TWI660240B - Red pigment dispersion resist composition for color filter - Google Patents
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Abstract
本發明的課題在於提供分散穩定性、著色力、對比度、亮度、耐熱性及耐溶劑性優異的彩色濾光片用紅色顏料分散抗蝕劑組成物。其為含有C.I.顏料紅221、C.I.顏料紅177、通式(1)及/或(2)所表示的顏料分散助劑、鹼可溶性樹脂、光聚合性化合物、光聚合引發劑及有機溶劑的彩色濾光片用紅色顏料分散抗蝕劑組成物。〔式中，X及Y相同或者不同，表示可以被F、Cl、Br、NO2、CH3或OCH3取代的苯基。M表示H、Na、K、NH4或NR1R2R3R4。m表示1以上的整數。］ An object of the present invention is to provide a red pigment-dispersed resist composition for a color filter that is excellent in dispersion stability, tinting power, contrast, brightness, heat resistance, and solvent resistance. It is a color containing CI Pigment Red 221, CI Pigment Red 177, a pigment dispersing aid represented by the general formula (1) and / or (2), an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and an organic solvent. The resist composition is dispersed with a red pigment for the filter. [In the formula, X and Y are the same or different and represent a phenyl group which may be substituted with F, Cl, Br, NO 2 , CH 3 or OCH 3 . M represents H, Na, K, NH 4 or NR 1 R 2 R 3 R 4 . m represents an integer of 1 or more. ]
Description
本發明是有關於一種用於彩色液晶顯示裝置、攝像元件等所使用的彩色濾光片的彩色濾光片用紅色顏料分散抗蝕劑組成物。The present invention relates to a red pigment-dispersed resist composition for a color filter used in a color filter used in a color liquid crystal display device, an image pickup element, and the like.
彩色液晶顯示裝置等所利用的彩色濾光片由以下構成：在玻璃等的透明基板的表面上平行配置2種以上不同色相的微細的帶（條帶）或者將微細的像素按照縱橫固定的排列進行配置。像素尺寸為數10 μm～數100 μm這樣微細的大小，而且每個色相按照規定的順序整齊地排列。A color filter used in a color liquid crystal display device or the like is configured by arranging two or more fine bands (stripes) of different hue in parallel on a surface of a transparent substrate such as glass, or arranging fine pixels in a vertical and horizontal arrangement. Configure it. The pixel size is as small as several tens of micrometers to several hundreds of micrometers, and each hue is neatly arranged in a predetermined order.
彩色液晶顯示裝置為使來自背光燈的白色光透過如上述般的彩色濾光片從而著色，並在畫面上顯示彩色圖像。因此，作為彩色濾光片的基本性能，需要高透明性。因此，以往藉由使用將在彩色特性方面優異的染料以分子狀態分散到樹脂中進行染色即所謂的染色法等進行製造。然而，近年來隨著用途的多樣化，當需要提高耐熱性、耐光性等對於長期使用的可靠性時，可使用有機顏料來代替對其可靠性的提高有限度的染料。此外，關於彩色濾光片的製造法，也提出了印刷法、噴墨法、光刻法等各種方法。 進而，最近尤其為了推進攜帶儀器的液晶顯示裝置的省電化，需要具有如下像素的彩色濾光片：提高可見光的透過性，在有限的電消耗中能夠更為高效地得到明亮的顯示畫面，而且能夠實現帶來整體圖像的高精細化的高對比化。A color liquid crystal display device transmits white light from a backlight through a color filter as described above to color it, and displays a color image on a screen. Therefore, as the basic performance of a color filter, high transparency is required. Therefore, conventionally, it is manufactured by using a so-called dyeing method in which a dye excellent in color characteristics is dispersed in a resin in a molecular state and dyed. However, in recent years, with the diversification of applications, when it is necessary to improve the reliability for long-term use such as heat resistance and light resistance, organic pigments can be used instead of dyes with limited improvement in reliability. In addition, various methods such as a printing method, an inkjet method, and a photolithography method have also been proposed as methods for manufacturing a color filter. Furthermore, recently, in order to promote the power saving of liquid crystal display devices with portable devices, a color filter having pixels is required to improve the transmittance of visible light, and to obtain a bright display screen more efficiently with limited power consumption. It is possible to realize high definition and high contrast that bring about an overall image.
上述可見光的透過、對比度性能很大程度依賴於分散在彩色濾光片的各色像素中的顏料的性能，對於紅色的像素而言僅使用1種顏料難以實現所需的性能，從而提出了合用其他的調色顏料。 例如，提出了相對於主紅色顏料的顏料紅177，合用調色紅色顏料的系統（例如，參照專利文獻1）。在此，作為調色紅色顏料，可列舉在535 nm～555 nm波長區域中具有最大吸收峰的紅色顏料，即顏料紅5、9、10、17、48：1、48：2、48：3、48：4、52：2、119、166、216、224、226。然而，對於上述紅色顏料的合用系統而言，對上述透過率、對比度性能的提高存在限度。The above-mentioned visible light transmission and contrast performance largely depend on the performance of the pigments dispersed in the pixels of each color of the color filter. For a red pixel, it is difficult to achieve the required performance using only one type of pigment. Hue pigment. For example, a system in which a red color pigment is used in combination with pigment red 177 as a main red pigment has been proposed (for example, refer to Patent Document 1). Here, as the toning red pigment, a red pigment having a maximum absorption peak in a wavelength region of 535 nm to 555 nm, that is, pigment red 5, 9, 10, 17, 48: 1, 48: 2, 48: 3 can be cited. , 48: 4, 52: 2, 119, 166, 216, 224, 226. However, in the combined system of the red pigments described above, there is a limit to the improvement of the transmittance and the contrast performance.
進而，提出了在主紅色顏料的顏料紅242中作為調色紅色顏料合用顏料紅177或254的系統（例如，參照專利文獻2）。而且，還提出了在主紅色顏料的顏料紅254中作為調色紅色顏料合用顏料紅177、207、209、224、242等的紅色顏料的系統（例如，參照專利文獻3及專利文獻4）等。 然而，作為主顏料使用顏料紅242時，會產生色調偏黃這樣的問題。另一方面，使用顏料紅254時，透過率增高，但在著色膜的膜厚增厚的同時對比度降低。進而，從顏料的特性出發，也具有耐溶劑性變差或耐熱性變差（產生昇華物）這樣的問題。Furthermore, a system in which pigment red 177 or 254 is used as a toning red pigment among pigment red 242 of the main red pigment has been proposed (for example, refer to Patent Document 2). In addition, a system of combining red pigments such as pigment reds 177, 207, 209, 224, and 242 as a toning red pigment among pigment red 254 of the main red pigment has also been proposed (for example, refer to Patent Documents 3 and 4). . However, when Pigment Red 242 is used as the main pigment, there is a problem that the color tone becomes yellowish. On the other hand, when pigment red 254 is used, the transmittance increases, but the contrast decreases as the film thickness of the colored film increases. Furthermore, from the characteristics of the pigment, there is also a problem that the solvent resistance is deteriorated or the heat resistance is deteriorated (sublimation products are generated).
而且，近年來藉由也採用將LED作為光源的背光燈等，彩色濾光片的色彩再現區域進行擴大。然而，由於照射在各個上的光的波長不同，可利用的著色顏料受限。例如，在將LED作為光源的背光燈的情況下，對於迄今為止的如上述那樣的顏料的組合而言，從光的吸收波長區域的關係不得不進一步提高像素的顏料濃度。因此，作為紅色顏料分散抗蝕劑組成物存在需要高濃度化，組成物自身的製造、經時穩定保存變得困難的問題。相對於此，若使顏料濃度成為以往普通的濃度，則此次會產生為了得到所需色密度的像素膜的膜厚變得過厚，製造彩色濾光片變得困難這樣的問題。In addition, in recent years, a color reproduction area of a color filter has been expanded by using a backlight or the like using an LED as a light source. However, since the wavelength of the light irradiated on each is different, the usable coloring pigments are limited. For example, in the case of a backlight using an LED as a light source, the pigment concentration of a pixel has to be further increased from the relationship of the absorption wavelength region of light for a combination of pigments as described above. Therefore, there is a problem that it is necessary to increase the concentration as a red pigment-dispersed resist composition, and it is difficult to manufacture the composition itself and to stably store it over time. On the other hand, if the pigment concentration is set to a conventionally common concentration, a problem arises this time that the film thickness of the pixel film becomes too thick in order to obtain a desired color density, making it difficult to produce a color filter.
為了解決該問題，當使用適於從LED照射的光的波長的顏料紅179、顏料紅208時，即使不提高像素的顏料濃度也能夠得到色密度，膜厚成為可控制的範圍內，然而在該系統中，具有亮度本質上降低這樣的問題。 進而，作為相對於從LED照射的光的波長維持高著色力且提高亮度的方法，認為使用顏料紅221等的紅色顏料（例如，參照專利文獻5）。 然而，由於顏料紅221在分散工序中的粘度升高增大而且確保分散液經時穩定性變得困難，故而以已知的方法無法得到分散液的適合的流動性、經時穩定性。 [現有技術文獻] [專利文獻]In order to solve this problem, when using pigment red 179 and pigment red 208 suitable for the wavelength of light irradiated from the LED, the color density can be obtained without increasing the pigment concentration of the pixel, and the film thickness becomes a controllable range. This system has a problem that the brightness is substantially reduced. Furthermore, as a method of maintaining high tinting power and increasing brightness with respect to the wavelength of light radiated from the LED, it is considered to use a red pigment such as Pigment Red 221 (for example, refer to Patent Document 5). However, since the increase in the viscosity of Pigment Red 221 during the dispersion step and the difficulty of ensuring the stability of the dispersion over time, it has been impossible to obtain suitable fluidity and stability over time of the dispersion by known methods. [Prior Art Literature] [Patent Literature]
專利文獻1 日本專利特開平10-148712號公報 專利文獻2 日本專利特開平11-014824號公報 專利文獻3 日本專利特開2002-372618號公報 專利文獻4 日本專利特開2003-248115號公報 專利文獻5 日本專利特開2012-208329號公報Patent Literature 1 Japanese Patent Laid-Open No. 10-148712 Patent Literature 2 Japanese Patent Laid-Open No. 11-014824 Patent Literature 3 Japanese Patent Laid-Open No. 2002-372618 Patent Literature 4 Japanese Patent Laid-Open No. 2003-248115 Patent Literature 5 Japanese Patent Laid-Open No. 2012-208329
本發明的課題在於提供分散穩定性、著色力、對比度、亮度、耐熱性及耐溶劑性優異的彩色濾光片用紅色顏料分散抗蝕劑組成物。An object of the present invention is to provide a red pigment-dispersed resist composition for a color filter that is excellent in dispersion stability, tinting power, contrast, brightness, heat resistance, and solvent resistance.
