JP2004002846A - Pigment dispersion composition, photosensitive coloring composition, color filter, and liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive coloring composition excellent in color characteristics, fine pattern formability, and physical characteristics after cured, to provide a pigment dispersion composition used for preparing the photosensitive coloring composition, to provide a color filter having pixels, especially blue pixels, formed by using the photosensitive coloring composition, and to provide a liquid crystal display device. <P>SOLUTION: A maleimide-based alkali-soluble copolymer is used as a binder for the photosensitive coloring composition, wherein the maleimide-based alkali-soluble copolymer contains cyclohexylmaleimide monomer units in an amount of 5-50 wt%, (meth)acrylic acid monomer units in an amount of 8-30 wt%, and (meth)acrylic ester monomer units in an amount of 30-87 wt% as essential components and satisfies the following expression: 0.4×X≤Y≤0.5×X+10Y (X is an amount of the cyclohexylmaleimide monomer units in wt%; and Y is an amount of the (meth)acrylic acid monomer units in wt%). A blue pigment or a phthalocyanine-based pigment is mixed into the photosensitive coloring composition which contains the maleimide-based copolymer. <P>COPYRIGHT: (C)2004,JPO

Description

【０１５５】
【表２】

【０１５６】
（１）シクロヘキシルマレイミド樹脂溶液１の分析方法
＜未反応単量体、共重合体組成＞
重合終了時の未反応モノマーをガスクロマトグラフィーで定量することにより決定した。
【０１５７】
＜固形分＞
アルミ皿に樹脂溶液０．３ｇを精秤し、１４０℃で５時間真空乾燥を行い揮発分を除去した後の質量から求めた。
【０１５８】
＜酸価＞
樹脂溶液３ｇを精秤し、アセトン７０ｇ／水３０ｇ混合溶媒に溶解し、チモールブルーを指示薬として０．１Ｎ　ＫＯＨ水溶液で滴定し、固形分の濃度から固形分１ｇ当たりの酸価を求めた。
【０１５９】
＜粘度＞
３００ｍｌトールビーカーに樹脂溶液を入れ、２５±０．２℃の恒温水槽中にて保持し、２５±０．５℃に調温し、Ｂ型デジタル粘度計（東機産業製ＤＶＭ−Ｂ型）でローターＮｏ．３、６ｒｐｍにて粘度を測定した。
【０１６０】
＜水分量＞
新カールフィッシャー滴定用溶媒ハヤシ−ソルベントＣＥ（ＨＡＹＡＳＨＩ−Ｓｏｌｖｅｎｔ　ＣＥ）脱水溶媒を用い、試料１ｇを滴定溶媒３０ｇに溶解し、カールフィッシャー測定装置（京都電子工業製ＭＫＳ−３Ｐ）にて水分量を測定した。
【０１６１】
＜二重結合量＞
樹脂溶液を７０℃で５時間真空乾燥を行い溶媒を揮発させた後、ＤＭＳＯ−ｄ６を溶媒、クロロホルムを内部標準物質として、２００ＭＨｚ　１Ｈ　ＮＭＲ（バリアン　テクノロジーズ　ジャパン　リミテッド製Ｇｅｍｉｎｉ２０００／２００ＢＢ）を測定し、二重結合の吸収強度から求めた。
【０１６２】
＜重量平均分子量（Ｍｗ）＞
ポリスチレンを標準物質とし、ＴＨＦを溶離液としてショウデックスＧＰＣシステム−２１Ｈ（Ｓｈｏｄｅｘ　ＧＰＣ　Ｓｙｓｔｅｍ−２１Ｈ）により重量平均分子量を測定した。
【０１６３】
＜ガラス転移点（Ｔｇ）＞
理学電気社製、ＤＳＣ８２３０（商品名）を使用し、ポリマー単体を窒素気流下、昇温速度１０℃／ｍｉｎで測定した。
【０１６４】
＜１％ＫＯＨ溶解性＞
重合液をテトラヒドロフラン（ＴＨＦ）で希釈し、大量のヘキサン中で析出させ濾過乾燥し、ポリマー単体を分離し、１％ＫＯＨ水溶液に対し２０％となるように入れ、３時間攪拌した。攪拌後、不溶物がある場合は濾過し、不溶分の量を測定し、下記の基準に従って評価した。
◎：完全溶解、
○：極わずかに濁りがある乃至、不溶分が１０％以下、
△：不溶分が１０％〜５０％、
×：不溶分が５０％以上
＜プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）、酢酸３−メトキシブチル（メトアセ）溶解性＞
析出溶解したポリマーを、２０％となるように各溶媒を加え、６０℃に加温し３時間攪拌した後、室温に放冷した。不溶物がある場合は濾過し、不溶分の量を測定し、下記の基準に従って評価した。
◎：完全溶解、
○：極わずかに濁りがある乃至、不溶分が１０％以下、
△：不溶分が１０％〜５０％、
×：不溶分が５０％以上
＜３８０ｎｍ透過率＞
共重合体溶液を、ジエチレングリコールジメチルエーテル（ＤＭＤＧ）を用いてポリマー濃度２０％まで希釈し、ガラス基板にスピンコーターを用いて塗膜を形成し、室温で３０分、９０℃で３０分、２００℃で３０分加熱乾燥し、２μｍ厚の塗膜を形成した。その後、２５０℃で１時間加熱し、３８０〜７８０ｎｍの範囲での光線透過率を測定した。
【０１６５】
（２）青色顔料分散組成物及び青色レジストの評価方法
（２−１）顔料分散性
青色顔料分散組成物の５０％平均顔料粒子径を、日機装（株）製レーザードップラー散乱光解析粒度分析計（Ｍｉｃｒｏｔｒａｃ９３４ＵＰＡ）を用いて測定した。
【０１６６】
（２−２）現像形態、現像時間、分光特性、耐熱性、パターンの断面形状
アルカリ洗浄済みのガラス基板上に、青色レジストをスピンコーティングした後、室温で３分間、さらに８０℃のホットプレート上で３分間乾燥させ、膜厚１．３μｍの塗膜を形成した。この塗膜を１００ｍＪ／ｃｍ^２でマスク露光し、スピン現像し、現像液に６０秒間接液させた後に純水で洗浄し、パターン形成された基板を２３０℃のオーブン中で３０分間ベイクした。この現像過程において、現像形態が溶解型か剥離型かを観察すると共に、現像時間を測定した。
【０１６７】
次に、得られた青色パターン付き基板を、国際照明委員会の規定するＣ光源を用い、オリンパス光学工業（株）製顕微分光測光装置（ＯＳＰ　ＳＰ−１００）により、ＪＩＳ　Ｚ８７０１に定める明るさＹ値を測定した。
【０１６８】
その後、当該青色パターン付き基板を２５０℃のオーブン中で１時間加熱し、同様の方法で明るさＹ値を測定し、耐熱試験前のＹ値を基準にして試験前後のＹ値の変化率を算出した。
【０１６９】
また、２３０℃、３０分間のベイク後の段階で得られた青色パターン付き基板の着色層の断面形状をＳＥＭ（走査型電子顕微鏡）で観察すると共に、ＳＥＭ写真を用いて着色層の立上がり角度と、下底の長さに対する上底の長さの比を算出した。
【０１７０】
（２−３）現像残渣
裏面にクロムを蒸着したガラス基板上に、青色レジスト液をスピンコーティングした後、室温で３分間、さらに８０℃のホットプレート上で３分間乾燥させ、膜厚１．３μｍの塗膜を形成した。この塗膜をスピン現像し、現像液に６０秒間接液させた後に純水で洗浄した。
【０１７１】
洗浄後、ガラス基板を投光器により目視観察し、残渣の有無を確認した。また、基板の表面をエタノール付きウエスで拭き取り、ウエス上に拭き取られた残渣の有無を確認した。
【０１７２】
（２−４）コントラスト比
実施例（２−２）で得られた青色レジスト塗布基板を２枚の偏光板（日東電工製ＮＰＦ−Ｇ　１２２０ＤＵ）で挟み込み、バックライト（東芝製メロウ５Ｄ　ＦＬ１０ＥＸ−Ｄ−Ｈ　色温度６５００Ｋ）を点灯し、偏光板の直交時と平行時の輝度を輝度計（ミノルタ製ＳＬ−１００）により測定した。コントラスト比は輝度の測定値を用い、以下の式により導き出せる。
【０１７３】
コントラスト比＝平行輝度（ｃｄ／ｍ^２）／直交輝度（ｃｄ／ｍ^２）
（２−５）表面粗度、密着性、解像度、碁盤目ピール試験
製版性（表面粗度（Ｒａ）、ラインアンドスペースによる密着性と解像度、碁盤目ピール試験）に関する評価を行った。１０ｃｍ画のガラス基板上に、硬化性樹脂組成物１をスピンコーター（ＭＩＫＡＳＡ製、形式１Ｈ−ＤＸ２）により、塗布、乾燥し、乾燥膜厚２．２μｍの塗布膜を形成した。この塗布膜をホットプレート上で９０℃、３分間加熱した。加熱後、塗布膜から１００μｍの距離にフォトマスクを配置して２．０ｋＷの超高圧水銀ランプを装着したＵＶアライナー（大日本スクリーン製、形式ＭＡ　１２００）によって１００ｍＪ／ｃｍ^２の強度（４０５ｎｍ照度換算）で紫外線を照射した。
【０１７４】
紫外線照射後、塗布膜に０．０５ｗｔ％の水酸化カリウム水溶液をスピン現像機（Ａｐｐｌｉｅｄ　Ｐｒｏｃｅｓｓ　Ｔｅｃｈｎｏｌｏｇｙ，ＩＮＫ、ＭＯＤＥＬ：９１５）にて６０秒間散布し、未露光部を溶解、除去し、残った露光部を純水で６０秒間水洗することにより現像した。現像後、露光部の膜をクリーンオーブン（忍足研究所（株）製、ＳＣＯＶ−２５０　Ｈｙ−Ｓｏ）により、２００℃で３０分間加熱した。
【０１７５】
アルカリ現像処理後の塗膜表面を、タカノ（株）製走査型プローブ顕微鏡（ＡＳ−７Ｂ）を使用してＡＦＭ測定を行い、ＪＩＳ　Ｂ０６０１−１９９４に規定される表面粗度（Ｒａ）（塗膜表面の平滑性）を決定し、下記の基準に従って評価した。
【０１７６】
＜表面粗度の評価基準＞
◎：極めて平滑である。（５０Å以下）
○：平滑である。（５０Å超、１００Å未満）
△：表面に荒れが見られる。（１００Å以上）
×：表面の荒れが激しく、塗膜白化が見られる。
【０１７７】
また、ラインアンドスペースのマスクを介して上記方法で露光を行い、得られたレリーフパターンの形状を光学顕微鏡（オリンパス光学工業（株）製、ＭＨＬ１００）で観察して塗膜が欠損を生じる線幅（密着性）及び解像度を決定した。
【０１７８】
さらに、硬化後の着色層を８０℃の純水に３０分浸漬した後、碁盤目ピール試験法を行い、下記の基準に従って密着性（耐温純水性）を評価した。
【０１７９】
＜碁盤目ピール試験の評価基準＞
○：塗膜の剥がれなし。
△：５０％未満の塗膜に剥がれ、欠損あり。
×：５０％以上の塗膜に剥がれ、欠損あり。
（実施例２）
仕込み量を表３に示す通りに変更した以外は実施例１と同様の操作を行い、シクロヘキシルマレイミド樹脂溶液２を得た。分析値を表３に示す。
実施例１において、シクロヘキシルマレミド樹脂溶液１の代わりに同量のシクロヘキシルマレイミド樹脂溶液２を用いて青レジスト２を調整した。
（実施例３）
仕込み量を表３に示す通りに変更した以外は実施例１と同様の操作を行い、シクロヘキシルマレイミド樹脂溶液３を得た。分析値を表３に示す。
実施例１において、シクロヘキシルマレミド樹脂溶液１の代わりに同量のシクロヘキシルマレイミド樹脂溶液３を用いて青レジスト３を調整した。
（分析及び評価）
以下の評価を行った結果を、第４表に示す。
＜水酸基価測定方法＞
ＪＩＳ−Ｋ００７０に従い、水酸基価を決定し、固形分濃度から、固形分１ｇあたりの水酸基価を決定した。
＜酸価測定方法＞
実施例１と同じ方法で酸価を測定した。
＜現像残渣＞
実施例１と同じ、残渣の拭き取り試験試験を行い、下記基準に従い評価した。◎：残渣なし（着色なし）
○：薄く着色
△：濃く着色
×：濃く着色（残渣黙示確認レベル）
【表３】

【表４】

【０１８０】
【発明の効果】
以上に述べたように本発明によれば、青色顔料又はフタロシアニン系顔料を含み、色特性、微細パターンの形成能、及び、硬化後物性に優れた感光性着色組成物及びその調製に用いられる顔料分散組成物が得られる。この感光性着色組成物はカラーフィルターの画素、特に青色画素を形成するのに非常に適しており、透明性及び耐黄変性に優れ、現像時には残渣を生じずに正確に画素パターンを形成することができ、硬化後には硬度、弾性等の物性に優れている。
【０１８１】
このような感光性着色組成物を用いてカラーフィルターの画素を形成することによって、表示性能に優れたカラーフィルター及び当該カラーフィルターを用いた表示性能に優れた表示装置、例えば液晶表示装置や有機ＥＬ表示装置等が得られる。
【図面の簡単な説明】
【図１】液晶パネルの一例についての模式的断面図である。
【図２】液晶パネルの別の例についての模式的断面図である。
【符号の説明】
１…カラーフィルター
２…電極基板
３…間隙部（Ｌ；液晶化合物）
４…シール材
５…透明基板
６…ブラックマトリックス層
７（７Ｒ、７Ｇ、７Ｂ）…着色層
８…保護膜
９…透明電極膜
１０…配向膜
１１…パール
１２…柱状スペーサー[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a pigment dispersion composition, a photosensitive coloring composition, a color filter, and a liquid crystal display. Specifically, the present invention relates to a pigment dispersion composition and a photosensitive coloring composition containing a maleimide-based alkali-soluble copolymer together with a blue pigment or a phthalocyanine pigment, and furthermore, a blue pigment using such a photosensitive coloring composition. The present invention also relates to a color filter formed with a pattern of pixels containing a phthalocyanine pigment and a liquid crystal display device assembled using the color filter.
