反應停止。將溶劑減壓去除,獲得嵌段共聚合體A。藉由GPC測定(NMP LiBr10mM)而求出之重量平均分子量為8,350,胺值為95mgKOH/g。 After depressurizing and drying a 500ml four-neck separable flask, it was replaced with Ar (argon). While allowing Ar to flow, add 100g of dehydrated THF, 2.0g of methyltrimethylsilyldimethylketene acetal, 0.15ml of 1M acetonitrile solution of tetrabutylammonium-3-chlorobenzoate (TBACB), uniform 0.2g of trimethylbenzene. Use a dropping funnel to dropwise add 2-ethylhexyl methacrylate (EHMA) 13.4 parts by mass, n-butyl methacrylate (BMA) 14.3 parts by mass, and benzyl methacrylate (BzMA) 9.9 parts by mass into it for 45 minutes. Parts, 35.7 parts by mass of methyl methacrylate (MMA). As the reaction progresses, heat is generated, so the temperature is kept below 40°C by ice cooling. After 1 hour, 26.7 parts by mass of dimethylaminoethyl methacrylate (DMMA) was added dropwise over 15 minutes. After reacting for 1 hour, 5 parts by mass of methanol was added to stop the reaction. The solvent was removed under reduced pressure, and a block copolymer A was obtained. The weight average molecular weight determined by GPC measurement (NMP LiBr10mM) was 8,350, and the amine value was 95mgKOH/g.
於100mL圓底燒瓶中將29.35質量份之嵌段共聚合體A溶解於PGMEA29.35質量份中,添加苯基膦酸(PPA,東京化成製造)3.96質量份(苯基膦酸(PPA)相對於嵌段共聚合體A之DMMA單元1莫耳為0.25莫耳,PPA為二元,因此為0.5莫耳當量),於反應溫度30℃下攪拌20小時,藉此獲得鹽型嵌段共聚合體A-1溶液。鹽形成後之胺值具體而言係以如下方式算出。向NMR試樣管中添加將9質量份之鹽型嵌段共聚合體A-1(再沈澱後之固形物)與91質量份之氯仿-D1NMR用加以混合而成之溶液1g,使用核磁共振裝置(日本電子製造,FT NMR、JNM-AL400)於室溫、積算次數10000次之 條件下測定13C-NMR圖譜。根據所獲得之圖譜資料中於末端之氮部位(胺基)與未形成鹽之氮原子相鄰之碳原子波峰及與形成鹽之氮原子相鄰之碳原子波峰之積分值之比率,算出形成鹽之胺基數相對於胺基總數之比率,確認到與理論性鹽形成比率相同(總苯基膦酸之2個酸性基與嵌段共聚合體A之DMMA之末端之氮部位形成鹽)。將鹽形成前之胺值95mgKOH/g減去DMMA單元之0.5莫耳量之胺值(47.5mgKOH/g),算出鹽形成後之胺值為47.5mgKOH/g。鹽形成後之鹽型嵌段共聚合體A-1之酸值與鹽形成前嵌段共聚合體A相同。將所獲得之鹽形成前及鹽形成後之嵌段共聚合體之酸值及胺值示於表2、3。再者,於表2、3中,鹽形成化合物之量由相對於通式(I)所表示之構成單元所具有之氮部位(DMMA)1莫耳之鹽形成化合物之莫耳數表示。 In a 100 mL round bottom flask, 29.35 parts by mass of block copolymer A was dissolved in 29.35 parts by mass of PGMEA, and 3.96 parts by mass of phenylphosphonic acid (PPA, manufactured by Tokyo Chemical Industry) was added (phenylphosphonic acid (PPA) relative to The
於合成例1之(2)中,以相對於DMMA單元1莫耳成為0.5莫耳之方式添加對甲苯磺酸代替苯基膦酸,除此以外,以與合成例1相同之方式獲得鹽型嵌段共聚合體A-2溶液。 In (2) of Synthesis Example 1, p-toluenesulfonic acid was added in place of phenylphosphonic acid so as to be 0.5 mol relative to 1 mol of DMMA unit, and the salt form was obtained in the same manner as Synthesis Example 1 except that Block copolymer A-2 solution.