藉由將主顏料設為顏色索引（Color Index，C.I.）顏料紅221，將調色顏料設為C.I.顏料紅177，即使使用各種背光燈裝置也能夠得到高亮度、可提高著色力的紅色像素。因此需要將上述顏料微粒化並使其穩定分散於彩色濾光片用紅色顏料分散抗蝕劑組成物中，然而以以往的技術無法充分得到包含C.I.顏料紅221的顏料的微粒的分散穩定性。 因此，本申請人對提高包含C.I.顏料紅221的顏料微粒的分散穩定性的技術進行了深入研究，結果發現了在將包含C.I.顏料紅221的顏料微粒化所得到的微粒化物中加入本發明特定的顏料分散助劑、具有三級胺基及／或四級銨基的丙烯酸類嵌段共聚物及有機溶劑並使其分散得到顏料分散物後來製成彩色濾光片用紅色顏料分散抗蝕劑組成物的方法。對於由該方法所得到的彩色濾光片用紅色顏料分散抗蝕劑組成物而言，由於包含C.I.顏料紅221的顏料微粒的分散穩定性與以往技術相比明顯提高，故而能夠全部解決本發明的課題，從而完成了本發明。By setting the main pigment as Color Index (C.I.) Pigment Red 221 and the color tone pigment as C.I. Pigment Red 177, red pixels with high brightness and improved tinting power can be obtained even with various backlight devices. Therefore, it is necessary to micronize the pigment and stably disperse it in the red pigment dispersion resist composition for color filters. However, the dispersion stability of the microparticles containing the pigment of C.I. Pigment Red 221 cannot be sufficiently obtained by the conventional technique. Therefore, the applicant conducted intensive research on a technique for improving the dispersion stability of pigment particles containing CI Pigment Red 221, and as a result, found that the particulate matter obtained by minimizing a pigment containing CI Pigment Red 221 was added to the present invention. Pigment dispersion aid, acrylic block copolymer with tertiary amine group and / or quaternary ammonium group, and organic solvent and disperse them to obtain pigment dispersion, and then make red pigment dispersion resist for color filter Composition method. As for the red pigment dispersion resist composition for color filters obtained by this method, since the dispersion stability of pigment particles containing CI Pigment Red 221 is significantly improved compared with the prior art, all of the present invention can be solved. The subject has thus completed the present invention.
即，本發明如下： 1.一種彩色濾光片用紅色顏料分散抗蝕劑組成物，其含有C.I.顏料紅221、C.I.顏料紅177、通式（1）及／或通式（2）所表示的顏料分散助劑、鹼可溶性樹脂、光聚合性化合物、光聚合引發劑及有機溶劑，〔式中，X及Y相同或者不同，表示可以被F、Cl、Br、NO2 、CH3 或OCH3 取代的苯基。M表示H、Na、K、NH4 或NR1 R2 R3 R4 （R1 、R2 、R3 及R4 相同或者不同，表示可以被其他取代基取代的碳原子數1～10的飽和或者不飽和的脂肪族烴基或可以被其他取代基取代的碳原子數6～10的芳香族烴基。）。m表示1以上的整數。〕That is, the present invention is as follows: 1. A red pigment-dispersed resist composition for a color filter, comprising CI Pigment Red 221, CI Pigment Red 177, and Formula (1) and / or Formula (2) Pigment dispersion aids, alkali-soluble resins, photopolymerizable compounds, photopolymerization initiators, and organic solvents, [In the formula, X and Y are the same or different and represent a phenyl group which may be substituted with F, Cl, Br, NO 2 , CH 3 or OCH 3 . M represents H, Na, K, NH 4 or NR 1 R 2 R 3 R 4 (R 1 , R 2 , R 3 and R 4 are the same or different, and represent 1 to 10 carbon atoms which may be substituted by other substituents Saturated or unsaturated aliphatic hydrocarbon groups or aromatic hydrocarbon groups having 6 to 10 carbon atoms which may be substituted by other substituents.). m represents an integer of 1 or more. A
2.一種彩色濾光片用紅色顏料分散抗蝕劑組成物，其為含有C.I.顏料紅221的顏料分散物、C.I.顏料紅177的顏料分散物、鹼可溶性樹脂、光聚合性化合物、光聚合引發劑及有機溶劑的彩色濾光片用紅色顏料分散抗蝕劑組成物， 所述C.I.顏料紅221的顏料分散物為在將C.I.顏料紅221微粒化所得到的微粒化物中加入通式（1）及／或通式（2）所表示的顏料分散助劑、具有三級胺基及／或四級銨基的丙烯酸類嵌段共聚物及有機溶劑並使其分散所得到的顏料分散物， 所述C.I.顏料紅177的顏料分散物為在將C.I.顏料紅177微粒化所得到的微粒化物中加入通式（1）及／或通式（2）所表示的顏料分散助劑、具有三級胺基及／或四級銨基的丙烯酸類嵌段共聚物及有機溶劑並使其分散所得到的顏料分散物，〔式中， X及Y相同或者不同，表示可以被F、Cl、Br、NO2 、CH3 或OCH3 取代的苯基，M表示H、Na、K、NH4 或NR1 R2 R3 R4 （R1 、R2 、R3 及R4 相同或者不同，表示可以被其他取代基取代的碳原子數1～10的飽和或者不飽和的脂肪族烴基或可以被其他取代基取代的碳原子數6～10的芳香族烴基。）。m表示1以上的整數。〕2. A red pigment dispersion resist composition for a color filter, which is a pigment dispersion containing CI Pigment Red 221, a pigment dispersion of CI Pigment Red 177, an alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiation The red pigment disperses the resist composition for color filters of organic solvents and organic solvents. The pigment dispersion of the CI Pigment Red 221 is obtained by adding the general formula (1) to a microparticulate product obtained by micronizing the CI Pigment Red 221. And / or a pigment dispersion obtained by dispersing and dispersing a pigment dispersion aid represented by the general formula (2), an acrylic block copolymer having a tertiary amine group and / or a quaternary ammonium group, and an organic solvent; The pigment dispersion of the CI Pigment Red 177 is obtained by adding a pigment dispersion aid represented by the general formula (1) and / or the general formula (2) to a micronized product obtained by micronizing the CI Pigment Red 177, and having a tertiary amine. Pigment dispersions obtained by dispersing and dispersing acrylic block copolymers and / or quaternary ammonium groups and organic solvents, [In the formula, X and Y are the same or different and represent a phenyl group which may be substituted by F, Cl, Br, NO 2 , CH 3 or OCH 3 , and M represents H, Na, K, NH 4 or NR 1 R 2 R 3 R 4 (R 1 , R 2 , R 3 and R 4 are the same or different and represent a saturated or unsaturated aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted by another substituent or a carbon which may be substituted by another substituent Aromatic hydrocarbon group having 6 to 10 atoms.). m represents an integer of 1 or more. A
3.一種彩色濾光片用紅色顏料分散抗蝕劑組成物，其為含有C.I.顏料紅221的顏料分散物、C.I.顏料紅177的顏料分散物、鹼可溶性樹脂、光聚合性化合物、光聚合引發劑及有機溶劑的彩色濾光片用紅色顏料分散抗蝕劑組成物， 所述C.I.顏料紅221的顏料分散物為在將C.I.顏料紅221微粒化所得到的微粒化物中加入通式（3）及／或通式（4）所表示的顏料分散助劑、具有三級胺基及／或四級銨基的丙烯酸類嵌段共聚物及有機溶劑並使其分散所得到的顏料分散物， 所述C.I.顏料紅177的顏料分散物為在將C.I.顏料紅177微粒化所得到的微粒化物中加入通式（3）及／或通式（4）所表示的顏料分散助劑、具有四級銨基的丙烯酸類嵌段共聚物及有機溶劑並使其分散所得到的顏料分散物，〔式中，M表示H、Na、K、NH4 或NR1 R2 R3 R4 （R1 、R2 、R3 及R4 相同或者不同，表示可以被其他取代基取代的碳原子數1～10的飽和或者不飽和的脂肪族烴基，或可以被其他取代基取代的碳原子數6～10的芳香族烴基。）。m表示1以上的整數。〕3. A red pigment-dispersed resist composition for a color filter, which is a pigment dispersion containing CI Pigment Red 221, a pigment dispersion of CI Pigment Red 177, an alkali-soluble resin, a photopolymerizable compound, and photopolymerization initiation A red pigment dispersing resist composition for a color filter of an organic solvent and an organic solvent. The pigment dispersion of the CI Pigment Red 221 is obtained by adding the generalized formula (3) to a micronized product obtained by micronizing the CI Pigment Red 221. And / or a pigment dispersion obtained by dispersing and dispersing a pigment dispersion aid represented by the general formula (4), an acrylic block copolymer having a tertiary amine group and / or a quaternary ammonium group, and an organic solvent, The pigment dispersion of CI Pigment Red 177 is obtained by adding a pigment dispersion aid represented by the general formula (3) and / or the general formula (4) to a micronized product obtained by micronizing CI Pigment Red 177 and having a quaternary ammonium Pigment dispersion obtained by dispersing a base acrylic block copolymer and an organic solvent, [In the formula, M represents H, Na, K, NH 4 or NR 1 R 2 R 3 R 4 (R 1 , R 2 , R 3 and R 4 are the same or different, and represents the number of carbon atoms which may be substituted by other substituents. 1 to 10 saturated or unsaturated aliphatic hydrocarbon groups, or aromatic hydrocarbon groups having 6 to 10 carbon atoms which may be substituted with other substituents.). m represents an integer of 1 or more. A
4.如1～3中任一項所述的彩色濾光片用紅色顏料分散抗蝕劑組成物，其中所述C.I.顏料紅221的顏料分散物含有具有與C.I.顏料紅221為相同骨架的化合物的磺化物。4. The red pigment dispersion resist composition for a color filter according to any one of 1 to 3, wherein the pigment dispersion of CI Pigment Red 221 contains a compound having the same skeleton as CI Pigment Red 221 Sulfide.
5.如4所述的彩色濾光片用紅色顏料分散抗蝕劑組成物，其中所述顏料紅221的顏料分散物為在具有與C.I.顏料紅221為相同骨架的化合物的磺化物的存在下，在將C.I.顏料紅221微粒化所得到的微粒化物中加入通式（3）及／或通式（4）所表示的顏料分散助劑、具有三級胺基及／或四級銨基的丙烯酸類嵌段共聚物及有機溶劑並使其分散所得到的顏料分散物， 所述C.I.顏料紅177的顏料分散物為在將C.I.顏料紅177微粒化所得到的微粒化物中加入通式（3）及／或通式（4）所表示的顏料分散助劑、具有三級胺基及／或四級銨基的丙烯酸類嵌段共聚物及有機溶劑並使其分散所得到的顏料分散物。5. The red pigment-dispersed resist composition for a color filter according to 4, wherein the pigment dispersion of Pigment Red 221 is in the presence of a sulfonate of a compound having the same skeleton as CI Pigment Red 221. To the micronized product obtained by micronizing CI Pigment Red 221, a pigment dispersing aid represented by the general formula (3) and / or general formula (4), a tertiary amine group and / or a quaternary ammonium group are added. A pigment dispersion obtained by dispersing an acrylic block copolymer and an organic solvent, and the pigment dispersion of CI Pigment Red 177 is obtained by adding the general formula (3 ) And / or pigment dispersion aids represented by the general formula (4), a pigment dispersion obtained by dispersing and dispersing an acrylic block copolymer having an tertiary amine group and / or a quaternary ammonium group and an organic solvent.
6.如1～5中任一項所述的彩色濾光片用紅色顏料分散抗蝕劑組成物，其中相對於所述C.I.顏料紅221的合計質量100質量份，所述C.I.顏料紅221的顏料分散物含有5～15質量份一次粒徑為5 nm～20 nm的硫酸鋇。6. The red pigment-dispersed resist composition for a color filter according to any one of 1 to 5, wherein the CI pigment red 221 is 100 parts by mass relative to a total mass of the CI pigment red 221. The pigment dispersion contains 5 to 15 parts by mass of barium sulfate having a primary particle diameter of 5 to 20 nm.
7.一種彩色濾光片，其藉由1～3中任一項所述的彩色濾光片用紅色顏料分散抗蝕劑組成物所得到的彩色濾光片的對比度（Bare：1000）為700以上。7. A color filter having a contrast ratio (Bare: 1000) of the color filter obtained by dispersing the resist composition with the red pigment for the color filter according to any one of 1 to 3, is 700 the above.