[0002]
[Prior art]
The liquid crystal panel has a structure in which a display side substrate and a liquid crystal driving side substrate are opposed to each other, and a liquid crystal compound is sealed between the two to form a thin liquid crystal layer. In a liquid crystal display device incorporating such a liquid crystal panel, the amount of transmitted light or reflected light of the display side substrate is selectively changed by electrically controlling the liquid crystal arrangement in the liquid crystal layer by the liquid crystal driving side substrate of the liquid crystal panel. Display is performed by causing
[0003]
Liquid crystal panels include various driving methods such as a static driving method, a simple matrix method, and an active matrix method.In recent years, as a flat display such as a personal computer or a portable information terminal, an active matrix method or a simple matrix method has been used. The used color liquid crystal display device is rapidly spreading.
[0004]
FIG. 1 shows a configuration example of an active matrix type liquid crystal panel. In the liquid crystal panel 101, a gap 3 of about 1 to 10 μm is provided by opposing a color filter 1 as a display side substrate and a TFT array substrate 2 as a liquid crystal driving side substrate, and the gap 3 is filled with liquid crystal L. The periphery is sealed with a sealing material 4. The color filter 1 includes a black matrix layer 6 formed in a predetermined pattern on a transparent substrate 5 to shield a boundary between pixels, and a plurality of colors (usually red (R) ), Green (G), and blue (B)) are arranged in a predetermined order, or a pixel portion using a hologram, recently a hologram, a protective film 8 and a transparent electrode film 9 are formed on a transparent substrate. It has a laminated structure in this order from the near side.
[0005]
On the other hand, the TFT array substrate 2 has a structure in which TFT elements are arranged on a transparent substrate and a transparent electrode film is provided (not shown). Further, an alignment film 10 is provided on the inner surface side of the color filter 1 and the TFT array substrate 2 facing the color filter. Then, a color image can be obtained by controlling the light transmittance of the liquid crystal layer behind the pixels colored in each color.
[0006]
As a method for maintaining the cell gap, as shown in FIG. 1, a large number of spherical or rod-shaped particulate spacers 11 of a certain size made of glass, alumina, plastic, or the like are scattered as spacers in the gap portion 3 so that the color filter 1 A method of bonding the TFT array substrate 2 and injecting liquid crystal, or as shown in FIG. 2, a cell gap is formed in a region on the inner surface side of the color filter and overlapping with the position where the black matrix layer 6 is formed. There is a method of forming a columnar spacer 12 having a corresponding height.
[0007]
In a liquid crystal display device incorporating a color filter having the above structure, a color image can be obtained by controlling the light transmittance of a liquid crystal layer behind each of the pixels arranged in a predetermined pattern and colored.
[0008]
The pixel portion of the color filter is formed of one or more kinds of pigments selected so as to be able to produce a predetermined color such as RGB by a so-called pigment dispersion method by using a binder resin, a photoinitiator, or the like. A photosensitive coloring composition is prepared by blending with the curable resin composition, applied on a transparent substrate, dried, and selectively exposed to a predetermined area of the obtained coating film to be cured, and an organic solvent or It can be formed by developing with an alkaline solution.
[0009]
In order for a liquid crystal display device to exhibit excellent display performance, the color space expression capability of a pixel is important. Each pixel of RGB is toned so that the color reproduction area determined by the chromaticity coordinates (x, y) in the XYZ color system can be sufficiently widened, and the brightness represented by the stimulus value Y is sufficiently high. It is required to be excellent in transparency and color purity as much as possible. In the process of manufacturing the color filter, there is a problem that the transparency and color characteristics of the pixel portion are impaired due to yellowing of the binder resin contained in the pixel portion. In particular, when a blue pixel takes on a yellow tint, transparency and color characteristics are significantly deteriorated. Therefore, preventing yellowing of a blue pixel is more important than pixels of other colors.
[0010]
The ability to form a fine pattern such as the developability and plate making characteristics of the photosensitive coloring composition forming the pixel portion also greatly affects the display performance of the liquid crystal display device. When producing a fine pattern such as a pixel portion by a pigment dispersion method, regarding the fine pattern forming ability, that there is no residue, that there is no loss of fine lines, that no foreign matter remains, that surface roughness does not occur, Performance such as high resolution, accurate shape after development, and uniform film thickness is required.
[0011]
The residue is a colored matter remaining in a portion that should not remain after development, and is likely to occur when the developability is poor due to a large amount of a pigment or a dispersant.
[0012]
Defects in fine lines are likely to occur when the adhesion is poor due to a small amount of a curing component in the photosensitive coloring composition, a low affinity for a substrate, and the like. Foreign matter is generated due to a lack of a hardening component in the photosensitive coloring composition, a lack of a part of a pixel, a small amount of a developing component, and adhesion of a colored piece generated by peeling development. Surface roughness also occurs when the amount of the curing component in the photosensitive coloring composition is small.
[0013]
In order to improve the resolution, a pattern with many curved parts and corners has appeared in the color filter due to the progress of the liquid crystal drive system unlike the conventional stripe pattern etc., and even such a complicated pattern can be formed accurately There is a need to.
[0014]
There is a problem that the shape after development becomes an inverted trapezoidal shape (an inverted tapered shape) when the photosensitive color composition has poor photosensitivity. If the shape after development is an inverted trapezoid, the upper portion of the pixel is likely to be chipped due to water pressure during development or the like, which causes the above-described foreign matter. Further, in the case of the inverted trapezoidal film, when the heat resistance is low, a portion protruding in a shape of eaves may hang down by heat and form a hole after post-baking. This void not only degrades display quality, but also lowers resolution. In addition, when the liquid crystal panel assembly is ruptured by being heated, the liquid crystal is contaminated.
[0015]
The uniformity of the film thickness is not a major problem at the individual pixel level. However, the size of the substrate has been steadily increasing for the purpose of cost reduction, and has been applied to the meter class. In this case, if the film thickness is different between the center and the end of the glass, the color will vary, resulting in a defective product.
[0016]
In order to accurately form a fine pattern, it is necessary to satisfy all of the above-described elements. However, in general, when the solubility of the photosensitive coloring composition in a developing solution is increased so that no residue remains, fine line defects, foreign matter, surface roughness, and the like are likely to occur, and it is very difficult to prevent the residue. It is.
[0017]
Further, the mechanical or chemical properties of the completed pixel are not only important for the mechanical or temporal durability of the color filter or the liquid crystal display device, but also greatly affect the display performance. As physical properties affecting display performance, for example, performance such as hardness, elasticity, and elution of impurities is required.
[0018]
Spacers such as spherical spacers and columnar spacers are not only formed directly on the substrate of the color filter, but may also be provided above the pixels and the black matrix. In the latter case, if the hardness or elastic modulus of the pixel is inferior, no matter how high the spacer is formed, the base will be deformed and the uniformity of the cell gap will be impaired. For this reason, a pixel is required to have high hardness and elastic modulus.
[0019]
Elution of impurities from the pixels causes liquid crystal contamination. Since the liquid crystal does not perform the switching function only by being mixed with a small amount of conductive impurities, it is important that the conductive molecules do not dissolve into the liquid crystal layer from the color filter. However, pigments and dispersants used for pixels often include conductive molecules as impurities. Therefore, it is required to suppress elution of impurities from the pixel portion.
[0020]
By sufficiently including the curable component in the photosensitive coloring composition, the post-curing physical properties of the pixel can be improved. However, if the pigment is finely dispersed in the photosensitive coloring composition and a large amount of a dispersing agent is added in order to increase the transparency of the pixel, the concentration of the curing component is reduced, and the physical properties of the pixel cannot be improved. . When a large amount of a dispersant is used, a decrease in the pigment concentration is caused, so that the color reproducibility is deteriorated.
[0021]
The binder resin of the photosensitive coloring composition that forms the pixels of the color filter has performances from various viewpoints as described above, for example, original transparency, heat resistance (yellowing resistance), curability, developability, Affinity with a pigment, adhesion to a substrate, and the like are required.
[0022]
JP-A-10-31308 discloses a photosensitive coloring composition using a copolymer of an N-substituted maleimide and a monomer having an acid group as a binder resin. In Examples, a binder resin obtained by reacting 60 parts by mass of cyclohexylmaleimide as an N-substituted maleimide, 20 parts by mass of methacrylic acid as a monomer having an acid group and 20 parts by mass of hydroxyethyl methacrylate in ethyl cellosolve is used. It is disclosed. However, the proportion of cyclohexylmaleimide in all the monomers is too large and tends to remain at the end of the reaction, and the remaining maleimide monomer is decomposed and colored, and the effect cannot be sufficiently exerted. In addition, when forming a thin film layer or a fine pattern such as a color filter, a resin composition is applied on a substrate by a spin coating method or the like, and a uniform film is formed if the boiling point of the solvent is low at this time. Because of the difficulty, a high-boiling-point solvent is used in consideration of the balance of drying properties and the like, but there is room for devising so that the copolymer is sufficiently dissolved in such a solvent.
[0023]
JP-A-10-300922 discloses a radiation-sensitive composition for a color filter containing an alkali-soluble resin containing a copolymer of an N-substituted maleimide monomer and another copolymerizable monomer. Discloses that a copolymer of N-phenylmaleimide / methacrylic acid / styrene / benzyl methacrylate = 30/20/20/30 (% by mass) is used. Japanese Patent Application Laid-Open No. 11-15147 relates to a colored image forming material containing a polymer having a maleimide group in a skeleton. In Examples, N-phenylmaleimide-styrene-methacrylic acid resin (molar ratio: 3: 4) is used. : 2) is disclosed. However, the copolymers using these N-phenylmaleimides have problems in that they have low solubility in solvents and are easily colored by heat.
[0024]
JP-A-10-60214 discloses that 1 to 6% by mass of an α, β-ethylenically unsaturated carboxylic acid, 10 to 80% by mass of an α, β-ethylenically unsaturated carboxylic acid ester and 5 to 30% by mass of an N-substituted maleimide. Regarding the acrylic resin composition for a color filter obtained by blending an acrylic resin obtained by polymerizing a monomer mixture containing 1% by mass of a monomer mixture containing 19% by mass of N-cyclohexylmaleimide, It is disclosed to use a polymer obtained from 2.8% by weight and 4.2% by weight of acrylic acid. However, in order to use such a polymer as a component of a photosensitive coloring composition capable of forming a thin film layer or a fine pattern such as a color filter, solubility in alkaline water is improved, and alkali developability is improved. There was room for devising both heat resistance and hardness. That is, in the production of a color filter or the like, a resin composition is applied on a transparent substrate to form a coating film, pattern exposure is performed through a mask if necessary, and then unexposed portions are undeveloped by development using alkaline water. Although it will go through the step of removing the hardened portion, it will be difficult to obtain a clear pattern if the solubility in alkaline water is not sufficient, and since the heat resistance and hardness will not be sufficient if the solubility in alkaline water is improved. There is room for devising to produce higher quality color filters and the like.
[0025]
[Problems to be solved by the invention]
The present invention has been made in consideration of such circumstances, and a first object of the present invention is to use a maleimide-based alkali-soluble copolymer that can be sufficiently dissolved in alkaline water as a binder, to improve transparency and Excellent color characteristics such as yellowing resistance, and more preferably, a color having excellent display performance in which pixels having excellent pattern forming ability such as the problem of residue and precision of fine patterns and physical properties after curing such as hardness and elasticity are formed. It is to provide a filter.
[0026]
Further, a second object of the present invention is to provide a color filter which is particularly excellent in the color characteristics of blue pixels, pattern forming ability, and physical properties after curing.