向具備冷凝管、添加用漏斗、氮氣用入口、機械攪拌機、數位溫度計之500mL圓底四口可分離式燒瓶中添加THF250質量份、氯化鋰0.6質量份,充分地進行氮氣置換。將反應燒瓶冷卻至-60℃後,使用注射器注入丁基鋰4.9質量份(15質量%己烷溶液)、二 異丙基胺1.1質量份、異丁酸甲酯1.0質量份。使用添加用漏斗歷時60分鐘滴加B嵌段用單體之甲基丙烯酸1-乙氧基乙酯(EEMA)3.3質量份、甲基丙烯酸2-羥基乙酯(HEMA)18.7質量份、甲基丙烯酸2-乙基己酯(EHMA)12.8質量份、甲基丙烯酸正丁酯(BMA)13.7質量份、甲基丙烯酸苄酯(BzMA)9.5質量份、甲基丙烯酸甲酯(MMA)17.5質量份。30分鐘後,歷時20分鐘滴加作為A嵌段用單體之甲基丙烯酸二甲胺基乙酯(DMMA)26.7質量份。反應30分鐘後,添加甲醇1.5質量份而使反應停止。使所獲得之前驅物嵌段共聚合體THF溶液於己烷中再沈澱,並藉由過濾、真空乾燥而進行精製,利用PGMEA進行稀釋而製成固形份30質量%溶液。添加32.5質量份之水,升溫至100℃並反應7小時,將源自EEMA之構成單元脫保護而製成源自甲基丙烯酸(MAA)之構成單元。使所獲得之嵌段共聚合體PGMEA溶液於己烷中再沈澱,並藉由過濾、真空乾燥而進行精製,獲得含有包含通式(I)所表示之構成單元之A嵌段與包含源自含羧基單體之構成單元且具有親溶劑性之B嵌段之嵌段共聚合體B(酸值8mgKOH/g)。利用GPC(凝膠滲透層析法)對以此種方式獲得之嵌段共聚合體B進行確認,結果,重量平均分子量Mw為7000。又,胺值為95mgKOH/g。 To a 500 mL round bottom four-neck separable flask equipped with a condenser, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, 250 parts by mass of THF and 0.6 parts by mass of lithium chloride were added, and nitrogen replacement was carried out sufficiently. After cooling the reaction flask to -60°C, 4.9 parts by mass of butyllithium (15% by mass hexane solution), 1.1 parts by mass of diisopropylamine, and 1.0 part by mass of methyl isobutyrate were injected using a syringe. Using the addition funnel, dropwise add 3.3 parts by mass of 1-ethoxyethyl methacrylate (EEMA), 18.7 parts by mass of 2-hydroxyethyl methacrylate (HEMA), methyl 12.8 parts by mass of 2-ethylhexyl acrylate (EHMA), 13.7 parts by mass of n-butyl methacrylate (BMA), 9.5 parts by mass of benzyl methacrylate (BzMA), and 17.5 parts by mass of methyl methacrylate (MMA) . After 30 minutes, 26.7 parts by mass of dimethylaminoethyl methacrylate (DMMA), which is a monomer for the A block, was added dropwise over 20 minutes. After reacting for 30 minutes, 1.5 parts by mass of methanol was added to stop the reaction. The obtained precursor block copolymer THF solution was reprecipitated in hexane, purified by filtration and vacuum drying, and diluted with PGMEA to prepare a solid content 30% by mass solution. 32.5 parts by mass of water was added, the temperature was raised to 100° C. and reacted for 7 hours, and the structural unit derived from EEMA was deprotected to obtain a structural unit derived from methacrylic acid (MAA). The obtained block copolymer PGMEA solution was reprecipitated in hexane, and purified by filtration and vacuum drying to obtain an A block containing the structural unit represented by the general formula (I) and containing Block copolymer B (acid value 8mgKOH/g) which is a constitutional unit of carboxyl monomer and has a solvent-philic B block. The block copolymer B obtained in this manner was confirmed by GPC (Gel Permeation Chromatography). As a result, the weight average molecular weight Mw was 7000. In addition, the amine value is 95 mgKOH/g.