根據本發明，可得到下述效果。 藉由作為彩色濾光片用顏料分散抗蝕劑組成物來進行使用，得到成為適合的色度ｘ及ｙ的紅色濾光片，進而得到亮度Ｙ更加明亮的顯示器。 在可將顏料分散抗蝕劑組成物的粘度成為適合的範圍的同時能夠使膜厚變薄，彩色濾光片的製造不會存在困難。 能夠使彩色濾光片用顏料分散抗蝕劑組成物具有優異的分散穩定性。 可提供耐溶劑性及耐熱性優異的紅色濾光片。According to the present invention, the following effects can be obtained. By using as a pigment-dispersed resist composition for color filters, a red filter having suitable chromaticities x and y is obtained, and a display with a brighter luminance Ｙ is obtained. While the viscosity of the pigment-dispersed resist composition can be in a suitable range, the film thickness can be reduced, and there is no difficulty in producing a color filter. The pigment-dispersed resist composition for a color filter can have excellent dispersion stability. Red filters with excellent solvent resistance and heat resistance are available.
以下，對本發明的彩色濾光片用紅色顏料分散抗蝕劑組成物（以下，也稱作「顏料分散抗蝕劑組成物」）進行進一步詳細說明。 （顏料） 本發明的彩色濾光片用紅色顏料分散抗蝕劑組成物為含有C.I.顏料紅221及C.I.顏料紅177的組成物，也可直接添加上述顏料作為彩色濾光片用紅色顏料分散抗蝕劑組成物，或也可預先在上述顏料中加入通式（1）及／或通式（2）所表示的顏料分散助劑、具有三級胺基及／或四級銨基的丙烯酸類嵌段共聚物及有機溶劑、進一步根據需要加入鹼可溶性樹脂並使其分散而成為C.I.顏料紅221的顏料分散物及C.I.顏料紅177的顏料分散物，之後使其含有上述顏料分散物。 由於使用含有該顏料分散物的顏料分散抗蝕劑組成物從而得到彩色濾光片，故而該彩色濾光片可為高對比度、高亮度、高耐熱性、高耐溶劑性。Hereinafter, the red pigment dispersion resist composition for a color filter of the present invention (hereinafter, also referred to as a “pigment dispersion resist composition”) will be described in further detail. (Pigment) The red pigment dispersion resist composition for a color filter of the present invention is a composition containing CI Pigment Red 221 and CI Pigment Red 177, and the above pigment may be directly added as a red pigment dispersion resistance for a color filter. The etchant composition, or a pigment dispersing aid represented by the general formula (1) and / or the general formula (2), and acrylic acid having a tertiary amine group and / or a quaternary ammonium group may be added to the pigment in advance. The block copolymer, the organic solvent, and an alkali-soluble resin are further added and dispersed as necessary to obtain a pigment dispersion of CI Pigment Red 221 and a pigment dispersion of CI Pigment Red 177, and the pigment dispersion is then contained. Since a color filter is obtained by using a pigment dispersion resist composition containing the pigment dispersion, the color filter can have high contrast, high brightness, high heat resistance, and high solvent resistance.
相對於上述顏料的合計質量，優選上述C.I.顏料紅221的含量為30質量%以上、小於100質量%、進一步優選40質量%以上、小於60質量%，優選C.I.顏料紅177為小於70質量%、進一步優選40質量%以上、小於60質量%。當上述C.I.顏料紅221的含量小於30質量%時，有時作為紅色濾光片無法得到適合的色度ｘ及ｙ。 優選上述C.I.顏料紅221及C.I.顏料紅177各自的平均一次粒徑為30 nm～50 nm。藉由具有上述範圍的平均粒徑，由所得到的彩色濾光片顯現的映像成為更高的對比度。 且，在本發明中，上述平均粒徑是指以激光衍射式粒度測定法、測定裝置：Nanotrac（UPA－EX150、日機裝公司製）測定的體積平均粒徑。 在本發明中，除上述著色顏料以外，在不損壞本發明的效果的範圍內還可添加混合其他顏料。作為上述其他顏料，例如可列舉黃色顏料、橙色顏料等。 本發明中的顏料的使用量相對於顏料分散抗蝕劑組成物的總固體成分作為質量分率，以使用的顏料的合計量計優選5～80質量%、更優選20～50質量%。The content of the CI Pigment Red 221 is preferably 30% by mass or more, less than 100% by mass, more preferably 40% by mass or more, and less than 60% by mass with respect to the total mass of the pigment, and preferably less than 70% by mass of CI Pigment Red 177, It is more preferably 40% by mass or more and less than 60% by mass. When the content of the C.I. Pigment Red 221 is less than 30% by mass, suitable chromaticities x and y may not be obtained as a red filter. The average primary particle diameter of each of the C.I. Pigment Red 221 and C.I. Pigment Red 177 is preferably 30 nm to 50 nm. By having an average particle diameter in the above range, an image developed by the obtained color filter becomes higher in contrast. In the present invention, the average particle diameter is a volume average particle diameter measured by a laser diffraction particle size measurement method and a measuring device: Nanotrac (UPA-EX150, manufactured by Nikkiso Co., Ltd.). In the present invention, in addition to the above-mentioned colored pigments, other pigments may be added and mixed as long as the effects of the present invention are not impaired. Examples of the other pigments include yellow pigments and orange pigments. The amount of the pigment used in the present invention is preferably 5 to 80% by mass, and more preferably 20 to 50% by mass based on the total solid content of the pigment-dispersed resist composition as a mass fraction.
（顏料分散助劑） 本發明的顏料分散抗蝕劑組成物所含有的顏料分散助劑優選含有作為下述通式（1）及／或通式（2）所表示的化合物的顏料分散助劑（Ａ）（以下，也簡稱為「顏料分散助劑（Ａ）」。）以及作為與C.I.顏料紅221具有相同骨架的化合物的磺化物的顏料分散助劑（Ｂ）（以下，也簡稱為「顏料分散助劑（Ｂ））。）的2種顏料分散助劑的兩者，也可僅含有顏料分散助劑（Ａ）而不含有顏料分散助劑（Ｂ）。 優選包含顏料分散助劑（Ａ）及顏料分散助劑（Ｂ）的兩者。 (Pigment Dispersion Aid) The pigment dispersing aid contained in the pigment-dispersed resist composition of the present invention preferably contains a pigment dispersing aid as a compound represented by the following general formula (1) and / or general formula (2) (A) (hereinafter also simply referred to as "pigment dispersing aid (A)") and pigment dispersing aid (B) (hereinafter, also simply referred to as "pigment dispersing aid" as a sulfonate of a compound having the same skeleton as CI Pigment Red 221) Pigment dispersing aid (B)).) Both of the two pigment dispersing aids may contain only the pigment dispersing aid (A) and not the pigment dispersing aid (B). The pigment dispersing aid (B) is preferably contained. A) and pigment dispersion aid (B).
作為本發明所使用的顏料分散助劑（Ａ），使用上述通式（1）及／或通式（2）所表示的化合物。 在上述通式（1）及通式（2）中，X及Y相同或者不同，表示可以被F、Cl、Br、NO2 、CH3 或OCH3 取代的苯基。M表示H、Na、K、NH4 或NR1 R2 R3 R4 。 上述通式（1）及通式（2）的Ｍ為NR1 R2 R3 R4 時的各R1 、R2 、R3 及R4 相同或者不同，表示可以被其他取代基取代的碳原子數1～10的飽和或者不飽和的脂肪族烴基或可以被其他取代基取代的碳原子數6～10的芳香族烴基。 在此，作為上述飽和或者不飽和的脂肪族烴基，可列舉甲基、乙基、丙基、異丙基、丁基、異丁基、仲丁基、叔丁基、戊基、己基、辛基、癸基等的烷基；乙烯基、烯丙基、1－丁烯基等的鏈烯基；乙炔基、丙炔基等的炔基等。作為上述芳香族烴基，可列舉苯基、萘基等。 而且，作為上述其他的取代基，可列舉羥基、鹵素、羧基、胺基、低級烷基（碳原子數1～5）等。且，上述R1 R2 R3 及R4 可以其中1個被其他取代基取代，也可以2個以上被其他取代基取代。進而，上述通式（1）及通式（2）的「ｍ」為1以上的整數。As the pigment dispersion aid (A) used in the present invention, a compound represented by the general formula (1) and / or the general formula (2) is used. In the general formula (1) and the general formula (2), X and Y are the same or different, and represent a phenyl group which may be substituted with F, Cl, Br, NO 2 , CH 3 or OCH 3 . M represents H, Na, K, NH 4 or NR 1 R 2 R 3 R 4 . When M in the general formula (1) and general formula (2) is NR 1 R 2 R 3 R 4 , each of R 1 , R 2 , R 3, and R 4 is the same or different, and represents a carbon that may be substituted with another substituent. A saturated or unsaturated aliphatic hydrocarbon group having 1 to 10 atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted with another substituent. Examples of the saturated or unsaturated aliphatic hydrocarbon group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, and octyl. Alkyl groups such as alkyl, decyl, and the like; alkenyl groups such as vinyl, allyl, and 1-butenyl; alkynyl groups such as ethynyl, propynyl, and the like. Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group. Examples of the other substituent include a hydroxyl group, a halogen group, a carboxyl group, an amine group, and a lower alkyl group (having 1 to 5 carbon atoms). In addition, one of the R 1 R 2 R 3 and R 4 may be substituted with another substituent, or two or more of them may be substituted with other substituents. Furthermore, "m" in said general formula (1) and general formula (2) is an integer of 1 or more.
在上述顏料分散助劑（Ａ）中，上述通式（1）所表示的化合物為烯醇型、上述通式（2）所表示的化合物為酮型的互變異構體，本發明的顏料分散抗蝕劑組成物可包含兩個化合物。即本發明中的顏料分散助劑（Ａ）包含由上述通式（1）或通式（2）所表示的化合物的情況，以及由上述通式（1）及通式（2）所表示的化合物的兩者所構成的情況中的任一種。 作為顏料分散助劑（Ａ）的優選例，即使在將有機顏料微細分散的狀態下，從在可得到具有良好的流動性與分散穩定性的同時，透明性、著色力處於更高水平的顏料分散物的觀點出發，優選C.I.顏料紅2的磺化物（下述通式（3）及／或通式（4））。In the pigment dispersion aid (A), the compound represented by the general formula (1) is an enol type, and the compound represented by the general formula (2) is a ketone type tautomer. The pigment of the present invention is dispersed The resist composition may include two compounds. That is, when the pigment dispersion aid (A) in the present invention includes the compound represented by the general formula (1) or the general formula (2), and the compound represented by the general formula (1) and the general formula (2) Either of the two cases of the compound. As a preferred example of the pigment dispersing assistant (A), even in a state where the organic pigment is finely dispersed, a pigment having good fluidity and dispersion stability can be obtained, and a pigment having higher transparency and coloring power can be obtained. From the viewpoint of a dispersion, a sulfide of CI Pigment Red 2 (the following general formula (3) and / or general formula (4)) is preferred.
相對於各顏料的合計100質量份，上述顏料分散助劑（Ａ）的使用量為0.5～30質量份、優選3～15質量份，相對於各顏料的合計100質量份，作為顏料分散助劑（Ｂ）的上述C.I.顏料紅221的磺化物的使用量為0.5～30質量份、優選3～15質量份。The pigment dispersing aid (A) is used in an amount of 0.5 to 30 parts by mass, preferably 3 to 15 parts by mass with respect to 100 parts by mass of each pigment as a pigment dispersing aid. The amount of the sulfonate of the CI Pigment Red 221 (B) used is 0.5 to 30 parts by mass, preferably 3 to 15 parts by mass.