[0027]
Further, a third object of the present invention is to use a maleimide-based alkali-soluble copolymer which can be sufficiently dissolved in alkaline water as a binder, to have excellent color characteristics such as transparency and yellowing resistance, and more preferably It is possible to form a colored coating film having excellent problems such as pattern forming ability such as accuracy of a fine pattern and physical properties after curing such as hardness and elasticity, and in particular, a pixel pattern of a color filter, particularly preferably a blue pixel. It is another object of the present invention to provide a photosensitive coloring composition suitable for the above.
[0028]
A fourth object of the present invention is to provide a pigment dispersion composition suitable for preparing the photosensitive coloring composition using a maleimide-based alkali-soluble copolymer having a pigment dispersing function together with a function as an alkali-soluble binder. To provide things.
[0029]
A fifth object of the present invention is to provide a liquid crystal display device having excellent display performance using the above-mentioned color filter, preferably having excellent transparency and color characteristics of a blue pixel.
[0030]
[Means for Solving the Problems]
The pigment dispersion composition according to the present invention is a pigment dispersion containing at least one or more pigments selected from the group consisting of a blue pigment and a phthalocyanine pigment, a maleimide-based alkali-soluble copolymer, a dispersant, and a solvent. A composition, wherein the maleimide-based alkali-soluble copolymer is composed of 5 to 50% by mass of cyclohexylmaleimide monomer units, 8 to 30% by mass of (meth) acrylic acid-based monomer units, and (meth) acrylic acid. When an acid ester monomer unit is essentially 30 to 87% by mass, and a cyclohexylmaleimide monomer unit amount is X mass% and a (meth) acrylic acid monomer unit amount is Y mass%, , The following formula
0.4 × X ≦ Y ≦ 0.5 × X + 10
Is satisfied.
[0031]
The maleimide-based alkali-soluble copolymer specified as described above not only functions as a binder component, but also has excellent pigment dispersing performance, so that by using this instead of a dispersant, excellent dispersibility is obtained. In addition, a pigment dispersion composition containing only a small amount or no dispersant can be prepared. Since the amount of the dispersant used can be reduced, the film physical properties of the photosensitive coloring composition prepared using the same can be improved.
[0032]
When the maleimide-based alkali-soluble copolymer has an acid value of 50 to 200 mgKOH / g and a hydroxyl value of 10 to 150 mgKOH / g, the effect of improving the residue (dirt) after development is large. In particular, a large improvement effect can be obtained in a high pigment concentration range, which is preferable.
In the above pigment dispersion composition, the mixing ratio (dispersant / pigment) of the dispersant to the total amount of the pigment including the pigment selected from the group consisting of the blue pigment and the phthalocyanine pigment is set to 0.5 or less by mass ratio. Is preferred.
[0033]
Next, the photosensitive coloring composition according to the present invention comprises at least one or more pigments selected from the group consisting of a blue pigment and a phthalocyanine pigment, a maleimide-based alkali-soluble copolymer, a radical polymerizable compound, and a photopolymerization initiator. Wherein the maleimide-based alkali-soluble copolymer comprises 5 to 50% by mass of a cyclohexylmaleimide monomer unit and 8 to 30% by mass of a (meth) acrylic acid-based monomer unit. % And a (meth) acrylic acid ester monomer unit of 30 to 87% by mass, and a cyclohexylmaleimide monomer unit amount of X% by mass, and a (meth) acrylic acid monomer When the unit amount is Y mass%, the following formula
0.4 × X ≦ Y ≦ 0.5 × X + 10
Is satisfied.
[0034]
By coating the photosensitive coloring composition of the present invention on a substrate of a color filter and exposing the same, the excellent physical properties and alkali developability of the maleimide-based alkali-soluble copolymer, and the three-dimensional structure formed by the radical polymerizable compound The network structure enables the formation of a cured film with excellent physical properties such as adhesion to the surface of the object to be coated (substrate surface), film strength, heat resistance, pure water resistance, and chemical resistance. When the pattern is exposed and developed, an accurate pattern can be formed, and no residue remains on the removed portion during development.
[0035]
Since the maleimide-based alkali-soluble copolymer has a particularly high affinity for the phthalocyanine-based pigment, in combination with the phthalocyanine-based pigment, extremely excellent transparency, color characteristics, ability to form a fine pattern, and a cured film are provided. Physical properties are obtained.
[0036]
Further, since the maleimide-based alkali-soluble copolymer is excellent in yellowing resistance as described above, it is very effective to combine with a blue pigment having a remarkable adverse effect of color tone due to yellowing. The above-mentioned phthalocyanine-based blue pigment is particularly preferable because of its excellent affinity.
[0037]
In a preferred embodiment, by using the photosensitive coloring composition, when the film thickness after curing is 1.35 μm or less, the x coordinate is 0.05 ≦ x ≦ 0 in a C light source colorimetric XYZ color system two-degree visual field. .30, a cured film capable of displaying a color space in a range where the y coordinate is 0.05 ≦ y ≦ 0.30 and the stimulus value Y is 20 or more can be formed.
[0038]
Further, in a preferred embodiment, by using the photosensitive coloring composition, the cured film thickness is set to 1.3 μm, and the C light source colorimetric XYZ color system before and after heating at 250 ° C. for 1 hour has a 2 degree visual field. When measuring the stimulus value Y at y = 0.1400, it is possible to form a cured film in which the rate of change (Y2 / Y1) of the measured value Y2 after heating to the measured value Y1 before heating is 97% or more.
[0039]
Further, in a preferred embodiment, a cured film having a contrast ratio of 2,000 or more can be formed by using the photosensitive coloring composition.
[0040]
In a preferred embodiment, by using the photosensitive coloring composition, a cured film having a surface roughness (Ra) of 50 ° or less can be formed by a measuring method based on JIS B0601-1994.
[0041]
Further, in a preferred embodiment, by using the above-mentioned photosensitive coloring composition, a cured film having a line width of 25 μm or less which causes a defect when exposed and cured through a line and space mask can be formed.
[0042]
Further, in a preferred embodiment, by using the above-mentioned photosensitive coloring composition, a cured film having a resolution of 24 μm or less when exposed and cured through a line and space mask can be formed.
[0043]
Further, in a preferred embodiment, by using the above-described photosensitive coloring composition, a cured film having a rising angle of a cross section of 50 degrees or less with respect to a surface to be coated can be formed.
[0044]
Next, the first color filter according to the present invention is characterized in that pixels formed by curing the photosensitive coloring composition are provided.
[0045]
Further, the second color filter according to the present invention, in a matrix consisting of a cured product of a binder containing a maleimide-based alkali-soluble copolymer, at least, one or more selected from the group consisting of blue pigments and phthalocyanine-based pigments A color filter provided with pixels formed by dispersing a pigment, wherein the maleimide-based alkali-soluble copolymer includes 5 to 50% by mass of a cyclohexylmaleimide monomer unit and 8 to 8% of a (meth) acrylic acid-based monomer unit. 30% by mass and 30 to 87% by mass of a (meth) acrylic acid ester monomer unit, and X mass% of a cyclohexylmaleimide monomer unit, and a (meth) acrylic acid monomer unit Assuming that the monomer unit amount is Y mass%, the following formula
0.4 × X ≦ Y ≦ 0.5 × X + 10
Is satisfied.
[0046]
The photosensitive coloring composition according to the present invention is particularly useful for forming a pattern of blue pixels or pixels containing a phthalocyanine-based pigment in a color filter, preferably a pattern of blue pixels containing a phthalocyanine-based blue pigment. Suitable, high performance and high quality color filters can be obtained.
[0047]
In a preferred embodiment, a blue pixel of the color filter has a rising angle of the cross section of 50 degrees or less with respect to the surface to be coated, or a cross section in which a ratio of a length of the upper base to a length of the lower base is less than 1. It is formed in a tapered shape having a shape.
[0048]
In a preferred embodiment, the blue pixel of the color filter has a film thickness of 1.35 μm or less and performs colorimetry with a single pixel. ≦ 0.30, a y coordinate of 0.05 ≦ y ≦ 0.30, and a stimulus value Y of 20 or more ≦ Y can be displayed.
[0049]
In a preferred embodiment, the blue pixel of the color filter has a thickness of 1.3 μm and has a single-pixel C light source colorimetric XYZ colorimetric 2 degree visual field before and after heating at 250 ° C. for 1 hour. When measuring the stimulus value Y at = 0.1400, the rate of change (Y2 / Y1) of the measured value Y2 after heating to the measured value Y1 before heating is 97% or more.
[0050]
Further, according to the present invention, a liquid crystal display device in which the color filter according to the present invention and the electrode substrate are opposed to each other and a liquid crystal compound is sealed between the two is obtained.
[0051]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in detail.
[0052]
In the present invention, the maleimide-based alkali-soluble copolymer used as a binder component of the photosensitive coloring composition contains 5 to 50% by mass of a cyclohexylmaleimide monomer unit and 8 to 30% by mass of a (meth) acrylic acid-based monomer unit. And 30 to 87% by mass of (meth) acrylate monomer units. These monomer units may be used alone or in combination of two or more. However, if the mass ratio is out of the above range, the effect exerted by each monomer unit will not be obtained. . Preferred embodiments of the above mass range include a cyclohexylmaleimide monomer unit of 10 to 45 mass%, a (meth) acrylic acid monomer unit of 10 to 25 mass%, and a (meth) acrylic acid ester monomer unit. 30 to 80% by mass, most preferably 12 to 45% by mass of cyclohexylmaleimide monomer unit, 15 to 25% by mass of (meth) acrylic acid monomer unit, and (meth) acrylic acid ester monomer The unit is 35 to 70% by mass. The above mass range is based on 100% by mass of the maleimide-based alkali-soluble copolymer. The composition of the copolymer can be determined, for example, by a method of quantifying unreacted monomers by gas chromatography at the end of polymerization.
[0053]
In the present invention, the monomer unit may or may not have a monomer unit other than the essential monomer unit, as a total mass ratio of the essential monomer unit, for example, 50 mass % Is preferable. It is more preferably at least 70% by mass, and even more preferably at least 90% by mass.
[0054]
The arrangement form of the monomer units in the maleimide-based alkali-soluble copolymer is not particularly limited. For example, any of a random copolymer, an alternating copolymer, a block copolymer and the like may be used.
[0055]
The maleimide-based alkali-soluble copolymer has the following formula when the cyclohexylmaleimide monomer unit amount is X% by mass and the (meth) acrylic acid monomer unit amount is Y% by mass.
0.4 × X ≦ Y ≦ 0.5 × X + 10
It satisfies.
[0056]
When the maleimide-based alkali-soluble copolymer satisfies the conditions defined by the above formula, both alkali water solubility and heat resistance and hardness are compatible, and the solubility in a solvent is excellent, which is suitable for a photosensitive coloring composition. It can be applied. That is, in the photosensitive coloring composition containing the maleimide-based alkali-soluble copolymer, in addition to having excellent hardness and excellent transparency and yellowing resistance during heating, and excellent uniformity in solvent solubility and uniform coating film Is easily formed, and is sufficiently dissolved in alkaline water to be excellent in alkali developability. If Y is less than 0.4 × X, the solubility in alkaline water decreases, and if it exceeds 0.5 × X + 10, the heat resistance and hardness are not sufficient, and such properties are deteriorated. As a result, the developability and the surface condition of the coating film are degraded.
[0057]
In a preferred embodiment of the present invention, 0.45 × X ≦ Y ≦ 0.5 × X + 8 is satisfied. More preferably, 0.5 × X ≦ Y ≦ 0.5 × X + 7.
[0058]
The maleimide-based alkali-soluble copolymer preferably has a monomer unit capable of imparting photocurability (crosslinkability) together with the above essential monomer units. That is, in order to impart photocurability to the photosensitive coloring composition of the present invention, a photocurable component having sensitivity at an appropriately selected irradiation wavelength such as ultraviolet light or ionizing radiation or visible light may be blended. However, when not only such a photocurable component but also the maleimide-based alkali-soluble copolymer itself has photocurability, the irradiation sensitivity of the photosensitive coloring composition can be improved. That is, since the photocurable property of the photosensitive coloring composition becomes excellent, it is possible to shorten the curing time to increase the efficiency and to improve the precision of the pattern shape after development.
[0059]
As the monomer unit capable of imparting photocurability, for example, a monomer unit having a copolymerizable unsaturated bond is preferable, whereby a maleimide-based alkali-soluble copolymer is not copolymerizable with a side chain. Saturated bonds are introduced, and the unsaturated bonds contribute to photocurability. In this case, the mass ratio of the monomer unit having an unsaturated bond in the maleimide-based alkali-soluble copolymer may be, for example, 1 to 60% by mass assuming that the maleimide-based alkali-soluble copolymer is 100% by mass. preferable. More preferably, it is 5 to 40% by mass.
[0060]
The method for producing the maleimide-based alkali-soluble copolymer is not particularly limited. For example, a cyclohexylmaleimide monomer, a (meth) acrylic acid-based monomer, and a (meth) acrylate-based monomer are essential. It can be produced by copolymerizing a monomer component contained as a. As a result, a corresponding monomer unit is formed from each monomer. In this case, the mass ratio of each monomer in the monomer component is appropriately set so that the mass ratio of each monomer unit in the maleimide-based alkali-soluble copolymer is within the above range. In addition, in response to the fact that the maleimide-based alkali-soluble copolymer may have a monomer unit other than the essential monomer unit, one or two monomers other than the above-mentioned essential monomer may be used. A monomer component containing at least one species may be used.