於100mL圓底燒瓶中將29.35質量份之嵌段共聚合體B溶解於PGMEA 29.35質量份中,添加苯基膦酸(東京化成製造)3.98質量份(苯基膦酸(PPA)相對於嵌段共聚合體B之DMMA單元1莫耳為0.25莫耳,PPA為二元,因此為0.5莫耳當量),於反應溫度30℃ 下攪拌20小時,藉此獲得鹽型嵌段共聚合體B-1溶液。鹽形成後之胺值以與合成例1相同之方式算出。將所獲得之鹽形成前及鹽形成後之嵌段共聚合體之酸值、及胺值示於表2。 In a 100 mL round bottom flask, 29.35 parts by mass of block copolymer B was dissolved in 29.35 parts by mass of PGMEA, and 3.98 parts by mass of phenylphosphonic acid (manufactured by Tokyo Chemical Industry) was added (phenylphosphonic acid (PPA) relative to block copolymerization). The
於氮氣流下、100℃下歷時3小時將BzMA 40質量份、MMA 15質量份、MAA 25質量份、及AIBN 3質量份之混合液滴加至添加有PGMEA 150質量份之聚合槽中。滴加結束後,進而於100℃下加熱3小時,獲得聚合體溶液。該聚合體溶液之重量平均分子量為7000。繼而,向所獲得之聚合體溶液中添加甲基丙烯酸縮水甘油酯(GMA)20質量份、三乙胺0.2質量份、及對甲氧基苯酚0.05質量份,於110℃下加熱10小時,向反應溶液中通入空氣。所獲得之鹼可溶性樹脂A係使用GMA將具有乙烯性雙鍵之側鏈導入至藉由BzMA與MMA、MAA之共聚合而形成之主鏈之樹脂,固形份為42.6質量%,酸值為74mgKOH/g,重量平均分子量為12000。將聚苯乙烯作為標準物質,將THF作為洗提液並藉由Shodex GPC System-21H測定重量平均分子量。又,酸值之測定方法係基於JIS K 0070進行測定。 A mixed solution of 40 parts by mass of BzMA, 15 parts by mass of MMA, 25 parts by mass of MAA, and 3 parts by mass of AIBN was added dropwise to a polymerization tank containing 150 parts by mass of PGMEA over 3 hours at 100°C under a nitrogen stream. After the dropwise addition, it was further heated at 100°C for 3 hours to obtain a polymer solution. The weight average molecular weight of the polymer solution was 7,000. Then, 20 parts by mass of glycidyl methacrylate (GMA), 0.2 parts by mass of triethylamine, and 0.05 parts by mass of p-methoxyphenol were added to the obtained polymer solution, and heated at 110°C for 10 hours. Air is introduced into the reaction solution. The obtained alkali-soluble resin A uses GMA to introduce the side chain with ethylenic double bond into the main chain formed by the copolymerization of BzMA, MMA and MAA. The solid content is 42.6% by mass and the acid value is 74mgKOH. /g, the weight average molecular weight is 12,000. Using polystyrene as a standard substance and THF as an eluent, the weight average molecular weight was measured by Shodex GPC System-21H. In addition, the acid value measurement method is based on JIS K 0070.
將11質量%發煙硫酸374.76質量份一面冷卻至10℃,一面進行攪拌,並添加74.96質量份之PY138。繼而,於90℃下攪拌6小時。將反應液添加至冰水1600質量份中並攪拌15分鐘後,對沈澱物進行過濾。利用800質量份之水將所獲得之濕濾餅洗淨3次。將 濕濾餅於80℃下真空乾燥,獲得Y138磺化物。Y138磺化物於上述通式(S)中,Z"=SO3H,w=1,藉由飛行時間-質譜法(TOF-MS,Time of Flight Mass Spectrometry)確認目標物之分子量。 374.76 parts by mass of 11% by mass oleum was cooled to 10° C. while stirring, and 74.96 parts by mass of PY138 was added. Then, it stirred at 90 degreeC for 6 hours. After adding the reaction liquid to 1,600 parts by mass of ice water and stirring for 15 minutes, the precipitate was filtered. The obtained wet cake was washed 3 times with 800 parts by mass of water. The wet cake was vacuum dried at 80°C to obtain Y138 sulfonate. The Y138 sulfonate is in the above general formula (S), Z"=SO 3 H, w=1, and the molecular weight of the target is confirmed by TOF-MS (Time of Flight Mass Spectrometry).