（具有三級胺基及／或四級銨基的丙烯酸類嵌段共聚物） 本發明的顏料分散抗蝕劑組成物含有具有三級胺基及／或四級銨基的丙烯酸類嵌段共聚物。 作為本發明中的具有三級胺基及／或四級銨基的丙烯酸類嵌段共聚物，例如，可列舉DISPERBYK－2000、DISPERBYK－2001、DISPERBYK－2020、DISPERBYK－2025、BYK－LPN21116、BYK－LPN22102（以上，畢克化學（BYK）公司製）。(Acrylic block copolymer having tertiary amine group and / or quaternary ammonium group) The pigment-dispersed resist composition of the present invention contains an acrylic block copolymer having tertiary amine group and / or quaternary ammonium group. Thing. Examples of the acrylic block copolymer having a tertiary amine group and / or a quaternary ammonium group in the present invention include, for example, DISPERBYK-2000, DISPERBYK-2001, DISPERBYK-2020, DISPERBYK-2025, BYK-LPN21116, BYK -LPN22102 (above, manufactured by BYK).
在本發明的顏料分散抗蝕劑組成物中，相對於使用的總有機顏料100質量份，具有上述三級胺基及／或四級銨基的丙烯酸類嵌段共聚物的含量通常優選1～200質量份、更優選1～60質量份。具有三級胺基及／或四級銨基的丙烯酸類嵌段共聚物的含量小於1質量份時，有時顏料分散性降低，另一方面，當超過200質量份時，有顯像性降低等的可能性。In the pigment-dispersed resist composition of the present invention, the content of the acrylic block copolymer having the tertiary amine group and / or quaternary ammonium group is usually preferably 1 to 100 parts by mass based on the total organic pigment used. 200 parts by mass, and more preferably 1 to 60 parts by mass. When the content of the acrylic block copolymer having a tertiary amine group and / or a quaternary ammonium group is less than 1 part by mass, the dispersibility of the pigment may be reduced. On the other hand, when it exceeds 200 parts by mass, the developability is lowered. The possibility of waiting.
（鹼可溶性樹脂） 本發明的顏料分散抗蝕劑組成物含有鹼可溶性樹脂。 作為鹼可溶性樹脂，只要是在製造彩色濾光片時在其顯像處理工序中所用的顯像液，特別優選對鹼顯像液具有可溶性的鹼可溶性樹脂，則沒有特別限定。其中，作為上述鹼可溶性樹脂，優選具有羧基的鹼可溶性樹脂，特別優選具有1個以上的羧基的乙烯性不飽和單體和其他可共聚的乙烯性不飽和單體的共聚物。 作為上述具有1個以上羧基的乙烯性不飽和單體和其他可共聚的乙烯性不飽和單體的共聚物，具體而言，可列舉丙烯酸、甲基丙烯酸等具有羧基的乙烯性不飽和單體與選自與具有羧基的乙烯性不飽和單體可共聚的苯乙烯、2-丙烯酸羥乙酯、2-甲基丙烯酸羥乙酯、丙烯酸烯丙酯（allyl acrylate）、甲基丙烯酸烯丙酯（allyl methacrylate）、丙烯酸苄酯、甲基丙烯酸苄酯、丙烯酸環己酯、甲基丙烯酸環己酯、甘油基單丙烯酸酯、甲基丙烯酸甘油酯、N-苯基馬來醯亞胺、聚苯乙烯大分子單體及聚甲基丙烯酸甲酯大分子單體中的至少1種的乙烯性不飽和單體的共聚物。(Alkali-soluble resin) The pigment-dispersed resist composition of the present invention contains an alkali-soluble resin. The alkali-soluble resin is not particularly limited as long as it is a developing solution used in the development processing step of the color filter, and particularly preferably an alkali-soluble resin having solubility in the alkali developing solution. Among them, the alkali-soluble resin is preferably an alkali-soluble resin having a carboxyl group, and particularly preferably a copolymer of an ethylenically unsaturated monomer having one or more carboxyl groups and another copolymerizable ethylenically unsaturated monomer. Examples of the copolymer of the ethylenically unsaturated monomer having one or more carboxyl groups and other copolymerizable ethylenically unsaturated monomers include ethylenically unsaturated monomers having carboxyl groups such as acrylic acid and methacrylic acid. Copolymerized with styrene selected from copolymerizable with ethylenically unsaturated monomers having a carboxyl group, hydroxyethyl 2-acrylate, hydroxyethyl 2-methacrylate, allyl acrylate, allyl methacrylate (Allyl methacrylate), benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, glyceryl monoacrylate, glyceryl methacrylate, N-phenylmaleimide, poly Copolymer of an ethylenically unsaturated monomer of at least one of a styrene macromonomer and a polymethylmethacrylate macromonomer.
作為上述鹼可溶性樹脂的酸值，優選50 mg KOH/g～300 mg KOH/g。此時，當酸值小於50 mg KOH/g時，存在抗蝕劑組成物對鹼顯像液的溶解性降低的可能性。另一方面，當超過300 mg KOH/g時，對鹼顯像液的溶解性變得過大，藉由鹼顯像液進行顯像時，存在帶來從著色層的基板的脫落、著色層表面的膜粗糙的可能性。 且，在本發明中，上述酸值為理論酸值，為基於具有羧基的乙烯性不飽和單體與其含量算術求得的值。The acid value of the alkali-soluble resin is preferably 50 mg KOH / g to 300 mg KOH / g. At this time, when the acid value is less than 50 mg KOH / g, there is a possibility that the solubility of the resist composition in the alkali developing solution is reduced. On the other hand, when it exceeds 300 mg KOH / g, the solubility in an alkali developing solution becomes too large, and when developing with an alkali developing solution, there is a possibility that it may fall off from the substrate of the colored layer and the surface of the colored layer. Possibility of rough film. In the present invention, the above-mentioned acid value is a theoretical acid value, which is a value obtained by arithmetically calculating an ethylenically unsaturated monomer having a carboxyl group and its content.
在本發明的顏料分散抗蝕劑組成物中含有鹼可溶性樹脂，其含量從後述的顏料分散時的分散性、分散穩定性的觀點出發優選為少量。 因此，優選在C.I.顏料紅221的顏料分散物及C.I.顏料紅177的顏料分散物的至少一種中含有，而且，也可以區別於上述顏料分散物來進行添加，從而得到彩色濾光片用紅色顏料分散抗蝕劑組成物。 本發明中的鹼可溶性樹脂的質均分子量通常優選1,000～10萬。鹼可溶性樹脂的質均分子量小於1,000時，有時對鹼顯像劑的溶解性升高、顯像特性降低。另一方面，超過10萬時，有時在有機溶劑中的溶解性降低且抗蝕劑組成物的粘度增高。 且在本發明中，上述鹼可溶性樹脂的質均分子量為基於膠體滲透層析儀（GPC，Gel Permeation Chromatography）所得到的聚苯乙烯換算的質均分子量。在本發明中，作為裝置使用Water 2690（沃特世公司製），作為色譜柱使用 PLgel 5μ MIXED-D（Polymer Laboratories公司製）。 在本發明的顏料分散抗蝕劑組成物中，相對於所含有的總有機顏料100質量份，上述鹼可溶性樹脂的含量通常優選10～1,000質量份、更優選20～500質量份。 上述鹼可溶性樹脂的含量小於10質量份時，例如，存在鹼顯像性降低或在未曝光部的基板上或遮光層上產生浮渣、膜殘留的可能性。另一方面，當超過1,000質量份時，由於有機顏料的濃度相對地降低，所以存在作為薄膜難以達到目標色密度的可能性。The pigment-dispersed resist composition of the present invention contains an alkali-soluble resin, and the content thereof is preferably a small amount from the viewpoint of dispersibility and dispersion stability during pigment dispersion described later. Therefore, it is preferable to include at least one of the pigment dispersion of CI Pigment Red 221 and the pigment dispersion of CI Pigment Red 177, and it may be added separately from the pigment dispersion to obtain a red pigment for a color filter. Disperse the resist composition. The mass-average molecular weight of the alkali-soluble resin in the present invention is usually preferably 1,000 to 100,000. When the mass-average molecular weight of the alkali-soluble resin is less than 1,000, the solubility to an alkali developer may increase and the developing characteristics may decrease. On the other hand, when it exceeds 100,000, the solubility in an organic solvent may decrease and the viscosity of a resist composition may increase. In the present invention, the mass average molecular weight of the alkali-soluble resin is a polystyrene-equivalent mass average molecular weight based on a gel permeation chromatography (GPC, Gel Permeation Chromatography). In the present invention, Water 2690 (manufactured by Waters Corporation) is used as a device, and PLgel 5 μMIXED-D (manufactured by Polymer Laboratories) is used as a chromatography column. In the pigment-dispersed resist composition of the present invention, the content of the alkali-soluble resin is usually preferably 10 to 1,000 parts by mass, and more preferably 20 to 500 parts by mass with respect to 100 parts by mass of the total organic pigment contained. When the content of the alkali-soluble resin is less than 10 parts by mass, for example, there is a possibility that alkali developability is lowered or scums or film residues are generated on a substrate or a light-shielding layer of an unexposed portion. On the other hand, when it exceeds 1,000 parts by mass, since the concentration of the organic pigment is relatively reduced, there is a possibility that it is difficult to achieve a target color density as a thin film.
（光聚合性化合物） 本發明的顏料分散抗蝕劑組成物中含有光聚合性化合物。 作為本發明的光聚合性化合物，可列舉分子內具有1個以上光聚合性不飽和鍵的單體、低聚物等。光聚合性不飽和鍵是指藉由下述作用可聚合的不飽和鍵：後述的光聚合引發劑藉由紫外線、電子射線等的活性能量線而在分解時產生自由基或陽離子。 作為分子內具有1個光聚合性不飽和鍵的單體，可例示甲基丙烯酸甲酯、甲基丙烯酸丁酯、2-甲基丙烯酸乙基己酯、丙烯酸甲酯（methylacrylate）、丙烯酸丁酯、丙烯酸2-乙基己酯（2-ethylhexyl acrylate）等的甲基丙烯酸烷酯（alkyl methacrylate）或丙烯酸酯；甲基丙烯酸苄酯、丙烯酸苄酯等的芳烷基丙烯酸甲酯或丙烯酸酯；丁氧基乙基丙烯酸甲酯（butoxyethyl methacrylate）、丁氧基乙基丙烯酸酯（butoxyethyl acrylate）等的烷氧基甲基丙烯酸烷酯（alkoxyalkyl methacrylate）或丙烯酸酯；N,N-甲基丙烯酸二甲胺乙酯、丙烯酸-N,N-二甲胺乙酯等的胺基甲基丙烯酸烷酯（aminoalkyl methacrylate）或丙烯酸酯；二乙二醇乙基醚、三乙二醇丁基醚、二丙二醇甲基醚等的聚亞烷基二醇烷基醚的甲基丙烯酸酯（methacrylic ester）或丙烯酸酯；六乙二醇苯基醚等的聚亞烷基二醇芳基醚的甲基丙烯酸酯或丙烯酸酯；甲基丙烯酸異冰片酯（isobornyl methacrylate）或丙烯酸酯；甲基丙烯酸甘油酯（glycerol methacrylate）或丙烯酸酯；2-甲基丙烯酸羥乙酯或丙烯酸酯等。(Photopolymerizable compound) The pigment-dispersed resist composition of the present invention contains a photopolymerizable compound. Examples of the photopolymerizable compound of the present invention include monomers and oligomers having one or more photopolymerizable unsaturated bonds in the molecule. The photopolymerizable unsaturated bond refers to an unsaturated bond that is polymerizable by the following action: a photopolymerization initiator described later generates free radicals or cations upon decomposition by active energy rays such as ultraviolet rays and electron rays. Examples of the monomer having one photopolymerizable unsaturated bond in the molecule include methyl methacrylate, butyl methacrylate, 2-hexyl methacrylate, methyl acrylate, and butyl acrylate. Alkyl methacrylate or acrylate, such as 2-ethylhexyl acrylate; aralkyl methyl acrylate or acrylate, such as benzyl methacrylate, benzyl acrylate, etc .; Alkoxyalkyl methacrylate or acrylate, such as butoxyethyl methacrylate, butoxyethyl acrylate, etc .; N, N-methacrylate Aminoalkyl methacrylate or acrylate such as methylamine ethyl ester, acrylic acid-N, N-dimethylamine ethyl ester; diethylene glycol ethyl ether, triethylene glycol butyl ether, Methacrylic ester or acrylate of polyalkylene glycol alkyl ether such as propylene glycol methyl ether; methacrylic acid of polyalkylene glycol aryl ether such as hexaethylene glycol phenyl ether Ester or Acrylate; isobornyl methacrylate or acrylate; glycerol methacrylate or acrylate; hydroxyethyl methacrylate or acrylate, etc.