[0061]
As the cyclohexylmaleimide monomer in the above monomer component, it is preferable to use a cyclohexylmaleimide in which the content of cyclohexylaminosuccinic anhydride contained as a by-product in cyclohexylmaleimide is reduced to 1% by mass or less. Examples of the (meth) acrylic acid-based monomer include acrylic acid and methacrylic acid. Further, as the (meth) acrylate monomer, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylic acid 2-ethylhexyl and the like. In addition, "(meth) acrylic acid" means that either acrylic acid or methacrylic acid may be used.
[0062]
The monomer other than the essential monomer is not particularly limited, and includes, for example, aromatic-substituted maleimides such as phenylmaleimide, benzylmaleimide, naphthylmaleimide, and o-chlorophenylmaleimide; methylmaleimide, ethylmaleimide, propylmaleimide, and isopropyl Alkyl-substituted maleimides such as maleimide; aromatic vinyl monomers such as styrene, α-methylstyrene, p-methylstyrene and p-chlorostyrene; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; And unsaturated dicarboxylic anhydrides.
[0063]
In the above production method, when photocuring is imparted to the maleimide-based alkali-soluble copolymer itself, among others, the maleimide-based alkali-soluble copolymer is a monomer unit having a copolymerizable unsaturated bond as a component. In the case of preparing a copolymer having a carboxyl group by performing copolymerization using an unsaturated carboxylic acid, a compound having a functional group capable of bonding to a carboxyl group and a copolymerizable unsaturated bond are prepared. It is produced by a method of reacting, or after preparing a copolymer having a cyano group by performing copolymerization using a compound having a cyano group and a copolymerizable unsaturated bond, and then reacting an unsaturated carboxylic acid. Is preferred.
[0064]
In the above case, it is preferable to use, for example, (meth) acrylic acid as the unsaturated carboxylic acid. Compounds having a functional group capable of binding to a carboxyl group and a copolymerizable unsaturated bond include, for example, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, α-ethyl glycidyl acrylate, crotonyl glycidyl ether, itaconic acid Compounds having an oxirane ring such as monoalkyl monoglycidyl ester and a copolymerizable unsaturated bond; unsaturated alcohols such as allyl alcohol, 2-bran-1-ol-free furyl alcohol, oleyl alcohol and cinnamyl alcohol; 2-hydroxyethyl (meth) acrylate; N-methylolacrylamide; 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, and the like can be used. It is preferable to use a compound having an unsaturated bond copolymerizable. More preferably, glycidyl (meth) acrylate is used. Further, as the compound having a cyano group and a copolymerizable unsaturated bond, for example, the above-mentioned vinyl cyanide compound is preferably used.
[0065]
As a preferable mode for producing the maleimide-based alkali-soluble copolymer, for example, a method of polymerizing a monomer component using a radical polymerization initiator and, if necessary, a molecular weight regulator is suitable. In this case, the polymerization can be performed by bulk polymerization, solution polymerization, suspension polymerization, dispersion polymerization, emulsion polymerization, or a mode in which these are appropriately combined. Among these, polymerization is preferably performed by solution polymerization. More preferably, the polymerization is performed by batch solution polymerization.
[0066]
When producing the maleimide-based alkali-soluble copolymer, the radical polymerization initiator, the polymerization conditions and the like are not particularly limited, and may be appropriately set according to the polymerization method, the type of the monomer to be copolymerized, the usage ratio, and the like. Good. For example, the solvent used when performing polymerization by solution polymerization is a liquid that does not hinder solution polymerization and that can dissolve both the monomer component as a raw material and the generated maleimide-based alkali-soluble copolymer. No particular limitation, for example, aliphatic alcohols having 1 to 3 carbon atoms such as methanol, ethanol and glycol; cellosolves such as cellosolve and butyl cellosolve; carbitols such as carbitol and butyl carbitol; cellosolve acetate; Esters such as carbitol acetate and propylene glycol monomethyl ether acetate; ethers such as diethylene glycol dimethyl ether; cyclic ethers such as tetrahydrofuran; ketones such as cyclohexanone, methyl ethyl ketone and methyl isobutyl ketone; dimethyl sulfoxide and dimethyl It can be used organic solvents having a polarity such as formamide. Further, as a solvent used when performing polymerization by non-aqueous dispersion polymerization, a liquid in which a monomer component as a raw material can be dissolved and a generated maleimide-based alkali-soluble copolymer is insoluble is used. For example, liquid hydrocarbons such as benzene, toluene, hexane, and cyclohexane, and other nonpolar organic solvents can be used. These may be used alone or in combination of two or more. The amount of the solvent used in the solution polymerization or the non-aqueous dispersion polymerization is preferably, for example, 20 to 80% by mass of the total amount of all the monomers and the solvent. If the amount is less than 20% by mass, sufficient stirring may not be performed due to thickening at the end of the polymerization. If the amount is more than 80% by mass, the molecular weight of the maleimide-based alkali-soluble copolymer produced is too small. There is fear. More preferably, it is 30 to 70% by mass.
[0067]
As the radical polymerization initiator, one or more known radical polymerization initiators such as a peroxide and an azo initiator can be used. The amount of the polymerization initiator used is, for example, preferably from 0.001 to 5.0% by mass, more preferably from 0.5 to 3.0% by mass, based on 100% by mass of all the monomer components. % By mass. Further, as the molecular weight regulator, for example, one or more kinds of α-methylstyrene dimer and mercaptan-based chain transfer agent can be used. Among them, long-chain alkyl mercaptans having 8 or more carbon atoms are preferred in terms of odor and little coloring.
[0068]
The polymerization temperature in the copolymerization may be appropriately set depending on the used radical polymerization initiator and the like, and is not particularly limited, but is preferably, for example, 50 to 200 ° C. If the temperature is lower than 50 ° C., it is necessary to use an initiator having a low decomposition temperature, and there is a possibility that it may be disadvantageous for industrial production, for example, a facility for cooling and storing the initiator is required. If it exceeds 200 ° C., the monomer component may start to thermally polymerize before the decomposition temperature of the initiator is reached. Preferably, it is 80 to 150 ° C.
[0069]
When the maleimide-based alkali-soluble copolymer is produced by the above production method, the maleimide-based alkali-soluble copolymer may be separated and used by removing volatile components from the reaction solution after completion of the polymerization reaction. The solution may be used in the form of a solution without separating the components. The method of separating the maleimide-based alkali-soluble copolymer is not particularly limited, and for example, a method of heating the reaction solution under vacuum, a method of putting the reaction solution in a poor solvent to precipitate it by filtration, and the like are applied. be able to.
[0070]
The amount of unreacted cyclohexylmaleimide monomer in the maleimide-based alkali-soluble copolymer, that is, the amount of remaining cyclohexylmaleimide monomer, is 3% by mass or less based on 100% by mass of the maleimide-based alkali-soluble copolymer. Is preferred. If it exceeds 3% by mass, the thermal stability may be reduced or coloring may be caused. In addition, since the cyclohexylmaleimide monomer has high toxicity, it is not preferable that the residual amount is large also in this respect. It is more preferably at most 1% by mass, most preferably at most 0.5% by mass.
[0071]
The remaining amount of the monomer components other than the cyclohexylmaleimide monomer in the maleimide-based alkali-soluble copolymer is preferably 5% by mass or less based on 100% by mass of the maleimide-based alkali-soluble copolymer. If the amount of the residual monomer exceeds 5% by mass, the thermal stability may be reduced or coloring may be caused. It is more preferably at most 3% by mass, most preferably at most 1% by mass.
[0072]
The molecular weight of the maleimide-based alkali-soluble copolymer is preferably, for example, a mass average molecular weight of 5,000 to 50,000. If it is less than 5,000, heat resistance and thermal stability may decrease. If it exceeds 50,000, the solubility in alkaline water may decrease. More preferably, it is 5,000 to 35,000, and still more preferably, 7000 to 32,000. Further, the ratio (Mw / Mn) of the mass average molecular weight to the number average molecular weight measured by GPC (gel permeation chromatography) is preferably 4.0 or less. If it exceeds 4.0, the thermal stability and the solubility in alkaline water may be reduced. More preferably, it is 3.0 or less, and still more preferably, it is 2.5 or less.
[0073]
The solubility of the maleimide-based alkali-soluble copolymer in alkaline water is preferably, for example, soluble in a 1% KOH aqueous solution. In this case, it is preferable that the copolymer be completely dissolved when 20% by mass of the copolymer is added to a 1% KOH aqueous solution and stirred for 3 hours. In a photosensitive coloring composition containing such a maleimide-based alkali-soluble copolymer, an uncured portion can be dissolved in alkaline water to form a clear pattern. Further, it is preferable that the insoluble content of the alkaline aqueous solution with respect to the 0.5% KOH aqueous solution is 10% by mass or less. More preferably, it is 5% by mass or less, and further preferably, it is 3% by mass or less. The insoluble content of the maleimide-based alkali-soluble copolymer in an aqueous alkali solution can be determined, for example, by using a 50-μm-thick film of the maleimide-based alkali-soluble copolymer in a solubility test in 200 ml of a 0.5% KOH aqueous solution at 50 ° C. It can be evaluated by determining the amount of water-insoluble components.
[0074]
When the maleimide-based alkali-soluble copolymer has a hydroxyl group, that is, in order to impart photocurability to the maleimide-based alkali-soluble copolymer itself, after copolymerization using an unsaturated carboxylic acid, the oxirane ring and In the case of a polymer obtained by reacting a compound having an unsaturated bond, not only the acid value but also the hydroxyl value has a preferable range. This is because not only the acid value of the maleimide-based alkali-soluble copolymer but also the hydroxyl value affects the residue (soil).
In the present invention, particularly in a region where the pigment is highly concentrated (for example, when the mass of the solid content in the photosensitive coloring composition is 100%, the mass of the pigment is 15% or more, preferably 20% or more), Residues are likely to remain, but by keeping the acid value and hydroxyl value of the maleimide-based alkali-soluble copolymer within the above ranges, residue residues can be extremely reduced.
Specific examples of the maleimide-based alkali-soluble copolymer having an acid value and a hydroxyl value within the above ranges include a cyclohexylmaleimide monomer, a (meth) acrylate-based monomer, and a (meth) acrylic acid monomer. After copolymerization, a copolymer obtained by reacting glycidyl (meth) acrylate as an unsaturated carboxylic acid for imparting photocurability, and a cyclohexylmaleimide monomer unit (A) constituting a main chain skeleton, Glycidyl (meth) acrylate is added to (meth) acrylic acid ester monomer unit (B), (meth) acrylic acid monomer unit (C), and (meth) acrylic acid monomer unit. The copolymerization ratio (A / B / C / D /) of the unit (D) is (5-10 / 15-85 / 5-5-30 / 5-60), preferably (5-25 / 20-80 / 5-15 10-50), most preferably include those in the range of (5-25 / 30-70 / 5-15 / 10-30).
[0075]
Since the binder component composed of such a maleimide-based alkali-soluble copolymer also has excellent pigment dispersing performance, a pigment dispersion composition and a photosensitive coloring composition are prepared by using the binder instead of the dispersant. be able to.
[0076]
A pigment dispersion composition can be prepared by blending the maleimide-based alkali-soluble copolymer with a pigment in a solvent, and replenishing a dispersant as necessary.
[0077]
The pigment that can be used in the pigment dispersion composition of the present invention is not particularly limited, and various organic or inorganic pigments can be used alone or in combination of two or more.
[0078]
As the organic colorant, for example, a dye, an organic pigment, a natural pigment, or the like can be used. Specific examples of the organic pigment include compounds classified as Pigment in a color index (CI; published by The Society of Dyers and Colorists), that is, the following color index (CI. ) Numbered ones can be mentioned.
[0079]
C. I. Pigment Yellow 1, C.I. I. Pigment Yellow 3, C.I. I. Pigment Yellow 12, C.I. I. Pigment yellow 138, C.I. I. Pigment Yellow 150, C.I. I. Pigment yellow 180, C.I. I. Yellow pigments such as CI Pigment Yellow 185; I. Pigment Red 1, C.I. I. Pigment Red 2, C.I. I. Pigment Red 3, C.I. I. Pigment red 254, C.I. I. Red-based pigments such as CI Pigment Red 177; I. Pigment Blue 15, C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Blue 15: 4, C.I. I. Blue-based pigments such as CI Pigment Blue 15: 6; C.I. I. Violet-based pigments such as CI Pigment Violet 23:19; and green-based pigments such as Pigment Green 36.
[0080]
In addition, as the inorganic colorant, for example, an inorganic pigment, an extender pigment, or the like can be used. Specific examples include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, and red iron ( Red iron oxide (III)), cadmium red, ultramarine blue, navy blue, chromium oxide green, cobalt green, amber, titanium black, synthetic iron black, carbon black and the like.