將作為分散劑之合成例1之鹽型嵌段共聚合體A-1溶液9.84質量份、下述化學式(2)所表示之吡咯并吡咯二酮系色材(BrDPP,商品名「Irgaphor RED S 3621CF」BASF公司製造)11.57質量份、製造例1中所獲得之R254磺化物A 0.65質量份(於色素及色素衍生物之合計含量100質量%中,R254磺化物A之比例為5質量%)、合成例5中所獲得之PY138磺化衍生物A 0.78質量份、合成例4中所獲得之鹼可溶性樹脂A溶液12.29質量份、PGMEA 64.87質量份、粒徑2.0mm氧化鋯珠100質量份添加至美乃滋瓶中,利用塗料振盪機(淺田鐵工(股)製造)振盪1小時作為預解碎,繼而,將粒徑2.0mm氧化鋯珠取出,添加粒徑0.1mm之氧化鋯珠200質量份,同樣地利用塗料振盪機進行4小時分散作為正式解碎,獲得色材分散液R1。 As a dispersant, 9.84 parts by mass of the salt-type block copolymer A-1 solution of Synthesis Example 1 and the diketopyrrolopyrrole color material (BrDPP, trade name "Irgaphor RED S 3621CF) represented by the following chemical formula (2) "Manufactured by BASF Corporation) 11.57 parts by mass, 0.65 parts by mass of R254 sulfonate A obtained in Manufacturing Example 1 (in the total content of pigment and pigment derivative 100% by mass, the proportion of R254 sulfonate A is 5% by mass), 0.78 parts by mass of the PY138 sulfonated derivative A obtained in Synthesis Example 5, 12.29 parts by mass of the alkali-soluble resin A solution obtained in Synthesis Example 4, 64.87 parts by mass of PGMEA, and 100 parts by mass of zirconia beads with a particle size of 2.0 mm were added to In the mayonnaise bottle, use a paint shaker (manufactured by Asada Iron Works Co., Ltd.) to shake for 1 hour as pre-crushing. Then, take out the zirconia beads with a diameter of 2.0 mm and add 200 parts by mass of zirconia beads with a diameter of 0.1 mm. In the same manner, dispersion was performed for 4 hours using a paint shaker as the main disintegration to obtain a color material dispersion liquid R1.
[化13]
添加上述(1)中所獲得之色材分散液R1 11.29質量份、合成例4中所獲得之鹼可溶性樹脂A溶液1.90質量份、多官能單體(商品名ARONIXM-403,東亞合成(股)公司製造)0.60質量份、2-甲基-1-(4-甲硫基苯基)-2-啉基丙烷-1-酮(光起始劑:商品名Irgacure 907(IRG907),BASF(股)製造)0.09質量份、2-苄基-2-二甲胺基-1-(4-啉基苯基)-丁酮-1(光起始劑:商品名Irgacure 369(IRG369),BASF製造)0.04質量部、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)(光起始劑:商品名ADEKA ARKLS NCI-831(NCI831),ADEKA公司製造)0.02質量份、氟系界面活性劑(商品名MEGAFAC F559,DIC(股)製造)0.07質量份、矽烷偶合劑(商品名KBM-503,信越矽利光製造)0.07質量份、巰基化合物(季戊四醇肆(3-巰基丁酸酯))0.05質量份、PGMEA 5.85質量份、乙酸3-甲氧基-3-甲基-1-丁酯3.92質量份,獲得彩色濾光片用著色樹脂 組成物R1。 Add 11.29 parts by mass of the color material dispersion R1 obtained in (1) above, 1.90 parts by mass of the alkali-soluble resin A solution obtained in Synthesis Example 4, and a multifunctional monomer (trade name ARONIXM-403, Toagosei Co., Ltd.) Company manufacture) 0.60 parts by mass, 2-methyl-1-(4-methylthiophenyl)-2- Linylpropan-1-one (photoinitiator: trade name Irgacure 907 (IRG907), manufactured by BASF Co., Ltd.) 0.09 parts by mass, 2-benzyl-2-dimethylamino-1-(4- Alolinophenyl)-butanone-1 (photoinitiator: trade name Irgacure 369 (IRG369), manufactured by BASF) 0.04 mass part, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzene) (Formyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime) (photoinitiator: trade name ADEKA ARKLS NCI-831 (NCI831), manufactured by ADEKA) 0.02 parts by mass , Fluorine-based surfactant (trade name MEGAFAC F559, manufactured by DIC Co., Ltd.) 0.07 parts by mass, silane coupling agent (trade name KBM-503, manufactured by Shin-Etsu Silicon Co., Ltd.) 0.07 parts by mass, mercapto compound (pentaerythritol 4 (3-mercapto) Butyrate)) 0.05 parts by mass, 5.85 parts by mass of PGMEA, and 3.92 parts by mass of 3-methoxy-3-methyl-1-butyl acetate to obtain a colored resin composition R1 for a color filter.