而且，作為分子內具有2個以上光聚合性不飽和鍵的單體，可列舉雙酚A二丙烯酸甲酯、1,4-丁二醇二丙烯酸甲酯、1,3-丁二醇二丙烯酸甲酯、二乙二醇二丙烯酸甲酯、甘油基二丙烯酸甲酯、新戊二醇二丙烯酸甲酯、聚乙二醇二丙烯酸甲酯、聚丙二醇二丙烯酸甲酯、四乙二醇二丙烯酸甲酯、三羥甲基丙烷三丙烯酸甲酯、季戊四醇三丙烯酸甲酯、季戊四醇四丙烯酸甲酯、二季戊四醇四丙烯酸甲酯、二季戊四醇六丙烯酸甲酯、二季戊四醇五丙烯酸甲酯、雙酚A二丙烯酸酯、1,4-丁二醇二丙烯酸酯、1,3-丁二醇二丙烯酸酯、二乙二醇二丙烯酸酯、甘油基二丙烯酸酯、新戊二醇二丙烯酸酯、聚乙二醇二丙烯酸酯、聚丙二醇二丙烯酸酯、四乙二醇二丙烯酸酯、三羥甲基丙烷三丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯、二季戊四醇四丙烯酸酯、二季戊四醇六丙烯酸酯、二季戊四醇五丙烯酸酯等。作為這些單體可單獨或2種以上组合使用。 在本發明中，相對於顏料分散抗蝕劑組成物中的總固體成分，上述光聚合性化合物的含量優選在3～50質量%的範圍。Examples of the monomer having two or more photopolymerizable unsaturated bonds in the molecule include bisphenol A methyl diacrylate, methyl 1,4-butanediol diacrylate, and 1,3-butanediol diacrylic acid. Methyl ester, diethylene glycol diacrylate, glyceryl methyl diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol methyl diacrylate, tetraethylene glycol diacrylate Methyl ester, methyl trimethylolpropane triacrylate, methyl pentaerythritol triacrylate, methyl pentaerythritol tetraacrylate, methyl dipentaerythritol tetraacrylate, methyl dipentaerythritol hexaacrylate, methyl dipentaerythritol pentaacrylate, bisphenol A di Acrylate, 1,4-butanediol diacrylate, 1,3-butanediol diacrylate, diethylene glycol diacrylate, glyceryl diacrylate, neopentyl glycol diacrylate, polyethylene glycol Alcohol diacrylate, polypropylene glycol diacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexa Acrylate, dipentaerythritol pentaacrylate and the like. These monomers can be used individually or in combination of 2 or more types. In this invention, it is preferable that content of the said photopolymerizable compound is the range of 3-50 mass% with respect to the total solid content in a pigment dispersion resist composition.
（光聚合引發劑） 本發明的顏料分散抗蝕劑組成物含有光聚合引發劑。 作為本發明中的光聚合引發劑，只要是藉由照射紫外線、電子射線等的活性能量線可產生自由基或陽離子，則沒有特別限定，例如，可列舉二苯甲酮、N,N’-四乙基-4,4’-二胺基二苯甲酮、4-甲氧基-4’-二甲基胺基二苯甲酮、苯偶醯（benzil）、2,2-二乙氧基苯乙酮、安息香、安息香甲基醚、安息香異丁基醚、苄基二甲基縮酮、α-羥基異丁基苯酮、噻噸酮、2-氯噻噸酮、1-羥基環己基苯酮、叔丁基蒽醌、1-氯蒽醌、2,3-二氯蒽醌、3-氯-2-甲基蒽醌、2-乙基蒽醌、1,4-萘醌、1,2-苯並蒽醌、1,4-二甲基蒽醌、2-苯蒽醌、2-甲基-1［4-(甲硫基)苯基］-2-嗎啉代丙烷-1-酮、三嗪類光聚合引發劑等。這些光聚合引發劑可單獨或2種以上組合使用。 在本發明中，上述光聚合引發劑的含量相對於顏料分散抗蝕劑組成物中的總固體成分，優選1～20質量%的範圍。(Photopolymerization Initiator) The pigment-dispersed resist composition of the present invention contains a photopolymerization initiator. The photopolymerization initiator in the present invention is not particularly limited as long as it can generate radicals or cations by irradiating active energy rays such as ultraviolet rays and electron rays, and examples thereof include benzophenone, N, N'- Tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, benzil, 2,2-diethoxy Acetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, α-hydroxyisobutyl phenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxy ring Hexyl phenone, tert-butyl anthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 1,2-benzoanthraquinone, 1,4-dimethylanthraquinone, 2-benzoanthraquinone, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropane- 1-ketone, triazine-based photopolymerization initiator, and the like. These photoinitiators can be used individually or in combination of 2 or more types. In this invention, it is preferable that content of the said photoinitiator is the range of 1-20 mass% with respect to the total solid content in a pigment dispersion resist composition.
（有機溶劑） 本發明的顏料分散物含有有機溶劑。 作為本發明中的有機溶劑，可例示在油墨、塗料、液晶彩色濾光片抗蝕劑、噴墨的領域適合地利用的有機溶劑。具體而言，可例示乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單異丙基醚、乙二醇單丁基醚、二乙二醇單甲基醚、二乙二醇單乙基醚、丙二醇單甲基醚、丙二醇單乙基醚、丙二醇單丁基醚、二乙二醇二乙基醚、二乙二醇二甲基醚、二乙二醇甲基乙基醚等的醚類有機溶劑；乙二醇單甲基醚乙酸酯、乙二醇單乙基醚乙酸酯、乙二醇單丁基醚乙酸酯、丙二醇單甲基醚乙酸酯、丙二醇單乙基醚乙酸酯等的醚酯類有機溶劑；甲基異丁基酮、環己酮、2-庚酮、δ-丁內酯等的酮類有機溶劑；2-羥基丙酸甲酯、2-羥基丙酸乙酯、2-羥基-2-甲基丙酸乙酯、3-甲基-3-甲氧基丁基丙酸酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、乙氧基乙酸乙酯、羥基乙酸乙酯、甲酸-n-戊酯等的酯類有機溶劑；甲醇、乙醇、異丙基醇、丁醇等的醇類溶劑；N-甲基吡咯烷酮、N，N-二甲基甲醯胺、N,N-二甲基乙醯胺等的含氮類有機溶劑等。這些可單獨或2種以上混合使用。(Organic Solvent) The pigment dispersion of the present invention contains an organic solvent. Examples of the organic solvent in the present invention include organic solvents that are suitably used in the fields of ink, paint, liquid crystal color filter resist, and inkjet. Specific examples include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, and diethyl ether. Glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl Ether organic solvents such as methyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate , Propylene glycol monoethyl ether acetate and other ether ester organic solvents; methyl isobutyl ketone, cyclohexanone, 2-heptanone, δ-butyrolactone and other ketone organic solvents; 2-hydroxypropionic acid Methyl ester, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, 3-methyl-3-methoxybutylpropionate, methyl 3-methoxypropionate, Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, n-pentyl formate, etc. Ester organic solvents; Alcohol solvents such as methanol, ethanol, isopropyl alcohol, butanol; N -A nitrogen-containing organic solvent such as methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, and the like. These can be used individually or in mixture of 2 or more types.
在這些有機溶劑中，在溶解性、分散性、塗布性等方面，優選二乙二醇二甲基醚、二乙二醇甲基乙基醚、乙二醇單甲基醚乙酸酯、丙二醇單甲基醚乙酸酯、丙二醇單乙基醚乙酸酯、環己酮、2-庚酮、2-羥基丙酸乙酯、3-甲基-3-甲氧基丁基丙酸酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、甲酸-n-戊酯等，更優選丙二醇單甲基醚乙酸酯。 進而，這些有機溶劑從上述鹼可溶性樹脂的溶解性、顏料分散性、塗布性等的方面來看，在紅色顏料分散抗蝕劑組成物中優選含有50質量%以上，更優選含有70質量%以上。Among these organic solvents, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, ethylene glycol monomethyl ether acetate, and propylene glycol are preferred in terms of solubility, dispersibility, and coatability. Monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 2-heptanone, ethyl 2-hydroxypropionate, 3-methyl-3-methoxybutylpropionate, Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, n-pentyl formate, and the like are more preferable, and propylene glycol monomethyl ether acetate is more preferable. Furthermore, these organic solvents preferably contain 50% by mass or more, and more preferably 70% by mass or more in the red pigment-dispersed resist composition from the viewpoints of the solubility of the alkali-soluble resin, pigment dispersibility, and coatability. .
（其他成分） 為了提高本發明的顏料分散物的耐熱性、亮度，優選含有硫酸鋇。在本發明中，硫酸鋇的含量相對於上述各顏料100質量份為0～15質量%、優選5～12質量%。當上述硫酸鋇超過15質量份時，著色力大幅度降低。優選上述硫酸鋇的一次粒徑為5 nm～20 nm。當上述硫酸鋇的一次粒徑超過20 nm時，具有對比度降低、產生異物的趨勢。上述硫酸鋇在經微粒化處理的顏料的分散時或分散後使用。 而且，本發明的顏料分散抗蝕劑組成物還可根據需要適當使用熱阻聚劑、紫外線吸收劑、抗氧化劑等的各種添加劑。(Other components) In order to improve the heat resistance and brightness of the pigment dispersion of the present invention, it is preferable to contain barium sulfate. In this invention, content of barium sulfate is 0-15 mass% with respect to 100 mass parts of each said pigment, Preferably it is 5-12 mass%. When the above-mentioned barium sulfate exceeds 15 parts by mass, the tinting power is greatly reduced. The primary particle diameter of the barium sulfate is preferably 5 nm to 20 nm. When the primary particle diameter of the above barium sulfate exceeds 20 nm, the contrast tends to decrease and foreign matter tends to be generated. The above barium sulfate is used during or after dispersion of the micronized pigment. In addition, the pigment-dispersed resist composition of the present invention may also suitably use various additives such as a thermal polymerization inhibitor, an ultraviolet absorber, and an antioxidant, as necessary.