[0081]
The maleimide-based alkali-soluble copolymer used in the present invention has excellent affinity with phthalocyanine-based pigments used as blue or green pigments. Examples of the phthalocyanine-based pigment include a phthalocyanine-based blue pigment such as copper phthalocyanine.
[0082]
Further, the maleimide-based alkali-soluble copolymer used in the present invention is excellent in yellowing resistance during heating, so that a blue coating film whose color characteristics are significantly deteriorated due to yellowing, particularly, a blue pixel of a color filter is formed. Very suitable as a binder component. Therefore, the maleimide-based alkali-soluble copolymer is preferably used for preparing a pigment dispersion composition and a photosensitive coloring composition containing a blue pigment, and when combined with a phthalocyanine-based blue pigment among the blue pigments. It is particularly preferable because it has excellent affinity.
[0083]
By mixing the maleimide-based alkali-soluble copolymer in an amount of usually 70 to 110 parts by mass, preferably 80 to 100 parts by mass with respect to 100 parts by mass of the pigment, excellent pigment dispersibility can be obtained.
[0084]
The maleimide-based alkali-soluble copolymer may be used in combination with one or more dispersants (however, the maleimide-based alkali-soluble copolymer as a binder component is not considered as a dispersant), Even when used in combination, the ratio of the pigment to the dispersant (dispersant / pigment) is preferably 0.5 or less, more preferably 0.3 or less. The smaller the amount of the dispersant, the more preferable. However, when used, the ratio of the pigment to the dispersant is generally 0.05 or more in order to make the dispersing action of the dispersant effective.
[0085]
The dispersant that can be used is not particularly limited. For example, cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, silicone surfactants, fluorine surfactants, and the like can be used. It is preferable to use a dispersant). Examples of the polymer surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, and the like. Polyoxyethylene alkyl phenyl ethers; polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid-modified polyesters; and tertiary amine-modified polyurethanes.
[0086]
As a solvent (dispersion solvent) for preparing the pigment dispersion composition, an organic solvent is preferably used. As the organic solvent, an organic solvent used as a diluting solvent for preparing a photosensitive coloring composition described later can be used.
[0087]
The dispersing solvent is used in a proportion of usually 100 to 1000 parts by mass, preferably 200 to 900 parts by mass, based on 100 parts by mass of the pigment.
[0088]
In the present invention, the pigment dispersion composition can be prepared by replacing a part or all of the dispersant with the above-mentioned maleimide-based alkali-soluble copolymer in a conventionally known procedure for preparing a pigment dispersion composition. That is, the above-mentioned pigment, the above-mentioned maleimide-based alkali-soluble copolymer, and, if necessary, other components are mixed in a solvent in an arbitrary order, and a kneader, a roll mill, an attritor, a super mill, a dissolver, a homomixer, and a sand mill are mixed. The pigment dispersion composition can be prepared by dispersing using a known disperser such as described above.
[0089]
Specifically, a method of adding and dispersing a mixture of an organic pigment and a binder to a solvent, a method of adding and dispersing a pigment and a binder to a solvent respectively; a liquid in which only a pigment is dispersed in a solvent, and a method of dispersing only a binder in a solvent Examples thereof include a method of mixing a dispersed liquid and a method of adding a binder to a liquid in which only a pigment is dispersed in a solvent.
[0090]
Thus, a pigment dispersion composition having excellent dispersibility of pigment particles can be obtained. This pigment dispersion composition is used as a preliminary preparation for preparing a coating liquid having excellent pigment dispersibility. If a pigment or a pigment dispersant is directly added to and mixed with a diluting solvent together with a binder component, sufficient dispersibility may not be obtained. On the other hand, the additional amount of the binder and other components are mixed with the pigment dispersion composition according to the present invention, or the additional amount of the pigment dispersion composition according to the present invention, the additional amount of the binder, and the other components are solid components. By adding to a solvent (diluting solvent) for adjusting the concentration, a coating liquid having excellent pigment dispersibility can be easily prepared.
[0091]
In the present invention, preparing a photosensitive coloring composition containing one or more pigments, the above maleimide-based alkali-soluble copolymer, a radical polymerizable compound and a photopolymerization initiator as essential binder components. Can be. The maleimide-based alkali-soluble copolymer, radical polymerizable compound and photopolymerization initiator may be used alone or in combination of two or more.
[0092]
By coating the photosensitive coloring composition of the present invention on a substrate of a color filter and exposing the same, the excellent physical properties and alkali developability of the maleimide-based alkali-soluble copolymer, and the three-dimensional structure formed by the radical polymerizable compound The network structure enables the formation of a cured film with excellent physical properties such as adhesion to the surface of the object to be coated (substrate surface), film strength, heat resistance, pure water resistance, and chemical resistance. When the pattern is exposed and developed, an accurate pattern can be formed, and no residue remains on the removed portion during development.
[0093]
The blending amount of the maleimide-based alkali-soluble copolymer is preferably, for example, 5 to 80% by mass based on 100% by mass of the photosensitive coloring composition. If the amount is less than 5% by mass, the viscosity becomes too low, and the stability of the coating film after coating and drying may not be sufficient. If the amount exceeds 80% by mass, the viscosity becomes too high and the fluidity decreases, Inconveniences such as poor applicability may occur. More preferably, it is 10 to 50% by mass.
[0094]
As the pigment to be blended in the photosensitive coloring composition, the same pigment that can be blended in the above-described pigment dispersion can be used. Since the maleimide-based alkali-soluble copolymer used in the present invention has a high affinity for the pigment, the pigment can be finely dispersed without reducing or using any dispersant in the photosensitive coloring composition. Since the pigment can be finely dispersed, the transparency of the colored cured film can be improved. Further, when the amount of the dispersant is reduced, the mixing ratio of the pigment and / or the binder component in the photosensitive coloring composition is relatively increased. Therefore, the color characteristics of the colored coating film can be improved by increasing the blending ratio of the pigment, and the fine pattern forming ability and the cured film can be improved by increasing the blending ratio of the binder component that contributes to the curability and developability. Physical properties can be improved.
[0095]
Since the maleimide-based alkali-soluble copolymer has a particularly high affinity for the phthalocyanine-based pigment, in combination with the phthalocyanine-based pigment, extremely excellent transparency, color characteristics, ability to form a fine pattern, and a cured film are provided. Physical properties are obtained.
[0096]
Further, since the maleimide-based alkali-soluble copolymer is excellent in yellowing resistance as described above, it is very effective to combine with a blue pigment having a remarkable adverse effect of color tone due to yellowing. The above-mentioned phthalocyanine-based blue pigment is particularly preferable because of its excellent affinity.
[0097]
The amount of the pigment is preferably, for example, 40 to 75% by mass relative to 100% by mass of the photosensitive coloring composition. If the amount is less than 40% by mass, the coloring power is not sufficient, so that it may be difficult to display a clear image. If the amount is more than 75% by mass, there is a possibility that the light transmittance of the colored film becomes insufficient and the like. is there. More preferably, it is 45 to 70% by mass.
[0098]
In order to disperse the pigment uniformly and stably, the photosensitive coloring composition may contain one or more dispersants. As such a dispersant, the same dispersants that can be blended in the above-described pigment dispersion can be used. In this case, the ratio of the pigment to the dispersant (dispersant / pigment) is preferably 0.5 or less, more preferably 0.3 or less, and generally 0.05 or more. Same as in the case.
[0099]
The radical polymerizable compound is not particularly limited as long as it is a compound capable of forming a cross-linking by light irradiation and curing the photosensitive coloring composition, and includes, for example, three ethylenically unsaturated bonds in one molecule. It is preferable to use a photopolymerizable compound having the above (a trifunctional or higher functional photopolymerizable compound), and in addition, a bifunctional photopolymerizable compound or the like can be used. As the trifunctional or higher functional photopolymerizable compound, for example, poly (meth) acrylates of trihydric or higher polyhydric alcohol, or dicarboxylic acid modified products thereof can be used, and specifically, trimethylol Propane (meth) acrylate, pentaerythritol tri (meth) acrylate, succinic acid-modified pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate And the like. Among these, it is preferable to use dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate. In addition, “(meth) acrylate” means that either acrylate or methacrylate may be used.
[0100]
The compounding amount of the radical polymerizable compound is preferably, for example, 5 to 70% by mass relative to 100% by mass of the photosensitive coloring composition. If the amount is less than 5% by mass, unexposed portions may not be easily removed during development. If the amount exceeds 70% by mass, the viscosity becomes too low, and the stability of the coating film after coating and drying becomes insufficient. Or inconvenience such as impairing the suitability for development. More preferably, it is 10 to 40% by mass.
[0101]
The photosensitive coloring composition of the present invention may contain one or more monofunctional photopolymerizable monomers as a reaction diluent, if necessary, together with the radical polymerizable compound. Specific examples of such a compound include (meth) acrylate, ethyl (meth) acrylate, and propyl (meth) acrylate.
[0102]
The photopolymerization initiator is not particularly limited as long as it is a compound capable of generating an active species such as a radical, a cation, or an anion by radiation having a wavelength of 365 nm or less and initiating a polymerization reaction of the above-described radically polymerizable compound. Although it is not a thing, it is preferable that it has high solubility in the solvent contained in the photosensitive coloring composition. As such a photoinitiator, a compound that generates free radicals by the energy of ultraviolet rays can be used. For example, benzophenone derivatives such as benzoin and benzophenone or derivatives thereof such as esters; xanthone and thioxanthone derivatives; chlorosulfonyl Chloromethyl polynuclear aromatic compounds, chloromethyl heterocyclic compounds, halogen-containing compounds such as chloromethylbenzophenones; triazines; imidazolines; fluorenones; haloalkanes; redox couples of a photoreducing dye and a reducing agent; Organic sulfur compounds; peroxides and the like. Among these, it is preferable to use triazines, imidazolines and the like.
[0103]
The amount of the photopolymerization initiator is preferably, for example, 0.05 to 20% by mass based on 100% by mass of the photosensitive coloring composition. If the amount is less than 0.05% by mass, the curability of the coating film formed from the photosensitive coloring composition may be insufficient, and if the amount is more than 20% by mass, the unexposed portion may not be easily removed during development. In addition, inconveniences such as yellowing of the coating film after post-baking may occur. More preferably, it is 2 to 15% by mass.
[0104]
The photosensitive coloring composition of the present invention may contain, if necessary, one or more components other than the above-mentioned essential components. For example, a sensitizer; It is preferable to contain a curable resin or the like.
[0105]
When the sensitizer is contained, the sensitivity of the photosensitive coloring composition can be improved. As such a sensitizer, a styryl-based compound or a coumarin-based compound is preferably used. Specifically, as the styryl-based compound, 2- (p-dimethylaminostyryl) quinoline, 2- (p-diethylaminostyryl) is used. ) Quinoline, 4- (p-dimethylaminostyryl) quinoline and the like, and as coumarin compounds, 7-diethylamino-4-methylcoumarin, 7-ethylamino-4-trifluoromethylcoumarin, 4,6-diethylamino- One or more of 7-ethylaminocoumarin and the like can be mentioned.
[0106]
The compounding amount of the sensitizer is preferably, for example, 0.01 to 50% by mass relative to 100% by mass of the photosensitive coloring composition.
[0107]
When containing a thermosetting resin that is cured by reacting with an acid by the above-described heating, a photosensitive colored composition is applied to the surface of a substrate, and a cured pattern is formed by exposing and developing into a desired pattern. After that, when the cured pattern is heated to a predetermined temperature, the thermosetting resin reacts with the carboxyl groups remaining in the cured pattern and consumes the carboxyl groups, thereby improving alkali resistance and improving the thermosetting resin. , The physical properties of the cured pattern are improved. As a result, the heat resistance, adhesion, hot pure water resistance, and chemical resistance (particularly, alkali resistance) of the film or pattern formed by the photosensitive coloring composition of the present invention are improved.
[0108]
As the acid-reactive thermosetting resin, for example, an epoxy resin, particularly an epoxy resin having two or more epoxy groups in one molecule is preferable, and specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin Phenol novolak type epoxy resin, cresol novolak type epoxy resin or the like.
[0109]
The blending amount of the thermosetting resin is preferably, for example, 1 to 20% by mass relative to 100% by mass of the photosensitive coloring composition. If the amount is less than 1% by mass, the coating film formed by curing the photosensitive coloring composition may not be able to impart sufficient alkali resistance. If the amount exceeds 20% by mass, the content of the photosensitive coloring composition may be reduced. There is a possibility that inconveniences such as deterioration of storage stability and developability may occur. More preferably, it is 3 to 15% by mass.
[0110]
The photosensitive coloring composition of the present invention may contain various additives other than those described above, if necessary. Such additives include, for example, silane coupling agents such as vinyl silane, acrylic silane, epoxy silane, and the like. Can be improved.