使用旋轉塗佈機將上述(2)中所獲得之著色樹脂組成物R1以厚度0.7mm塗佈於100mm×100mm之玻璃基板(NH TECHNO GLASS(股)公司製造,「NA35」)上後,使用加熱板於80℃下乾燥3分鐘,使用超高壓水銀燈照射60mJ/cm2之紫外線,進而於230℃之無塵烘箱中後烘烤30分鐘,藉此,以硬化後之膜厚成為2.00μm之方式調整膜厚而形成著色層R1。 Use a spin coater to coat the colored resin composition R1 obtained in (2) above with a thickness of 0.7mm on a 100mm×100mm glass substrate (manufactured by NH TECHNO GLASS Co., Ltd., "NA35"), and then use The heating plate was dried at 80°C for 3 minutes, and an ultra-high pressure mercury lamp was used to irradiate 60mJ/cm 2 of ultraviolet rays, and then post-baked in a dust-free oven at 230°C for 30 minutes, so that the cured film thickness became 2.00μm. In this way, the film thickness is adjusted to form the colored layer R1.
於實施例1之(1)中,將色材及色素衍生物之種類及調配比率、以及分散劑之種類如表2及表3所示般變更,將分散劑之使用量以與固形份成為相同質量份之方式變更,以合計成為100質量份之方式調整PGMEA量,除此以外,以與實施例1之(1)相同之方式獲得色材分散液R2~R14、RC1~RC5。再者,於表2及表3中示出將色材及色素衍生物之合計含量設為100質量份時之各色材及各色素衍生物之調配比例(質量%)。各色材分散液中所添加之色材及色素衍生物之合計添加量為13質量份。 In (1) of Example 1, the types and blending ratios of color materials and pigment derivatives, and the types of dispersants were changed as shown in Tables 2 and 3, and the amount of dispersant used was changed to the solid content. The method of the same parts by mass was changed, and the amount of PGMEA was adjusted so that the total was 100 parts by mass, except that the color material dispersion liquids R2 to R14 and RC1 to RC5 were obtained in the same manner as in Example 1 (1). In addition, in Table 2 and Table 3, the blending ratio (mass %) of each color material and each pigment derivative when the total content of the color material and the pigment derivative is 100 parts by mass is shown. The total addition amount of the color material and the pigment derivative added to each color material dispersion liquid was 13 parts by mass.
於實施例1之(2)中,使用色材分散液R2~R14、RC1~RC5代替色材分散液R1,為了將著色層之膜厚設為2.00μm,以使P/V比 成為表2及表3所示之值之方式調整鹼可溶性樹脂之量,除此以外,以與實施例1之(2)相同之方式獲得彩色濾光片用著色樹脂組成物R2~R14、RC1~RC5。 In Example 1 (2), the color material dispersion liquid R2~R14, RC1~RC5 were used instead of the color material dispersion liquid R1, in order to set the film thickness of the color layer to 2.00μm, so that the P/V ratio became Table 2 The amount of alkali-soluble resin was adjusted according to the values shown in Table 3, except that the colored resin compositions R2 to R14 and RC1 to RC5 for color filters were obtained in the same manner as in Example 1 (2).