（顏料分散物的製造方法） 本發明中的顏料分散物，例如可由以上的構成材料藉由以下的製法進行製造。 首先，對各未處理顏料進行微粒化處理（鹽磨處理）從而得到經微粒化處理的顏料。更優選在作為具有與各顏料為相同骨架的化合物的磺化物的顏料分散助劑的存在下進行微粒化處理。藉由在作為具有與各顏料為相同骨架的化合物的磺化物的顏料分散助劑的存在下進行微粒化處理，能夠在抑制顏料的結晶化的同時均勻地微細化。由經微細化的顏料構成的分散液的粒徑為50 nm～70 nm左右。 該顏料分散助劑的使用量相對於顏料100質量份為0.5～30質量份、優選3～10質量份。 作為上述微粒化處理，可列舉使用捏合機、使3根攪拌刮板各自一邊進行自轉運動一邊進行公轉運動的混練裝置（kneading apparatus）等，在具有與顏料為相同骨架的化合物的磺化物的存在下將顏料用無機鹽磨碎從而將顏料的一次粒徑進一步微細化的鹽磨處理。在這樣的具有與顏料為相同骨架的化合物的磺化物的存在下進行鹽磨處理所得到的顏料進行微粒化以便使一次粒徑進一步微細且均勻。且，也將使用使3根攪拌刮板各自一邊進行自轉運動一邊進行公轉運動的混練裝置的鹽磨處理特別地稱作TRI-MIX處理。(Manufacturing method of pigment dispersion) The pigment dispersion in this invention can be manufactured from the said structural material by the following manufacturing method, for example. First, each untreated pigment is micronized (salt milling) to obtain a micronized pigment. It is more preferable to perform the micronization treatment in the presence of a pigment dispersion aid as a sulfonate of a compound having the same skeleton as each pigment. By performing the micronization treatment in the presence of a pigment dispersing aid that is a sulfonate of a compound having the same skeleton as each pigment, it is possible to uniformly refine the pigment while suppressing the crystallization of the pigment. The particle diameter of the dispersion liquid composed of the finely divided pigment is about 50 nm to 70 nm. The used amount of the pigment dispersing assistant is 0.5 to 30 parts by mass, and preferably 3 to 10 parts by mass based on 100 parts by mass of the pigment. Examples of the above-mentioned micronization treatment include a kneading apparatus using a kneader, a kneading apparatus that orbits each of the three stirring blades while performing a rotation motion, and the like. The presence of a sulfonate of a compound having the same skeleton as the pigment The salt is ground by grinding the pigment with an inorganic salt to further refine the primary particle size of the pigment. The pigment obtained by the salt milling treatment in the presence of such a sulfonate having a compound having the same skeleton as the pigment is micronized so that the primary particle diameter is further fine and uniform. In addition, a salt grinding process using a kneading device that rotates the three stirring blades while performing a revolution motion is particularly referred to as a TRI-MIX process.
以下，對TRI-MIX處理進行進一步詳細說明。 上述TRI-MIX處理為藉由將包含顏料、水溶性無機鹽（以下，也簡稱為「無機鹽」）及實質上不溶解無機鹽的水溶性分散介質（以下，也簡稱為「分散介質」）的混合物用使3根攪拌刮板一邊進行自轉運動一邊進行公轉運動的混練裝置混練後除去無機鹽及分散介質來進行。 在該處理中，作為混練裝置使用3根攪拌刮板進行行星運動即一邊進行自轉運動一邊進行公轉運動的混練裝置。據此，攪拌刮板相互間及攪拌刮板與裝置內面的死角變得非常少，可得到更為強勁、均勻的剪切力。在該剪切力下由無機鹽進行磨碎處理的顏料粒徑比一次粒徑變得更微細且均勻，可得到透明性、對比度比與以往相比更高的彩色濾光片。 且，在此「公轉運動」是指攪拌刮板在槽（tank）內進行轉圈的運動。而且，「使攪拌刮板進行公轉運動的混練裝置」是指本來使攪拌刮板自身進行移動並使其在槽內進行轉圈運動的混練裝置。然而，在本說明書中，只要槽與攪拌刮板的相對運動相同（例如，使槽進行旋轉等），則其混練裝置包含於“使攪拌刮板進行公轉運動的混練裝置”中。Hereinafter, the TRI-MIX process will be described in further detail. The above-mentioned TRI-MIX treatment is performed by including a pigment, a water-soluble inorganic salt (hereinafter, also simply referred to as "inorganic salt"), and a water-soluble dispersion medium (hereinafter, also simply referred to as "dispersion medium") that does not substantially dissolve the inorganic salt. The mixture was kneaded with a kneading device that made three stirring blades perform a revolution motion while performing a revolution motion, and then removed the inorganic salt and the dispersion medium. In this process, as a kneading device, a kneading device using three stirring blades for planetary motion, that is, a revolution motion while performing a rotation motion. Accordingly, the dead angles between the stirring blades and between the stirring blades and the inner surface of the device become very small, and a stronger and uniform shearing force can be obtained. Under this shearing force, the particle diameter of the pigment subjected to the pulverization treatment with the inorganic salt becomes finer and more uniform than the primary particle diameter, and a color filter having higher transparency and contrast than in the past can be obtained. In addition, the "revolution motion" herein refers to a motion in which the stirring blade rotates in a tank. Further, the "kneading device for revolving the stirring blade" refers to a kneading device that originally moves the stirring blade itself and makes it rotate in a groove. However, in this specification, as long as the relative movement of the groove and the stirring blade is the same (for example, the groove is rotated, etc.), the kneading device is included in the "kneading device that makes the stirring blade perform revolution motion".
進而，作為混練裝置的結構，優選滿足以下（1）及（2）的條件。 （1）相對於與3根攪拌刮板的自轉軸正交的平面，將3根自轉軸相交的點作為頂點所得到的三角形為等邊三角形。 （2）公轉軸相交於該等邊三角形的重心位置。 而且，攪拌刮板優選具有從槽的底部到液面為止的長度與從槽的內壁到中心為止的程度的寬度。作為這樣的混練裝置，例如，可列舉TRI-MIX（井上製作所公司製）等。 且，在該處理中可利用在槽內加入顏料、無機鹽及分散介質進行混練的濕式處理方法。 作為上述無機鹽，只要為水溶性則沒有特別限定，但從成本的觀點出發，優選使用食鹽（氯化鈉）。 而且，上述無機鹽的粒徑優選為200 μm以下、更優選50 μm以下。據此，能夠使著色顏料的粒徑比一次粒徑更為微細且均勻。 且，在本發明中，上述無機鹽的粒徑是指以激光衍射式粒度測定法、測定裝置：Nanotrac（UPA－EX150、日機裝公司製）測定的體積平均粒徑。Furthermore, as a structure of a kneading apparatus, it is preferable to satisfy the following conditions (1) and (2). (1) With respect to a plane orthogonal to the rotation axes of the three stirring blades, a triangle obtained by using the points where the three rotation axes intersect as vertices is an equilateral triangle. (2) The revolution axis intersects the position of the center of gravity of the equilateral triangle. The stirring blade preferably has a length from the bottom of the tank to the liquid surface and a width from the inner wall of the tank to the center. Examples of such a kneading device include TRI-MIX (manufactured by Inoue Seisakusho). In addition, in this treatment, a wet treatment method in which a pigment, an inorganic salt, and a dispersion medium are added to the tank for kneading can be used. The inorganic salt is not particularly limited as long as it is water-soluble, but from the viewpoint of cost, it is preferable to use common salt (sodium chloride). The particle diameter of the inorganic salt is preferably 200 μm or less, and more preferably 50 μm or less. Accordingly, the particle diameter of the colored pigment can be made finer and more uniform than the primary particle diameter. In the present invention, the particle diameter of the inorganic salt refers to a volume average particle diameter measured by a laser diffraction particle size measurement method and a measuring device: Nanotrac (UPA-EX150, manufactured by Nikkiso Co., Ltd.).
作為上述分散介質，只要是具有以下兩個條件的水溶性分散介質，即水溶性與不溶解無機鹽，則沒有特別限定。其中，由於鹽磨時溫度升高且溶劑成為易於蒸發的狀態，故而從安全性的觀點出發優選沸點為120℃以上的高沸點溶劑。 作為這樣的水溶性分散介質，例如可列舉2-甲氧基乙醇、2-丁氧基乙醇、2-（異戊氧基）乙醇、2-（己氧基）乙醇、1-甲氧基-2-丙醇、1-乙氧基-2-丙醇等的烷氧基醇類；二乙二醇、三乙二醇、液體聚乙二醇、二丙二醇、低分子量聚丙二醇等的二元醇類；二乙二醇單甲基醚、二乙二醇單乙基醚、二乙二醇單丁基醚、三乙二醇單甲基醚、二丙二醇單甲基醚、二丙二醇單乙基醚等的醚類等。The above-mentioned dispersion medium is not particularly limited as long as it is a water-soluble dispersion medium having the following two conditions, that is, water-soluble and insoluble inorganic salts. Among them, a high-boiling-point solvent having a boiling point of 120 ° C. or higher is preferred from the viewpoint of safety because the temperature is increased during salt milling and the solvent is easily evaporated. Examples of such a water-soluble dispersion medium include 2-methoxyethanol, 2-butoxyethanol, 2- (isopentoxy) ethanol, 2- (hexyloxy) ethanol, and 1-methoxy- Alkoxy alcohols such as 2-propanol, 1-ethoxy-2-propanol; diethylene glycol, triethylene glycol, liquid polyethylene glycol, dipropylene glycol, low molecular weight polypropylene glycol, etc. Alcohols; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether Ethers and the like.
作為使用以上的材料與裝置來進行TRI-MIX處理的方法，可列舉以下的方法等。 將顏料、作為具有與各顏料為相同骨架的化合物的磺化物的顏料分散助劑、無機鹽及分散介質加入到槽內。接著，使混練裝置的3根攪拌刮板一邊進行自轉運動一邊進行公轉運動從而將顏料用無機鹽進行磨碎處理。其後，將加入溫水成為漿狀的物質進行過濾並藉由水洗將殘留的無機鹽與分散介質除去。在該顏料的磨碎處理中，優選適當調節材料的加入量（粘度）、槽的內徑等，以便充分發揮用於混練的應力。例如，優選如下進行調配、處理，以便使用上述TRI-MIX進行處理時的負荷電流成為發動機的額定電流值的50%～85%的範圍。 接著，得到包含上述各微粒化物與上述具有三級胺基及／或四級銨基的丙烯酸類嵌段共聚物、上述顏料分散助劑（Ａ）、上述鹼可溶性樹脂、有機溶劑及根據需要硫酸鋇的各混合物。將所得到的各混合物使用輥磨機、捏合機、高速攪拌裝置、珠磨機、球磨機、砂磨機、超聲波分散機、高壓分散機等的各種分散機進行混練、分散處理，從而得到各顏料分散物。且，也可使顏料分散物中預先含有光聚合性化合物。As a method of performing TRI-MIX processing using the above materials and devices, the following methods and the like can be cited. A pigment, a pigment dispersing aid as a sulfonate of a compound having the same skeleton as each pigment, an inorganic salt, and a dispersion medium were added to the tank. Next, the three stirring blades of the kneading device were subjected to a revolution motion while performing a rotation motion to grind the pigment with an inorganic salt. After that, the substance which was added with warm water to form a slurry was filtered, and the remaining inorganic salt and the dispersion medium were removed by washing with water. In the grinding process of the pigment, it is preferable to appropriately adjust the amount of addition of the material (viscosity), the inner diameter of the groove, and the like, so that the stress for kneading can be fully exerted. For example, it is preferable to perform blending and processing as follows so that the load current when processing using the TRI-MIX is in a range of 50% to 85% of the rated current value of the engine. Next, the fine particles and the acrylic block copolymer having the tertiary amine group and / or the quaternary ammonium group, the pigment dispersion aid (A), the alkali-soluble resin, the organic solvent, and sulfuric acid as necessary are obtained. Various mixtures of barium. Each obtained mixture is kneaded and dispersed using various dispersers such as a roll mill, a kneader, a high-speed stirring device, a bead mill, a ball mill, a sand mill, an ultrasonic disperser, and a high-pressure disperser to obtain each pigment. Dispersion. In addition, a photopolymerizable compound may be contained in the pigment dispersion in advance.