[0111]
The method for producing the photosensitive coloring composition of the present invention is not particularly limited, and includes, for example, a pigment, a maleimide-based alkali-soluble copolymer, a radically polymerizable compound and a photopolymerization initiator, and, if necessary, It can be produced by mixing or adding components other than the components to a solvent, stirring and uniformly dissolving and dispersing the components. Further, it is also possible to produce a photosensitive coloring composition using the above-described pigment dispersant. In such a manufacturing method, the mixing order and the like are not particularly limited. Examples of an apparatus used for stirring include a paint shaker, a bead mill, a sand grind mill, a ball mill, an attritor mill, a two-roll mill, and a three-roll mill.
[0112]
The form of use of the photosensitive coloring composition of the present invention is not particularly limited, but it is usually diluted with a solvent in consideration of paintability and applicability. As such a solvent, it is preferable to use a solvent which dissolves a maleimide-based alkali-soluble copolymer, a radical polymerizable compound, a photopolymerization initiator and the like, has a high boiling point, and has good spin coating properties. For example, alcohol solvents such as methyl alcohol, ethyl alcohol, N-propyl alcohol and i-propyl alcohol; cellosolve solvents such as methoxy alcohol and ethoxy alcohol; carbitol solvents such as methoxyethoxy ethanol and ethoxyethoxy ethanol; ethyl acetate Ester solvents such as butyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, and ethyl lactate; ketone solvents such as acetone, methyl isobutyl ketone and cyclohexanone; cellosolve acetate such as methoxyethyl acetate, ethoxyethyl acetate, and ethyl cellosolve acetate Carbitol acetate solvents such as methoxyethoxyethyl acetate and ethoxyethoxyethyl acetate; diethyl ether Ether solvents such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and tetrahydrofuran; aprotic amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; lactone solvents such as γ-butyrolactone; Unsaturated solvents such as benzene, toluene, xylene and naphthalene; organic solvents such as saturated hydrocarbon solvents such as N-heptane, N-hexane and N-octane; and one or more kinds thereof. Can be used. Among them, it is preferable to use 3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether and the like.
[0113]
The amount of the solvent to be used is appropriately adjusted depending on the dissolving state of the components and the applicability, but it is usually preferable that the solid content be 5 to 50% by mass.
[0114]
An example of a method for forming a cured film (including those formed in a predetermined pattern) using the photosensitive coloring composition of the present invention will be described below. First, the photosensitive coloring composition of the present invention is applied to the surface of an object to be coated such as a substrate, and the formed coating film is irradiated with ionizing radiation such as an ultraviolet ray or an electron beam to be exposed and cured. When the coating film is irradiated with ionizing radiation, an active species is first generated from the photopolymerization initiator by the action of the ionizing radiation in the coating film, and a cross-linking reaction of the radical polymerizable compound is started by the action of the active species. The film cures.
[0115]
At this time, when it is desired to form the coating film in a predetermined pattern such as a pixel of a color filter, exposure is performed through a photomask or the like to form a predetermined pattern and development is performed. Since the coating film has a carboxyl group in the maleimide-based alkali-soluble copolymer, unexposed portions where no cross-linking of the radically polymerizable compound is formed can be removed by alkali development, and a predetermined pattern can be obtained. A cured film can be formed.
[0116]
After the above-mentioned coating film is exposed and cured, and developed if necessary, the coating film is further heated and cured to obtain a cured film. When the ethylenically unsaturated bond derived from the radical polymerizable compound remains in the exposed and cured coating film, the crosslinking reaction can be further advanced by a heating step. Furthermore, when a thermosetting resin such as a bifunctional epoxy resin is contained in the coating film, it reacts with a carboxyl group of the maleimide-based alkali-soluble copolymer remaining in the coating film. Consumes carboxyl groups and causes cross-linking. As a result, the heat resistance, adhesion, warm pure water resistance and chemical resistance (particularly alkali resistance) of the cured film are improved.
[0117]
The colored cured film formed by using the photosensitive colored composition of the present invention has color characteristics such as heat resistance related to transparency and color tone, fine pattern forming ability such as developability and plate making characteristics, and hardness and elasticity. Excellent physical properties.
[0118]
Regarding the color characteristics, particularly when a blue cured film is formed, bright pixels having high transparency can be formed. Specifically, the photosensitive coloring composition is applied on a glass substrate by spin coating, dried at 80 ° C. for 3 minutes, and dried at 100 mJ / cm. ² After the exposure with the irradiation amount of, the substrate is heated at 230 ° C. for 30 minutes to form a blue cured film. When the color of the cured blue film obtained in this manner is set to 1.35 μm or less and colorimetry is performed with a single pixel, the x coordinate in the C light source colorimetric XYZ color system 2 degree visual field is 0.05 ≦. A color space in the range of x ≦ 0.30, y coordinate of 0.05 ≦ y ≦ 0.30, and stimulus value Y of 20 or more, preferably 21.0 or more can be displayed.
[0119]
The color filter is manufactured through a heating step involving a high temperature such as post-baking or forming a polyimide alignment film.In such a heating step, when the material for forming the colored layer turns yellow, it causes wavelength absorption around 400 nm, so that the color filter is colored. The color characteristics of the layer are deteriorated, and the color tone and luminance of blue pixels are most remarkably reduced among the colors. On the other hand, the photosensitive coloring composition according to the present invention uses a maleimide-based alkali-soluble copolymer having high heat resistance, so that yellowing hardly occurs and a blue cured film having high heat resistance with respect to color tone is formed. be able to.
[0120]
Specifically, the photosensitive coloring composition of the present invention is applied on a glass substrate by spin coating, dried at 80 ° C. for 3 minutes, and dried at 100 mJ / cm. ² After exposure at an irradiation amount of, a blue cured film having a thickness of about 1.3 μm can be formed by heating at 230 ° C. for 30 minutes. Assuming a heating step for producing a color filter on the blue cured film, a heat resistance test was conducted by heating at 250 ° C. for 1 hour, and before and after the heat resistance test, a C light source colorimetric XYZ color system, a 2-degree visual field, y When the stimulus value Y at 0.1400 is measured, the rate of change (Y2 / Y1) of the measured value Y2 after the test to the measured value Y1 before the test can be maintained at 97% or more.
[0121]
Regarding the ability to form fine patterns such as plate making characteristics and developability, the photosensitive coloring composition of the present invention is excellent in various aspects such as development form, development time, residue, surface roughness, adhesion, resolution, cross-sectional shape, and contrast. I have.
[0122]
In the development process of the negative resist, unexposed portions of the resist layer that have not been cured are dissolved by the alkali developing solution and are separated from the substrate, but in the development form, the separated portions are mainly large. There are a peeling type that separates as a lump and a dissolving type that gradually dissolves and diffuses the dye as it dissolves in water. The former peeling type is an unfavorable developing mode because solid masses are left as foreign matter in the system and easily contaminate pixels of other colors. On the other hand, the photosensitive coloring composition of the present invention is the latter dissolvable type and takes a preferable development form.
[0123]
Since the photosensitive coloring composition of the present invention has a shorter development time as compared with the case of using an acrylic resin-based binder, the throughput is shortened by that amount, and the amount of the developer used and the development line can be reduced. is there.
[0124]
In the development process of the negative resist, the uncured unexposed portion of the resist layer is dissolved by the alkali developing solution and is separated from the substrate, but the resist is not sufficiently separated and remains on the substrate. There are cases. If a resist of another color is applied and developed at a position where such a development residue remains to form a pixel, adverse effects such as a change in color characteristics and a decrease in smoothness are exerted. On the other hand, the photosensitive coloring composition of the present invention does not leave a residue in a dissolved portion at the time of development, so that the quality of pixels other than blue is also improved.
[0125]
In general, when the amount of the residue is reduced, the solubility of the resist becomes too strong, and the accuracy of the pattern is impaired by causing problems such as surface roughness, reduced adhesion and reduced resolution. The colored cured film produced using the product is accurately formed in a predetermined pattern without leaving a residue in a portion to be removed by development.
[0126]
Specifically, the obtained colored cured film can have a surface roughness (Ra) of 50 ° or less, preferably 30 ° or less in a measuring method based on JIS B0601-1994.
[0127]
The colored cured film may have a line width at which a defect occurs when a coating film of the photosensitive colored composition is exposed and cured through a line and space mask to 25 μm or less, preferably 20 μm or less. Excellent in nature.
[0128]
The colored cured film may have a resolution of 24 μm or less, preferably 20 μm or less, when a coating film of the photosensitive colored composition is exposed and cured through a line and space mask.
[0129]
The photosensitive coloring composition of the present invention is also preferable in that the cross-sectional shape of the cured film can be formed into a tapered shape. When a colored resist is applied on a substrate and the coating film is developed, the cross-sectional shape of the obtained colored layer is such that the length of the lower bottom (the surface in contact with the substrate) is the length of the upper bottom (the surface facing the contact surface with the substrate). When the taper shape (trapezoidal) is larger than the length (ie, (upper surface / lower surface) <1), when the cross-sectional shape is rectangular (ie, (upper surface / lower surface) = 1), May have an inverted tapered shape (inverted trapezoidal shape) in which the length is smaller than the length of the upper base (that is, (upper surface / lower surface)> 1).
[0130]
When the cross section of the coloring layer has a reverse tapered shape, when the ITO electrode layer is deposited on the coloring layer, the ITO does not sufficiently turn to the side surface of the coloring layer, and a portion where the ITO layer cannot be formed is located near the lower bottom. The electrode layer is left, and conduction is not obtained, or a large resistance value is partially generated, which causes a problem in the electrode layer. Such a problem occurs when a pixel pattern of a color filter is formed using a colored resist. In addition, the colored layer having an inverted taper shape is rounded off and falls off during various processes, and adheres to other portions of the color filter, thereby causing background contamination. Therefore, it is desirable that the pattern of the colored layer formed by applying, developing, and post-baking a resist on a substrate has a tapered (trapezoidal) cross-sectional shape. In response to such a demand, a tapered (substantially trapezoidal, (upper surface / lower surface) <1) blue layer pattern is formed by using the photosensitive coloring composition of the present invention. Alternatively, it is possible to prevent soiling.
[0131]
Specifically, the rising angle of the cross section of the colored cured film produced using the photosensitive coloring composition of the present invention is 90 degrees or less, preferably 50 degrees or less with respect to the surface to be coated. it can. Alternatively, the cross-sectional shape of the colored cured film may be such that the ratio of the length of the upper base to the length of the lower base is less than 1.
[0132]
As for the contrast, when a blue cured film is formed using the photosensitive coloring composition of the present invention, the contrast ratio can be 2,000 or more.
[0133]
Regarding mechanical and chemical properties, the photosensitive coloring composition of the present invention is excellent in various points such as hardness, elasticity, film strength, adhesion, heat resistance, hot pure water resistance, chemical resistance, and impurity elution property. .
[0134]
For example, regarding the hardness, the photosensitive coloring composition of the present invention is applied on a glass substrate by spin coating, and is applied at 100 mJ / cm. ² In the case of forming a coating film having a thickness of 5 μm by heating at 200 ° C. for 30 minutes after exposure at the irradiation amount of, the surface hardness of the coating film is measured under the conditions of a surface temperature of 180 ° C. and a Vickers indenter of a maximum load of 20 mN. Hardness (test load / surface area of Vickers indenter under test load) at 200 N / mm ² It is possible to do the above. Regarding the universal hardness, material testing technology vol. 43, no. 2 (1998) p. 72 and can be evaluated according to German Standard DIN 50359-1.
[0135]
By using such a photosensitive coloring composition, it is possible to form a blue colored cured film or a colored coating film containing a phthalocyanine pigment in various fields. This photosensitive coloring composition is particularly suitable for forming a pattern of blue pixels or pixels containing a phthalocyanine pigment in a color filter, preferably a pattern of blue pixels containing a phthalocyanine blue pigment, A high-performance and high-quality color filter can be obtained.
[0136]
The color filter essentially includes a transparent substrate and a coloring layer formed on the transparent substrate, and further maintains a gap between a protective film covering the coloring layer and / or an electrode substrate facing the color filter, if necessary. And a spacer provided at a position overlapping with the non-display portion on the transparent substrate. In the present invention, such a pixel pattern of a color filter, particularly a blue pixel, is formed using the photosensitive coloring composition.
[0137]
Examples of the form of the color filter include (1) a form provided with a colored layer on a transparent substrate, (2) a form provided with a colored layer and a protective film, (3) a form provided with a colored layer and a spacer, (4) Examples include a form having a colored layer, a protective film, and a spacer.For example, a part of the colored layer is formed in a predetermined pattern on a black matrix layer formed in a predetermined pattern on a transparent substrate. Is preferred. Further, a transparent electrode for driving a liquid crystal may be formed on the protective film as needed. The method for forming the black matrix is not particularly limited. For example, the black matrix can be formed by a dyeing method, a pigment dispersion method, a printing method, an electrodeposition method, or the like. Further, it may be formed by chromium evaporation or the like.
[0138]
The coloring layer is usually arranged in a desired form such as a mosaic pattern, a stripe pattern, a triangle pattern, a four-pixel arrangement pattern, an island pattern in which the pixel patterns of red, green and blue are arranged in a “U” shape. The black matrix is provided between the colored patterns and in a predetermined area outside the colored layer forming area.