於實施例1之(3)中,分別使用上述著色樹脂組成物R2~R14、RC1~R5代替著色樹脂組成物R1,除此以外,以與實施例1之(3)相同之方式獲得著色層R2~R14、RC1~RC5。 In Example 1 (3), the above colored resin composition R2~R14, RC1~R5 were used instead of the colored resin composition R1, except that the colored layer was obtained in the same manner as in Example 1 (3) R2~R14, RC1~RC5.
此處,表中各簡稱如下所述。 Here, the abbreviations in the table are as follows.
Br-DPP:商品名Irgaphor RED S 3621CF,BASF公司製造 Br-DPP: Trade name Irgaphor RED S 3621CF, manufactured by BASF
R254:C.I.顏料紅254(商品名Hostaperm Red D2B-COF LV3781,CLARIANT製造) R254: C.I. Pigment Red 254 (trade name Hostaperm Red D2B-COF LV3781, manufactured by CLARIANT)
Y150:C.I.顏料黃150(G04,Lanxess股份有限公司製造) Y150: C.I. Pigment Yellow 150 (G04, manufactured by Lanxess Co., Ltd.)
Byk2001:商品名Disperbyk-2001,BYK-Chemie製造 Byk2001: Trade name Disperbyk-2001, manufactured by BYK-Chemie
針對實施例1~10及比較例1~4中所獲得之色材分散液,分別測定剛製備後及於25℃下保存30天後之黏度,根據保存前後之黏度算出黏度變化率,對黏度穩定性進行評價。黏度測定係使用振 動式黏度計測定25.0±0.5℃下之黏度。黏度變化率(%)係藉由{[於25℃下保存30天後之黏度(mPa.s)-剛製備後之黏度(mPa.s)]/剛製備後之黏度(mPa.s)}×100而算出。將實施例1~10及比較例1~4中之剛製備後之黏度(初始黏度)及黏度變化率(%)示於表2。其中,相對於包含色材分散液之溶劑之合計質量,為將色材及色素衍生物之合計含量設為13質量%時之值。若黏度變化率未滿25%,則色材分散液可於實際使用中使用,黏度變化率越小,色材分散液之分散穩定性越優異。又,將黏度變化率300%以上者設為「無法測定」。 For the color material dispersions obtained in Examples 1 to 10 and Comparative Examples 1 to 4, the viscosity was measured immediately after preparation and after storage at 25°C for 30 days, and the viscosity change rate was calculated based on the viscosity before and after storage. Stability is evaluated. The viscosity measurement system uses a vibrating viscometer to measure the viscosity at 25.0±0.5°C. Viscosity change rate (%) is determined by {[Viscosity (mPa·s) after 30 days storage at 25°C-Viscosity immediately after preparation (mPa·s)]/Viscosity immediately after preparation (mPa·s)} ×100 and calculated. Table 2 shows the viscosity (initial viscosity) and viscosity change rate (%) immediately after preparation in Examples 1-10 and Comparative Examples 1-4. Here, the total mass of the solvent containing the color material dispersion liquid is a value when the total content of the color material and the pigment derivative is 13% by mass. If the viscosity change rate is less than 25%, the color material dispersion can be used in actual use. The smaller the viscosity change rate, the better the dispersion stability of the color material dispersion. Also, those with a viscosity change rate of 300% or more are set as "unmeasurable".