（顏料分散抗蝕劑組成物的製造方法） 對從各顏料分散物得到本發明的顏料分散抗蝕劑組成物的方法進行說明。 關於從各顏料分散物得到本發明的顏料分散抗蝕劑組成物的方法，例如，可藉由下述（1）、（2）得到。 （1）將C.I.顏料紅221顏料分散物與C.I.顏料紅177顏料分散物的各顏料分散物混合成為規定的顏料比例後，加入光聚合性化合物、光聚合引發劑、剩餘的鹼可溶性樹脂、有機溶劑、根據需要的硫酸鋇，從而得到顏料分散抗蝕劑組成物。 （2）在各顏料分散物中加入光聚合性化合物、光聚合引發劑、剩餘的鹼可溶性樹脂、有機溶劑、根據需要的硫酸鋇從而得到各顏料分散抗蝕劑組成物後，將C.I.顏料紅264顏料分散抗蝕劑組成物與C.I.顏料紅177顏料分散抗蝕劑組成物混合成為規定的顏料比例，從而得到顏料分散抗蝕劑組成物。(Manufacturing method of pigment dispersion resist composition) The method of obtaining the pigment dispersion resist composition of this invention from each pigment dispersion is demonstrated. The method for obtaining the pigment-dispersed resist composition of the present invention from each pigment dispersion can be obtained, for example, by the following (1) and (2). (1) After mixing each pigment dispersion of CI Pigment Red 221 pigment dispersion and CI Pigment Red 177 pigment dispersion to a predetermined pigment ratio, add a photopolymerizable compound, a photopolymerization initiator, the remaining alkali-soluble resin, organic A solvent and, if necessary, barium sulfate, to obtain a pigment-dispersed resist composition. (2) After adding a photopolymerizable compound, a photopolymerization initiator, the remaining alkali-soluble resin, an organic solvent, and barium sulfate as needed to each pigment dispersion to obtain each pigment dispersion resist composition, the CI pigment red The 264 pigment-dispersed resist composition and the CI Pigment Red 177 pigment-dispersed resist composition are mixed to a predetermined pigment ratio to obtain a pigment-dispersed resist composition.
使用藉由上述方法所得到的顏料分散抗蝕劑組成物來製造彩色濾光片，以便成為規定的膜厚，由此可得到對比度（Bare：1000）為700以上的彩色濾光片。 且，本發明中的對比度的測定條件如下，將彩色濾光片的膜厚作為1.0 μm，將其各抗蝕劑的彩色特性（ｘ，ｙ，Ｙ）用分光光度計(島津製作所公司製、UV-2500PC、C光源2°視野)測定的值為色度ｘ＝0.6730、ｙ＝0.3200時的對比度（Bare：1000）。 在本發明中，作為對比度更優選700以上（Bare：1000）、進一步優選705以上。 [實施例]By using the pigment-dispersed resist composition obtained by the above method to produce a color filter so as to have a predetermined film thickness, a color filter having a contrast (Bare: 1000) of 700 or more can be obtained. The conditions for measuring the contrast in the present invention are as follows. The film thickness of the color filter is 1.0 μm, and the color characteristics (x, y, Ｙ) of each resist are measured with a spectrophotometer (manufactured by Shimadzu Corporation, UV-2500PC, C light source 2 ° field of view) The measured values are contrast (Bare: 1000) when chromaticity x = 0.6730 and y = 0.3200. In the present invention, the contrast is more preferably 700 or more (Bare: 1000), and even more preferably 705 or more. [Example]
以下列舉實施例來進一步詳細地說明本發明，但本發明並不僅限定於這些實施例。且在沒有特別聲明的情況下，「%」是指「質量%」的意思，「份」是指「質量份」的意思。而且，本說明書中，「TRI-MIX」為股份有限公司井上製作所的註冊商標，「豔佳固」為Ciba Japan公司的註冊商標。Examples are given below to further explain the present invention, but the present invention is not limited to these examples. And unless otherwise stated, "%" means "mass%" and "part" means "mass part". In this manual, "TRI-MIX" is a registered trademark of Inoue Co., Ltd., and "Yanjiagu" is a registered trademark of Ciba Japan.
＜顏料分散助劑＞ （C.I.顏料紅221的磺化物） 在100 ml三角燒瓶中加入30 ml濃硫酸，一邊用磁力攪拌器攪拌一邊投入10 g C.I.顏料紅221，在室溫下攪拌30分鐘。在1 L燒杯中裝入50 g水和50 g冰的混合物，將上述反應物倒入該冰水中，用磁力攪拌器攪拌30分鐘。將其在減壓下過濾・水洗，再將所得到的固體乾燥，從而得到12 g C.I.顏料紅221的磺化物。 （C.I.顏料紅2的磺化物） 在100 ml三角燒瓶中加入30 ml濃硫酸，一邊用磁力攪拌器攪拌一邊投入10 g C.I.顏料紅2，在室溫下攪拌30分鐘。在1 L燒杯中裝入50 g水和50 g冰的混合物，將上述反應物倒入該冰水中，用磁力攪拌器攪拌30分鐘。將其在減壓下過濾・水洗，再將所得到的固體乾燥，從而得到12 g C.I. 顏料紅2的磺化物。 （C.I.顏料橙71的磺化物） 在100 ml三角燒瓶中加入30 ml濃硫酸，一邊用磁力攪拌器攪拌一邊投入10 g C.I.顏料橙71，在室溫下攪拌30分鐘。在1 L燒杯中裝入50 g水和50 g冰的混合物，將上述反應物倒入該冰水中，用磁力攪拌器攪拌30分鐘。將其在減壓下過濾・水洗，再將所得到的固體乾燥，從而得到12 g C.I. 顏料橙71的磺化物。<Pigment dispersing aid> (C.I. sulfonate of pigment red 221) In a 100 ml Erlenmeyer flask, 30 ml of concentrated sulfuric acid was added, while stirring with a magnetic stirrer, 10 g of C.I. pigment red 221 was added, and the mixture was stirred at room temperature for 30 minutes. A 1 L beaker was charged with a mixture of 50 g of water and 50 g of ice, the above reactants were poured into the ice water, and stirred with a magnetic stirrer for 30 minutes. This was filtered and washed under reduced pressure, and the obtained solid was dried to obtain 12 g of a sulfide of C.I. Pigment Red 221. (C.I.sulfonate of Pigment Red 2) 30 ml of concentrated sulfuric acid was added to a 100 ml Erlenmeyer flask, and 10 g of C.I. Pigment Red 2 was added while stirring with a magnetic stirrer, and stirred at room temperature for 30 minutes. A 1 L beaker was charged with a mixture of 50 g of water and 50 g of ice, the above reactants were poured into the ice water, and stirred with a magnetic stirrer for 30 minutes. This was filtered and washed under reduced pressure, and the obtained solid was dried to obtain 12 g of a sulfide of C.I. Pigment Red 2. (C.I.sulfonate of Pigment Orange 71) In a 100 ml Erlenmeyer flask, add 30 ml of concentrated sulfuric acid, and while stirring with a magnetic stirrer, put 10 g of C.I. Pigment Orange 71, and stir at room temperature for 30 minutes. A 1 L beaker was charged with a mixture of 50 g of water and 50 g of ice, the above reactants were poured into the ice water, and stirred with a magnetic stirrer for 30 minutes. This was filtered and washed under reduced pressure, and the obtained solid was dried to obtain 12 g of a sulfide of C.I. Pigment Orange 71.
＜微粒化處理＞ 製備例1（微粒化處理PR221（顏料紅221）） 在TRI-MIX TX-15(商品名、井上製作所製)的槽中投入800份C.I.顏料紅221、8000份粒徑20 μm的氯化鈉、1920份二乙二醇。在成為額定電流值9.3A的70%的範圍內，且在45℃混練3小時來進行鹽磨處理。接下來將1300份所得到的混練物投入3升的溫水中，一邊在70℃加熱一邊攪拌1小時成為漿狀。反覆過濾、水洗除去氯化鈉及二乙二醇後，在40℃乾燥一晝夜，得到720份的微粒化處理PR221。<Micronization Treatment> Preparation Example 1 (Micronization Treatment PR221 (Pigment Red 221)) 800 parts of CI Pigment Red 221 and 8000 parts of particle size 20 were put into a tank of TRI-MIX TX-15 (trade name, manufactured by Inoue Seisakusho). μm of sodium chloride, 1920 parts of diethylene glycol. The salt milling process was performed within the range of 70% of the rated current value of 9.3A, and kneading was performed at 45 ° C for 3 hours. Next, 1300 parts of the obtained kneaded product was poured into 3 liters of warm water, and stirred for 1 hour while being heated at 70 ° C. to form a slurry. After repeated filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 40 ° C for one day and night to obtain 720 parts of micronized PR221.
製備例2（含顏料分散助劑的微粒化處理PR221（顏料紅221）） 在TRI-MIX TX-15(商品名、井上製作所製)的槽中投入800份C.I.顏料紅221、40份C.I.顏料紅221的磺化物、8000份粒徑20 μm的氯化鈉、1920份二乙二醇。在成為額定電流值9.3A的70%的範圍內，且在45℃混練3小時來進行鹽磨處理。接下來將1300份所得到的混練物投入3升的溫水中，一邊在70℃加熱一邊攪拌1小時成為漿狀。反覆過濾、水洗除去氯化鈉及二乙二醇後，在40℃乾燥一晝夜，得到740份含顏料分散助劑的微粒化處理PR221。Preparation Example 2 (Micronized PR221 (Pigment Red 221) with Pigment Dispersion Aid) 800 parts of CI Pigment Red 221 and 40 parts of CI Pigment were placed in a tank of TRI-MIX TX-15 (trade name, manufactured by Inoue Seisakusho). Red 221 sulfonate, 8000 parts of sodium chloride with a particle size of 20 μm, and 1920 parts of diethylene glycol. The salt milling process was performed within the range of 70% of the rated current value of 9.3A, and kneading was performed at 45 ° C for 3 hours. Next, 1300 parts of the obtained kneaded product was poured into 3 liters of warm water, and stirred for 1 hour while being heated at 70 ° C. to form a slurry. After repeated filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 40 ° C for one day and night to obtain 740 parts of a micronized PR221 containing a pigment dispersion aid.
製備例3（含顏料分散助劑的微粒化處理PR254（顏料紅254）） 在TRI-MIX TX-15(商品名、井上製作所製)的槽中投入800份C.I.顏料紅254、40份C.I.顏料橙71的磺化物、8000份粒徑20 μm的氯化鈉、1920份二乙二醇。在成為額定電流值9.3A的70%的範圍內，且在45℃混練3小時來進行鹽磨處理。接下來將1300份所得到的混練物投入3升的溫水中，一邊在70℃加熱一邊攪拌1小時成為漿狀。反覆過濾、水洗除去氯化鈉及二乙二醇後，在40℃乾燥一晝夜，得到740份含顏料分散助劑的微粒化處理PR254。Preparation Example 3 (Micronized PR254 (Pigment Red 254) Containing Pigment Dispersion Aid) 800 parts of CI Pigment Red 254 and 40 parts of CI Pigment were placed in a tank of TRI-MIX TX-15 (trade name, manufactured by Inoue Seisakusho). Orange 71 sulfonate, 8000 parts of sodium chloride with a particle size of 20 μm, and 1920 parts of diethylene glycol. The salt milling process was performed within the range of 70% of the rated current value of 9.3A, and kneading was performed at 45 ° C for 3 hours. Next, 1300 parts of the obtained kneaded product was poured into 3 liters of warm water, and stirred for 1 hour while being heated at 70 ° C. to form a slurry. After repeated filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 40 ° C for one day and night to obtain 740 parts of a micronized PR254 containing a pigment dispersion aid.