[0139]
In the present invention, at least one of the pixel patterns constituting such a colored layer, in particular, the pattern of a blue pixel is prepared using the above-mentioned photosensitive colored composition. For example, the above-mentioned photosensitive coloring composition is applied to one surface side of a transparent substrate, exposed by irradiating radiation such as ultraviolet rays through a photomask, and after alkali development, the coloring layer is cured by heating in a clean oven or the like. Can be formed. Usually, the thickness of the coloring layer is preferably about 1.5 μm.
[0140]
The protective film can be formed, for example, by applying a coating solution of a transparent photosensitive coloring composition by a method such as a spin coater, a roll coater, a spray, or printing. When a spin coater is used, the number of rotations is set within the range of 500 to 1500 rotations / minute. The coating film of the photosensitive coloring composition is exposed by irradiating ionizing radiation through a photomask, and after alkali development, is heated and cured in a clean oven or the like to form a protective film. Normally, the thickness of the protective film is preferably about 2 μm.
[0141]
When a transparent electrode is formed on the protective film, the transparent electrode is usually formed by sputtering using indium tin oxide (ITO), zinc oxide (ZnO), tin oxide (SnO), or an alloy thereof. It is formed by a general method such as a vacuum evaporation method and a CVD method, and a predetermined pattern is formed by etching using a photoresist or using a jig as necessary. The thickness of the transparent electrode is preferably, for example, about 20 to 500 nm. More preferably, it is about 100 to 300 nm.
[0142]
The spacer is preferably a columnar spacer having a height corresponding to the cell gap. The position where such a spacer is provided is preferably, for example, on the transparent electrode, on the colored layer, or on the protective film, in accordance with the region where the black matrix layer is formed. As a method of forming a columnar spacer on a transparent electrode or the like, for example, a coating solution of a transparent photosensitive coloring composition is applied by a method such as a spin coater, a roll coater, a spray, or printing, and radiation through a photomask is applied. After exposure by irradiation, alkali development, and heat curing in a clean oven or the like, it can be formed. The number of rotations of the spin coater may be set in the range of 500 to 1500 rotations / minute as in the case of forming the protective film. The thickness (height) of the columnar spacer is preferably, for example, about 5 μm.
[0143]
The color filter and the electrode substrate thus manufactured are opposed to each other, and a liquid crystal display device in which a liquid crystal compound is sealed between the two is obtained. The liquid crystal display device of the present invention can be manufactured, for example, by forming an alignment film on the inner surface side of the color filter, facing the electrode substrate, filling the gap with a liquid crystal compound, and sealing. The liquid crystal compound used for the liquid crystal display device of the present invention is not particularly limited. The electrode substrate is not particularly limited, and a substrate manufactured by a usual method can be used.
[0144]
Such a liquid crystal display device can sufficiently exhibit the function and effect of the photosensitive coloring composition, and is excellent in basic performance, and in addition, since it has excellent display image quality, such as a flat display such as a personal computer. It can be suitably applied as a display device.
[0145]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to only these Examples. Unless otherwise specified, “parts” means “parts by mass”, and “%” means “% by mass”.
[0146]
(Example 1)
(1) Synthesis of cyclohexylmaleimide resin
In a 30 L polymerization tank, 40.0 parts of diethylene glycol dimethyl ether (DMDG) was charged as a solvent, and the temperature was raised to 90 ° C. under a nitrogen atmosphere. 6.16 parts, 12.12 parts of methyl methacrylate (MMA), 12.55 parts of methacrylic acid (MAA), 0.62 parts of perbutyl O (PBO) (trade name, manufactured by NOF CORPORATION) as a dropping system 2, 1.23 parts of n-dodecyl mercaptan (n-DM) was continuously supplied as the dropping system 3 over 3 hours. Thereafter, the temperature was maintained at 90 ° C. for 30 minutes, then the temperature was raised to 105 ° C., and the polymerization was continued for 3 hours. The unreacted monomer determined by gas chromatography (GC) was 0.1% CHMI, 0.2% MMA, and 0.3% MAA.
[0147]
Then, 12.73 parts of glycidyl methacrylate (GMA), 0.13 part of triethylamine as a catalyst, and 2,2′-methylenebis (4-methyl-6-t-butylphenol) as a polymerization inhibitor (trade name of “ANTAGE”) were added to the reaction mixture. The reaction was continued for 8 hours while adding 0.07 parts of W400 (manufactured by Kawaguchi Chemical Industry Co., Ltd.) and bubbling air and nitrogen mixed gas adjusted to 5% oxygen concentration at a flow rate of 200 ml / min. When the reaction solution was measured by GC, no unreacted GMA was detected. After adding and diluting 7.5 parts of DMDG, the mixture was cooled to obtain a cyclohexylmaleimide resin solution 1.
[0148]
(2) Preparation of blue pigment dispersion composition
The cyclohexylmaleimide resin solution 1 was mixed with the pigment and the dispersant in the following amounts, and the mixture was dispersed with 0.3 mm zirconia beads for 3 hours using a paint shaker to obtain a blue pigment dispersion composition 1. The obtained blue pigment dispersion composition 1 had a solid content mass ratio (pigment / dispersant / cyclohexylmaleimide resin) of the pigment, the dispersant and the cyclohexylmaleimide resin of 1 / 0.2 / 0.4.
[0149]
<Composition of Blue Pigment Dispersion Composition 1>
-Pigment Blue 15: 6 (copper phthalocyanine blue pigment): 13 parts by mass (trade name "Lionol Blue ES, manufactured by Toyo Ink Co., Ltd.)
-Dispersant (trade name: PB-821, manufactured by Ajinomoto Co., Inc.): 5.65 parts by mass (solid content: 46.0% by mass)
-Cyclohexylmaleimide resin solution 1 (CHMI / MMA / MAA / GMA-MAA copolymer, solid content: 44.7% by mass): 11.56 parts by mass
-Propylene glycol monomethyl ether acetate: 69.79 parts by mass
(3) Preparation of blue resist
Cyclohexylmaleimide resin solution 1 and other components were blended with the above blue pigment dispersion composition 1 in the following amounts to prepare blue resist 1. The obtained blue resist 1 was obtained by adding cyclohexylmaleimide resin as a main polymer, dipentaerythritol pentaacrylate (trade name: Sartomer SR399E, manufactured by Nippon Kayaku Co., Ltd.) as a monomer, and the mass of solids of initiators 1 and 2. The ratio (cyclohexylmaleimide resin / dipentaerythritol pentaacrylate / sum of initiators 1 and 2) was 35/45/35.
[0150]
<Composition of Blue Resist 1>
-Blue pigment dispersion composition 1: 34.3 parts by mass
-Cyclohexylmaleimide resin solution 1 (CHMI / MMA / MAA / GMA-MAA copolymer, solid content: 44.7% by mass): 8.03 parts by mass
Dipentaerythritol pentaacrylate (trade name: Sartomer SR399E, manufactured by Nippon Kayaku Co., Ltd.): 6.03 parts by mass
Initiator 1 (trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals): 3.87 parts by mass
Initiator 2 (trade name: High Cure ABP, manufactured by Kawaguchi Chemical): 0.35 parts by mass
-Propylene glycol monomethyl ether acetate: 52.6 parts by mass
(Comparative Example 1)
A blue pigment dispersion composition C1 of a comparative example was prepared in the same manner as in Example 1, except that the composition was different from the blue pigment dispersion composition 1 except for the cyclohexylmaleimide resin solution 1.
[0151]
Further, in Example 1, the same amount of an acrylic resin (trade name: B-7500, manufactured by Shin-Nakamura Chemical Co., Ltd.) was used in place of the cyclohexylmaleimide resin solution 1 to prepare a blue resist C1 of a comparative example.
[0152]
(Analysis and evaluation)
The cyclohexylmaleimide resin solution 1 obtained in Example 1 was sampled and analyzed by the method described below. The results are shown in Table 1 together with the charged amount.
[0153]
Table 2 shows the results of evaluation using the blue pigment dispersion compositions and blue resists obtained in Examples and Comparative Examples by the following method.
[0154]
[Table 1]

[0155]
[Table 2]

[0156]
(1) Method for analyzing cyclohexylmaleimide resin solution 1
<Unreacted monomer, copolymer composition>
The unreacted monomer at the end of the polymerization was determined by quantifying it by gas chromatography.
[0157]
<Solid content>
0.3 g of the resin solution was precisely weighed in an aluminum dish, and vacuum-dried at 140 ° C. for 5 hours to obtain a mass after removing volatile components.
[0158]
<Acid value>
3 g of the resin solution was precisely weighed, dissolved in a mixed solvent of 70 g of acetone / 30 g of water, and titrated with a 0.1N KOH aqueous solution using thymol blue as an indicator, and the acid value per 1 g of the solid was determined from the concentration of the solid.
[0159]
<Viscosity>
Put the resin solution in a 300 ml tall beaker, hold in a constant temperature water bath at 25 ± 0.2 ° C., adjust the temperature to 25 ± 0.5 ° C., and use a digital viscometer type B (DVM-B manufactured by Toki Sangyo). Rotor No. The viscosity was measured at 3.6 rpm.
[0160]
<Moisture content>
1 g of a sample is dissolved in 30 g of a titration solvent using a dehydrated solvent of a new Karl Fischer titration solvent, Hayashi-Solvent CE, and the water content is measured with a Karl Fischer measuring device (MKS-3P manufactured by Kyoto Electronics Industry). did.
[0161]
<Double bond amount>
After vacuum drying the resin solution at 70 ° C. for 5 hours to evaporate the solvent, 200 MHz 1H NMR (Gemini 2000 / 200BB manufactured by Varian Technologies Japan Limited) was measured using DMSO-d6 as a solvent and chloroform as an internal standard substance. It was determined from the absorption intensity of the heavy bond.
[0162]
<Weight average molecular weight (Mw)>
The weight average molecular weight was measured using Shodex GPC System-21H using polystyrene as a standard substance and THF as an eluent.
[0163]
<Glass transition point (Tg)>
Using a DSC8230 (trade name) manufactured by Rigaku Denki Co., the polymer alone was measured at a temperature rising rate of 10 ° C./min under a nitrogen stream.
[0164]
<1% KOH solubility>
The polymerization solution was diluted with tetrahydrofuran (THF), precipitated in a large amount of hexane, filtered and dried to separate a polymer alone, added to a 20% aqueous solution of 1% KOH, and stirred for 3 hours. After the stirring, if there was any insoluble matter, it was filtered, the amount of the insoluble matter was measured, and evaluated according to the following criteria.
：: Complete dissolution,
：: very slight turbidity or insoluble content of 10% or less,
△: 10% to 50% of insoluble matter,
×: Insoluble content is 50% or more
<Solubility of propylene glycol monomethyl ether acetate (PGMEA) and 3-methoxybutyl acetate (methacetate)>
Each solvent was added to the precipitated and dissolved polymer so as to have a concentration of 20%, heated to 60 ° C., stirred for 3 hours, and allowed to cool to room temperature. When there was an insoluble matter, the insoluble matter was filtered, the amount of the insoluble matter was measured, and evaluated according to the following criteria.
：: Complete dissolution,
：: very slight turbidity or insoluble content of 10% or less,
△: 10% to 50% of insoluble matter,
×: Insoluble content is 50% or more
<380 nm transmittance>
The copolymer solution was diluted with diethylene glycol dimethyl ether (DMDG) to a polymer concentration of 20%, and a coating film was formed on a glass substrate using a spin coater. The coating film was formed at room temperature for 30 minutes, at 90 ° C. for 30 minutes, and at 200 ° C. for 30 minutes. It was dried by heating for 30 minutes to form a coating film having a thickness of 2 μm. Then, it heated at 250 degreeC for 1 hour, and measured the light transmittance in the range of 380-780 nm.
[0165]
(2) Blue pigment dispersion composition and evaluation method of blue resist
(2-1) Pigment dispersibility
The 50% average pigment particle size of the blue pigment dispersion composition was measured using a laser Doppler scattered light analysis particle size analyzer (Microtrac 934UPA) manufactured by Nikkiso Co., Ltd.
[0166]
(2-2) Development form, development time, spectral characteristics, heat resistance, pattern cross-sectional shape
After spin-coating a blue resist on the alkali-cleaned glass substrate, it was dried at room temperature for 3 minutes and further on a hot plate at 80 ° C. for 3 minutes to form a 1.3 μm-thick coating film. 100 mJ / cm ² Exposure was carried out with a mask, spin-developed, indirectly applied to a developing solution for 60 seconds, washed with pure water, and the patterned substrate was baked in an oven at 230 ° C. for 30 minutes. In this developing process, whether the developing mode was a dissolving type or a peeling type was observed, and the developing time was measured.
[0167]
Next, the obtained substrate with a blue pattern was illuminated with a brightness Y defined by JIS Z8701 by a microspectrophotometer (OSP SP-100) manufactured by Olympus Optical Industry Co., Ltd. using a C light source specified by the International Commission on Illumination. The value was measured.
[0168]
Thereafter, the blue-patterned substrate is heated in an oven at 250 ° C. for 1 hour, the brightness Y value is measured in the same manner, and the rate of change of the Y value before and after the test is determined based on the Y value before the heat resistance test. Calculated.