使用旋轉塗佈機將實施例及比較例中所獲得之著色樹脂組成物塗佈於玻璃基板(NH TECHNO GLASS(股)公司製造,「NA35」)上後,使用加熱板於80℃下乾燥3分鐘,使用超高壓水銀燈以60mJ/cm2之紫外線隔著線寬1μm至100μm之獨立細線圖案光罩對該著色層進行曝光,藉此於玻璃基板上形成厚度2.0μm之著色層。繼而,藉由將0.05wt%鉀(KOH)作為顯影液進行旋轉顯影,與顯影液接觸60秒後利用純水洗淨而進行顯影處理,進行圖案形成並對顯影性進行評價。於該顯影處理中,測定未曝光部溶解並被去除為止之時間。藉由目視判斷顯影之結束。將測定結果示於表2、3。比較例1、3、4、5即便與顯影液接觸60秒,亦未能將未曝光部溶解、去除。再者,若未曝光部溶解並被去除為止之時間為45秒以下,則評價為實用級別。 The colored resin composition obtained in the examples and comparative examples was coated on a glass substrate (manufactured by NH TECHNO GLASS Co., Ltd., "NA35") using a spin coater, and then dried at 80°C using a
於在實施例及比較例中形成著色層時,使用大塚電子製造之分光特性測定裝置LCF-1500M與壺阪電氣製造之對比度測定裝置CT-1B測定曝光後之著色層之對比度、及後烘烤後之著色層之對比度與色度(x、y)。將測定結果示於表2、3。又,作為耐熱性評價,將藉由(後烘烤後之對比度/曝光後之對比度)×100而算出之對比度保持率(%)示於表2、3。對比度保持率越大,越能抑制加熱所導致之對比度之降低,而耐熱性越優異。 When forming the colored layer in the examples and comparative examples, the spectroscopic characteristic measuring device LCF-1500M made by Otsuka Electronics and the contrast measuring device CT-1B made by Kosaka Electric were used to measure the contrast of the colored layer after exposure, and after post-baking The contrast and chromaticity (x, y) of the colored layer. The measurement results are shown in Tables 2 and 3. In addition, as heat resistance evaluation, the contrast retention rate (%) calculated by (contrast after post-baking/contrast after exposure)×100 is shown in Tables 2 and 3. The higher the contrast retention rate, the more the reduction in contrast caused by heating can be suppressed, and the better the heat resistance.
根據表2及表3所示之結果明確顯示,將以既定比例將吡咯并吡咯二酮系色材之單磺化衍生物與吡咯并吡咯二酮系色材之二磺化衍生物加以混合而成之混合物、及具有通式(I)所表示之構成單元之聚合體之分散劑與包含吡咯并吡咯二酮系色材之色材組合而成之實施例1~14之色材分散液及著色樹脂組成物,抑制加熱所導致之對比度之降低,從而可形成對比度提高之著色層。又,實施例1~14之色材分散液之黏度穩定性良好,分散穩定性優異,實施例1~14之著色樹脂組成物之顯影性良好,顯影殘渣較少。又,實施例11~14之色材分散液含有C.I.顏料黃150、或由上述通式(A)所表示之偶氮化合物及其互變異構結構之偶氮化合物之陰離子與特定之2種金屬離子構成之金屬錯合物與上述通式(B)所表示之化合物之複合分子之Azo顏料作為黃色色材,故而對比度進一步提高,對比度保持率較高。其中,含有上述Azo顏料之實施例12、13、14之對比度保持率較高,後烘烤後之對比度較高。 According to the results shown in Table 2 and Table 3, it is clearly shown that the monosulfonated derivative of the diketopyrrolopyrrole color material and the disulfonated derivative of the diketopyrrolopyrrole color material will be mixed in a predetermined ratio. The color material dispersion liquid of Examples 1 to 14 formed by combining the dispersant of the polymer having the structural unit represented by the general formula (I) and the color material containing the diketopyrrolopyrrole color material and The colored resin composition suppresses the decrease in contrast caused by heating, thereby forming a colored layer with improved contrast. In addition, the color material dispersions of Examples 1 to 14 have good viscosity stability and excellent dispersion stability, and the coloring resin compositions of Examples 1 to 14 have good developability and less development residue. In addition, the color material dispersions of Examples 11 to 14 contain CI Pigment Yellow 150, or the anion of the azo compound represented by the above general formula (A) and the azo compound of its tautomeric structure, and two specific metals The Azo pigment, which is a composite molecule of a metal complex composed of ions and a compound represented by the general formula (B), is used as a yellow color material, so the contrast is further improved and the contrast retention rate is higher. Among them, Examples 12, 13, and 14 containing the above-mentioned Azo pigment have higher contrast retention rates, and higher contrast after post-baking.
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