製備例4（微粒化處理PR177（顏料紅177）） 在TRI-MIX TX-15(商品名、井上製作所公司製)的槽中投入800份C.I.顏料紅177、8000份粒徑20 μm的氯化鈉、1920份二乙二醇。在成為額定電流值9.3A的70%的範圍內，且在45℃混練3小時來進行鹽磨處理。接下來將1300份所得到的混練物投入3升的溫水中，一邊在70℃加熱一邊攪拌1小時成為漿狀。反覆過濾、水洗除去氯化鈉及二乙二醇後，在40℃乾燥一晝夜，得到720份的微粒化處理PR177。Preparation Example 4 (Micronized PR177 (Pigment Red 177)) 800 parts of CI Pigment Red 177 and 8000 parts of chlorinated chlorinated particles having a particle size of 20 μm were placed in a tank of TRI-MIX TX-15 (trade name, manufactured by Inoue Seisakusho). Sodium, 1920 parts of diethylene glycol. The salt milling process was performed within the range of 70% of the rated current value of 9.3A, and kneading was performed at 45 ° C for 3 hours. Next, 1300 parts of the obtained kneaded product was poured into 3 liters of warm water, and stirred for 1 hour while being heated at 70 ° C. to form a slurry. After repeated filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 40 ° C for one day and night to obtain 720 parts of micronized PR177.
＜具有三級胺基及／或四級銨基的丙烯酸類嵌段共聚物＞ BYK－LPN22102（畢克化學（BYK）公司製）、固體成分濃度40質量% ＜鹼可溶性樹脂＞ BzMA／MAA共聚物（甲基丙烯酸苄酯／甲基丙烯酸共聚物、理論酸值：120 mg KOH/g、質均分子量：25,000） ＜光聚合性化合物＞ DPEHA（二季戊四醇六丙烯酸酯） ＜光聚合引發劑＞ 豔佳固369（Ciba Japan公司製、2-苄基-2-(二甲基胺基)-1-(4-嗎啉苯基)-丁酮-1） ＜有機溶劑＞ PGMEA（丙二醇單甲基醚乙酸酯） ＜硫酸鋇＞ BF－40（平均一次粒徑0.01 μm、堺化學工業公司製）<Acrylic block copolymer having tertiary amine group and / or quaternary ammonium group> BYK-LPN22102 (manufactured by BYK), solid content concentration of 40% by mass <alkaline soluble resin> BzMA / MAA copolymerization Substance (benzyl methacrylate / methacrylic acid copolymer, theoretical acid value: 120 mg KOH / g, mass average molecular weight: 25,000) <photopolymerizable compound> DPEHA (dipentaerythritol hexaacrylate) <photopolymerization initiator> Yanjiagu 369 (2-benzyl-2- (dimethylamino) -1- (4-morpholinyl) -butanone-1 manufactured by Ciba Japan) <organic solvent> PGMEA (propylene glycol monomethyl Ether ether acetate) <barium sulfate> BF-40 (average primary particle size 0.01 μm, manufactured by Sakai Chemical Industry Co., Ltd.)
（分散液及抗蝕劑組成物的製造） ＜紅色顏料分散物＞ 為了成為表1 的組成，將各分散液用的各個微粒化物與其他各成分進行混合，用珠磨機在40℃～50℃的溫度下混練3小時從而得到各紅色顏料分散物。 ＜彩色濾光片用顏料分散抗蝕劑組成物＞ 將藉由上述的工序所得到的各顏料分散組成物與其他材料（BzMA／MAA共聚物、DPEHA、豔佳固、PGMEA）為了成為表1的組成使用高速攪拌機均勻混合後，用孔徑3 μm的過濾器進行過濾，並得到各彩色濾光片用紅色顏料分散抗蝕劑組成物。(Production of dispersion liquid and resist composition) <Red pigment dispersion> In order to have the composition shown in Table 1, each particulate material for each dispersion liquid was mixed with other components, and the bead mill was used at 40 ° C to 50 ° C. Kneading was performed at a temperature of 3 ° C for 3 hours to obtain each red pigment dispersion. <Pigment-dispersed resist composition for color filters> Each pigment-dispersed composition obtained by the above-mentioned steps and other materials (BzMA / MAA copolymer, DPEHA, Yanjiagu, PGMEA) are used to make Table 1 The composition was uniformly mixed using a high-speed stirrer, and then filtered with a filter having a pore size of 3 μm to obtain a red pigment-dispersed resist composition for each color filter.
＜實施例、比較例的彩色濾光片用紅色顏料分散抗蝕劑組成物＞ 將各彩色濾光片用紅色顏料分散抗蝕劑組成物為了成為表2-1、表2-2及表2-3所示的調配進行組合，從而得到實施例1～實施例9、比較例1～比較例3的彩色濾光片用紅色顏料分散抗蝕劑組成物。<Red pigment dispersion resist composition for color filters of Examples and Comparative Examples> The red pigment dispersion resist composition for each color filter was used to form Table 2-1, Table 2-2, and Table 2 The formulation shown in -3 is combined to obtain a red pigment-dispersed resist composition for a color filter of Examples 1 to 9 and Comparative Examples 1 to 3.
評價方法 進行下述評價，將評價結果示於表1及表2-1、表2-2及表2-3。 ＜粘度＞ 對於實施例及比較例的彩色濾光片用顏料分散抗蝕劑組成物，分別採集入玻璃瓶，密封並在室溫保存1天後，使用E型粘度計（東機產業股份有限公司製、R100型粘度計、型號RE100Ｌ）測定25℃下的粘度。粘度越低流動性越好，則意味著作為顏料分散物越優異。Evaluation method The following evaluations were performed, and the evaluation results are shown in Table 1 and Table 2-1, Table 2-2, and Table 2-3. <Viscosity> The pigment dispersion resist compositions for color filters of Examples and Comparative Examples were collected into glass bottles, sealed and stored at room temperature for 1 day, and then E-type viscometers (Toki Sangyo Co., Ltd. (Made by the company, R100 viscometer, model RE100L) to measure the viscosity at 25 ° C. The lower the viscosity, the better the fluidity, which means that the work is more excellent as a pigment dispersion.
＜分散穩定性＞ 對於實施例及比較例的彩色濾光片用顏料分散抗蝕劑組成物分別採集入玻璃瓶，密封在室溫下保存7天後，將其狀態依照下述評價標準進行評價。 ○：增粘、沉澱物均沒有發現。 △：發現輕輕振盪時恢復原本程度的增粘、沉澱物。 ×：發現即使強烈振盪也沒有恢復原本程度的增粘、沉澱物。<Dispersion stability> The pigment-dispersed resist compositions for color filters of Examples and Comparative Examples were collected into glass bottles, sealed and stored at room temperature for 7 days, and their states were evaluated according to the following evaluation criteria. . ○: No thickening or sediment was found. (Triangle | delta): Thickness and deposit which recovered to the original degree when it shakes lightly are found. X: Even if it shakes strongly, it turns out that the original thickening and deposit were not restored.
＜彩色濾光片用顏料分散抗蝕劑組成物的彩色特性的評價＞ 將上述膜厚為1.0 μm的實施例及比較例的各抗蝕劑的彩色特性(x，y，Y)使用分光光度計(島津製作所公司製、UV-2500PC、C光源2°視野)進行測定。在此，在實施例1～實施例3及比較例1中求得色度ｘ＝0.6730、ｙ＝0.3200時的對比度、亮度Ｙ、膜厚。在實施例4～實施例6及比較例2中，求得色度ｘ＝0.6700、ｙ＝0.3122時的對比度、亮度Ｙ、膜厚。在實施例7～實施例9及比較例3中，求得色度ｘ＝0.6800、ｙ＝0.3150時的對比度、亮度Ｙ、膜厚。<Evaluation of the color characteristics of the pigment-dispersed resist composition for a color filter> The color characteristics (x, y, Y) of each of the resists of the examples and comparative examples having the above-mentioned film thickness of 1.0 μm were spectrophotometric. The measurement was performed using a meter (manufactured by Shimadzu Corporation, UV-2500PC, C light source 2 ° field of view). Here, in Example 1 to Example 3 and Comparative Example 1, the contrast, brightness Ｙ, and film thickness when chromaticity x = 0.6730 and y = 0.3200 were obtained. In Examples 4 to 6 and Comparative Example 2, the contrast, brightness Ｙ, and film thickness at the time of chromaticity x = 0.6700 and y = 0.3122 were obtained. In Examples 7 to 9 and Comparative Example 3, the contrast, brightness Ｙ, and film thickness at the time of chromaticity x = 0.6800 and y = 0.3150 were obtained.
＜耐熱性＞ 將實施例及比較例的彩色濾光片用顏料分散抗蝕劑組成物使用旋塗機（spin coater）塗佈在玻璃基板上使膜厚成為1.0 μm，並在100℃預烘（pre-bake）3分鐘後用高壓汞燈曝光，再進一步在270℃後烘（post-bake)60分鐘。其後，將所得到的抗蝕劑塗膜的表面以顯微鏡（KEYENCE股份有限公司製、VHS-500、倍率500倍）進行觀察，並觀察後烘中伴隨顏料昇華的表面粗糙的程度，且根據下述評價標準進行評價。 ○：未發現表面粗糙 ×：發現表面粗糙<Heat resistance> The pigment-dispersed resist compositions for color filters of Examples and Comparative Examples were coated on a glass substrate using a spin coater so that the film thickness became 1.0 μm, and prebaked at 100 ° C. After 3 minutes (pre-bake) exposure with a high-pressure mercury lamp, and further post-bake at 270 ° C for 60 minutes. Thereafter, the surface of the obtained resist coating film was observed with a microscope (manufactured by KEYENCE Corporation, VHS-500, 500 times magnification), and the degree of surface roughness accompanied by sublimation of the pigment in post-baking was observed. Evaluation was performed by the following evaluation criteria. ○: No surface roughness was found ×: Surface roughness was found
＜耐溶劑性＞ 將在上述彩色特性的評價中使用的試驗用基板在N-甲基吡咯烷酮中浸漬30分鐘。將基板取出後，根據下述評價標準進行評價。 ○：未發現塗膜的溶出 ×：發現塗膜的溶出<Solvent resistance> The test substrate used for the evaluation of the above-mentioned color characteristics was immersed in N-methylpyrrolidone for 30 minutes. After the substrate was taken out, evaluation was performed according to the following evaluation criteria. ○: No elution of the coating film was observed ×: No elution of the coating film was found
[表1]
[表2-1]
根據實施例1～實施例3的例子，作為彩色濾光片的必需色度ｘ＝0.6730、ｙ＝0.3200時的亮度為15.90～16.00時明亮。進而，此時的對比度相對於Bare中的1000，在實施例1及實施例2中為730任一個均高，根據實施例3時為530充分高。而且，實施例1～實施例3的彩色濾光片中的任一個耐熱性及耐溶劑性均良好。 相對於此，根據未使用C.I.顏料紅221的比較例1時，所得到的彩色濾光片的亮度良好，但對比度、耐熱性及耐溶劑性差。 同樣的趨勢在實施例4～實施例6與比較例2的組合中，而且在實施例7～實施例9與比較例3的組合中也得到確認。 根據以上結果可知，與使用C.I.顏料紅254相比，藉由採用C.I.顏料紅221能夠發揮更顯著的效果。According to the examples of Examples 1 to 3, the required chromaticity as a color filter is bright when the brightness is 15.90 to 16.00 and the brightness is 15.90 to 16.00. Furthermore, the contrast at this time is high with respect to 1000 in Bare, and is high in any of Examples 1 and 2 and 530 in Example 3, which is sufficiently high. In addition, any of the color filters of Examples 1 to 3 had good heat resistance and solvent resistance. In contrast, according to Comparative Example 1 in which C.I. Pigment Red 221 was not used, the obtained color filter had good brightness, but had poor contrast, heat resistance, and solvent resistance. The same trend was confirmed in the combination of Examples 4 to 6 and Comparative Example 2, and also in the combination of Examples 7 to 9 and Comparative Example 3. From the above results, it can be seen that the use of C.I. Pigment Red 221 can exhibit a more significant effect than the use of C.I. Pigment Red 254.
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