[0169]
In addition, the cross-sectional shape of the colored layer of the substrate with a blue pattern obtained at a stage after baking at 230 ° C. for 30 minutes was observed with an SEM (scanning electron microscope), and the rising angle of the colored layer and the rising angle of the colored layer were determined using an SEM photograph. The ratio of the length of the upper base to the length of the lower base was calculated.
[0170]
(2-3) Development residue
A blue resist solution was spin-coated on a glass substrate having chromium deposited on the back surface, and then dried at room temperature for 3 minutes and further on a hot plate at 80 ° C. for 3 minutes to form a 1.3 μm-thick film. This coating film was spin-developed, indirectly applied to a developing solution for 60 seconds, and then washed with pure water.
[0171]
After the washing, the glass substrate was visually observed with a light projector, and the presence or absence of a residue was confirmed. In addition, the surface of the substrate was wiped with a rag with ethanol, and the presence or absence of the residue wiped on the rag was confirmed.
[0172]
(2-4) Contrast ratio
The blue resist-coated substrate obtained in Example (2-2) was sandwiched between two polarizing plates (NPF-G 1220DU manufactured by Nitto Denko), and a backlight (Merrow 5D FL10EX-DH manufactured by Toshiba, color temperature: 6500K) was used. The light was turned on, and the brightness of the polarizing plate when it was orthogonal and when it was parallel was measured by a brightness meter (SL-100 manufactured by Minolta). The contrast ratio can be derived from the following equation using the measured value of luminance.
[0173]
Contrast ratio = parallel luminance (cd / m ² ) / Orthogonal luminance (cd / m ² )
(2-5) Surface roughness, adhesion, resolution, cross-cut peel test
The plate making properties (surface roughness (Ra), adhesion and resolution by line and space, cross-cut peel test) were evaluated. The curable resin composition 1 was applied on a 10 cm glass substrate by a spin coater (manufactured by MIKASA, model 1H-DX2) and dried to form a coating film having a dry film thickness of 2.2 μm. This coating film was heated on a hot plate at 90 ° C. for 3 minutes. After heating, a photomask was placed at a distance of 100 μm from the coating film, and a UV aligner (manufactured by Dainippon Screen, model MA 1200) equipped with a 2.0 kW ultra-high pressure mercury lamp was set to 100 mJ / cm. ² UV light was applied at an intensity of 405 nm (in terms of illuminance).
[0174]
After the ultraviolet irradiation, a 0.05 wt% aqueous solution of potassium hydroxide was sprayed on the coating film by a spin developing machine (Applied Process Technology, INK, MODEL: 915) for 60 seconds to dissolve and remove the unexposed portion, and to expose the remaining exposed portion. The part was developed by washing with pure water for 60 seconds. After the development, the film in the exposed area was heated at 200 ° C. for 30 minutes using a clean oven (SCOV-250 Hy-So, manufactured by Oshitari Research Laboratory Co., Ltd.).
[0175]
The surface of the coating film after the alkali development treatment was subjected to AFM measurement using a scanning probe microscope (AS-7B) manufactured by Takano Co., Ltd., and the surface roughness (Ra) (coating film) defined in JIS B0601-1994 was determined. Surface smoothness) was determined and evaluated according to the following criteria.
[0176]
<Surface roughness evaluation criteria>
：: Extremely smooth. (50Å or less)
：: smooth. (More than 50Å, less than 100Å)
Δ: The surface is rough. (Over 100Å)
×: The surface is severely roughened, and whitening of the coating film is observed.
[0177]
Exposure is performed by a method described above through a line and space mask, and the shape of the obtained relief pattern is observed with an optical microscope (MHL100, manufactured by Olympus Optical Industrial Co., Ltd.). (Adhesion) and resolution were determined.
[0178]
Further, after the cured colored layer was immersed in pure water at 80 ° C. for 30 minutes, a cross-cut peel test was performed, and the adhesion (warm pure water resistance) was evaluated according to the following criteria.
[0179]
<Evaluation criteria for cross-cut peel test>
：: No peeling of the coating film.
C: Less than 50% of the coating film peeled off and had defects.
X: 50% or more of the coating film peeled off and had a defect.
(Example 2)
The same operation as in Example 1 was carried out except that the charged amount was changed as shown in Table 3, to obtain a cyclohexylmaleimide resin solution 2. The analysis values are shown in Table 3.
In Example 1, the same amount of cyclohexylmaleimide resin solution 2 was used in place of cyclohexylmaleimide resin solution 1 to prepare blue resist 2.
(Example 3)
The same operation as in Example 1 was performed except that the charged amount was changed as shown in Table 3, to obtain a cyclohexylmaleimide resin solution 3. The analysis values are shown in Table 3.
In Example 1, the same amount of cyclohexylmaleimide resin solution 3 was used in place of cyclohexylmaleimide resin solution 1 to prepare blue resist 3.
(Analysis and evaluation)
Table 4 shows the results of the following evaluations.
<Hydroxyl value measurement method>
According to JIS-K0070, the hydroxyl value was determined, and the hydroxyl value per 1 g of the solid content was determined from the solid content concentration.
<Acid value measurement method>
The acid value was measured in the same manner as in Example 1.
<Development residue>
The same residue wiping test test as in Example 1 was performed and evaluated according to the following criteria. ：: No residue (no coloring)
○: Lightly colored
△: deeply colored
×: deeply colored (residual implied confirmation level)
[Table 3]

[Table 4]

[0180]
【The invention's effect】
As described above, according to the present invention, a photosensitive coloring composition containing a blue pigment or a phthalocyanine-based pigment, having excellent color characteristics, fine pattern forming ability, and physical properties after curing, and a pigment used for preparing the same. A dispersion composition is obtained. This photosensitive coloring composition is very suitable for forming a pixel of a color filter, particularly a blue pixel, has excellent transparency and yellowing resistance, and forms an accurate pixel pattern without generating a residue during development. After curing, it has excellent physical properties such as hardness and elasticity.
[0181]
By forming pixels of a color filter using such a photosensitive coloring composition, a color filter having excellent display performance and a display device having excellent display performance using the color filter, for example, a liquid crystal display device and an organic EL device A display device and the like are obtained.
[Brief description of the drawings]
FIG. 1 is a schematic sectional view of an example of a liquid crystal panel.
FIG. 2 is a schematic sectional view of another example of the liquid crystal panel.
[Explanation of symbols]
1 ... Color filter
2 ... Electrode substrate
3: gap (L; liquid crystal compound)
4: Seal material
5. Transparent substrate
6 Black matrix layer
7 (7R, 7G, 7B): colored layer
8 ... Protective film
9 ... Transparent electrode film
10. Alignment film
11 ... Pearl
12 ... pillar spacer

Claims (24)

A pigment dispersion composition comprising at least one or more pigments selected from the group consisting of a blue pigment and a phthalocyanine pigment, a maleimide-based alkali-soluble copolymer, a dispersant, and a solvent, wherein the maleimide-based alkali The soluble copolymer is composed of 5 to 50% by mass of a cyclohexylmaleimide monomer unit, 8 to 30% by mass of a (meth) acrylic acid monomer unit, and 30 to 87% of a (meth) acrylic acid ester monomer unit. % By mass, and the cyclohexylmaleimide monomer unit amount is defined as X mass% and the (meth) acrylic acid-based monomer unit amount is defined as Y mass%. ≦ 0.5 × X + 10
A pigment dispersion composition characterized by satisfying the following. The pigment dispersion composition according to claim 1, wherein the maleimide-based alkali-soluble copolymer has an acid value of 50 to 200 mgKOH / g and a hydroxyl value of 10 to 150 mgKOH / g. 2. The compounding ratio of a dispersant (dispersant / pigment) to the total amount of pigments containing a pigment selected from the group consisting of blue pigments and phthalocyanine pigments is not more than 0.5 in mass ratio. Or the pigment dispersion composition according to 2. At least one or more pigments selected from the group consisting of blue pigments and phthalocyanine pigments, a maleimide-based alkali-soluble copolymer, a photosensitive coloring composition containing a radically polymerizable compound and a photopolymerization initiator, The maleimide-based alkali-soluble copolymer comprises cyclohexylmaleimide monomer units 5 to 50% by mass, (meth) acrylic acid-based monomer units 8 to 30% by mass, and (meth) acrylate-based monomers Assuming that the unit has a unit of 30 to 87% by mass and that the amount of the cyclohexylmaleimide monomer is X% by mass and the amount of the (meth) acrylic acid-based monomer is Y% by mass, the following formula: 0.4 × X ≦ Y ≦ 0.5 × X + 10
A photosensitive coloring composition characterized by satisfying the following. The photosensitive coloring composition according to claim 4, wherein the maleimide-based alkali-soluble copolymer has an acid value of 50 to 200 mgKOH / g and a hydroxyl value of 10 to 150 mgKOH / g. When the film thickness after curing is 1.35 μm or less, the x coordinate is 0.05 ≦ x ≦ 0.30 and the y coordinate is 0.05 ≦ y ≦ 0.30 in the C light source colorimetric XYZ color system two-degree visual field. The photosensitive coloring composition according to claim 4, wherein a cured film capable of displaying a color space having a stimulus value Y of 20 or more can be formed. When measuring the stimulus value Y at a C light source colorimetric XYZ color system 2 degree visual field before and after heating at 250 ° C. for 1 hour, y = 0.1400, the film thickness after curing was set to 1.3 μm, and before heating. The photosensitive coloring composition according to any one of claims 4 to 6, wherein a cured film having a rate of change (Y2 / Y1) of the measured value Y2 after heating to the measured value Y1 of 97% or more can be formed. The photosensitive coloring composition according to any one of claims 4 to 7, wherein a cured film having a contrast ratio of 2,000 or more can be formed. The photosensitive coloring composition according to any one of claims 4 to 8, wherein a cured film having a surface roughness (Ra) of 50 ° or less can be formed by a measuring method based on JIS B0601-1994. The photosensitive coloring composition according to any one of claims 4 to 9, wherein a cured film having a line width that causes a defect when exposed to light and cured through a line and space mask is 25 µm or less can be formed. The photosensitive colored composition according to any one of claims 4 to 10, wherein a cured film having a resolution of 24 µm or less when exposed and cured through a line-and-space mask can be formed. The photosensitive coloring composition according to any one of claims 4 to 11, wherein a cured film having a rising angle of a cross section of 50 degrees or less with respect to a surface to be coated can be formed. A color filter comprising a pixel formed by curing the photosensitive coloring composition according to claim 4. A color filter provided with pixels formed by dispersing at least one pigment selected from the group consisting of a blue pigment and a phthalocyanine pigment in a matrix composed of a cured product of a binder containing a maleimide-based alkali-soluble copolymer. In addition, the maleimide-based alkali-soluble copolymer has a cyclohexylmaleimide monomer unit of 5 to 50% by mass, a (meth) acrylic acid-based monomer unit of 8 to 30% by mass, and a (meth) acrylate-based monomer unit. Assuming that the monomer unit has 30 to 87% by mass as an essential component, the cyclohexylmaleimide monomer unit amount is X% by mass, and the (meth) acrylic acid monomer unit amount is Y% by mass, the following formula is obtained. 0.4 × X ≦ Y ≦ 0.5 × X + 10
A color filter characterized by satisfying the following. The color filter according to claim 13, wherein the pixel has a surface roughness (Ra) of 50 ° or less in a measuring method based on JIS {B0601-1994 ”. The color filter according to any one of claims 13 to 15, wherein the pixel has a line width which causes a defect when exposed and cured through a line and space mask is 25 µm or less. 17. The color filter according to claim 13, wherein the pixel has a resolution of 24 [mu] m or less when exposed and cured through a line and space mask. 18. The color filter according to claim 13, wherein a rising angle of a cross section of the pixel is 50 degrees or less with respect to a surface to be coated. 19. The color filter according to claim 13, wherein a cross-sectional shape of the pixel is such that a ratio of a length of the upper base to a length of the lower base is less than 1. 20. The color filter according to claim 13, wherein the pixel is a blue pixel. When the blue pixel has a thickness of 1.35 μm or less and performs color measurement with a single pixel, the x coordinate is 0.05 ≦ x ≦ 0.30 and the y coordinate is 2 in the C light source colorimetric XYZ color system two-degree visual field 21. The color filter according to claim 20, wherein a color space in a range of 0.05 ≦ y ≦ 0.30 and a stimulus value Y of 20 or more can be displayed. The blue pixel has a thickness of 1.3 μm, and before and after heating at 250 ° C. for 1 hour, a stimulus value Y of a single pixel C light source colorimetric XYZ color system with a 2 degree visual field, y = 0.400. 22. The color filter according to claim 20, wherein a rate of change (Y2 / Y1) of the measured value Y2 after the heating to the measured value Y1 before the heating is 97% or more when the measurement is performed. 23. The color filter according to claim 20, wherein a contrast ratio of the blue pixel is 2,000 or more. 24. A liquid crystal display device comprising a color filter according to claim 13 and an electrode substrate facing each other, and a liquid crystal compound sealed between the two.

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