JP4092245B2 - Pigment dispersion composition, photosensitive coloring composition, color filter, and liquid crystal display device - Google Patents

Description

【０１５２】
【表２】

【０１５３】
（１）ベンジ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。
【０１５４】
＜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。
【０１５５】
＜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。
【０１５６】
＜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。
【０１５７】
＜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−ＳｏｌｖｅｎｔＣＥ）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。
【０１５８】
＜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Ｇｅｍｉｎｉ ２０００／２００ＢＢ）を測定し、二重結合の吸収強度から求めた。
【０１５９】
＜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。
【０１６０】
＜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。
【０１６１】
＜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。
【０１６２】
（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。
【０１６３】
（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。
【０１６４】
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。
【０１６５】
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。
【０１６６】
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。
【０１６７】
（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。
【０１６８】
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。
【０１６９】
（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。
【０１７０】
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。
【０１７１】
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。
【０１７２】
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。
【０１７３】
＜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。
【０１７４】
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。
【０１７５】
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。
【０１７６】
＜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。
【０１７７】
（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、ベンジ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、ベンジルマレイミド樹脂溶液１の代わりに同量のベンジ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、ベンジルマレイミド樹脂溶液３を得た。分析値を表１に示す。
実施例１において、ベンジルマレイミド樹脂溶液１の代わりに同量のベンジルマレイミド樹脂溶液３を用いて青レジスト３を調製した。
【０１７８】
（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）
【０１７９】
【表３】

【０１８０】
【表４】

【０１８１】
【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。
【０１８２】
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]
BACKGROUND OF THE INVENTION
The present invention relates to a pigment dispersion composition, a photosensitive coloring composition, a color filter, and a liquid crystal display device. 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 further, a blue pigment using such a photosensitive coloring composition. Alternatively, the present invention relates to a color filter in which a pixel pattern containing a phthalocyanine pigment is formed 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 them to form a thin liquid crystal layer. A liquid crystal display device incorporating such a liquid crystal panel selectively changes the amount of transmitted or reflected light of the display side substrate by electrically controlling the liquid crystal alignment in the liquid crystal layer by the liquid crystal drive side substrate of the liquid crystal panel. Display.
[0003]
There are various drive systems such as static drive system, simple matrix system, and active matrix system, but in recent years, liquid crystal panels of active matrix system or simple matrix system have been used as flat displays for personal computers and personal digital assistants. The used color liquid crystal display devices are rapidly spreading.
[0004]
FIG. 1 is a configuration example of an active matrix type liquid crystal panel. The liquid crystal panel 101 is provided with a gap portion 3 of about 1 to 10 μm so that the color filter 1 as a display side substrate and the TFT array substrate 2 as a liquid crystal drive side substrate face each other, and the liquid crystal L is filled in the gap portion 3. 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 the transparent substrate 5 to shield the boundary between pixels, and a plurality of colors (usually red (R (R)) to form each pixel. ), Green (G), blue (B) three primary colors) arranged in a predetermined order, or recently a pixel portion using a hologram, a protective film 8, and a transparent electrode film 9 on a transparent substrate. It has a stacked 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). 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 1. A color image is obtained by controlling the light transmittance of the liquid crystal layer behind the pixels colored in the respective colors.
[0006]
As a method of maintaining the cell gap, as shown in FIG. 1, a large number of spherical or rod-like particle spacers 11 of a certain size made of glass, alumina, plastic, or the like are scattered in the gap 3 as a spacer. A method of injecting liquid crystal by laminating with the TFT array substrate 2, or as shown in FIG. 2, in the cell gap in a region overlapping the position where the black matrix layer 6 is formed on the inner surface side of the color filter. 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 is obtained by controlling the light transmittance of the liquid crystal layer behind each pixel that is colored in each color and arranged in a predetermined pattern.
[0008]
The pixel portion of the color filter is a light composed of a binder resin, a photoinitiator, or the like, using one or two or more pigments selected so as to develop a predetermined color such as RGB by a so-called pigment dispersion method. A photosensitive coloring composition is prepared by blending with a curable resin composition, this is applied onto a transparent substrate, dried, and a predetermined region of the obtained coating film is selectively exposed and cured to obtain 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 representation capability of pixels is important. Each RGB pixel is toned so that the color reproduction region 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 have excellent transparency and color purity. In the manufacturing process of the color filter, there is a problem that 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 the blue pixel is yellowish, the transparency and the color characteristics are significantly deteriorated. Therefore, it is more important to prevent the blue pixel from yellowing than other pixels.
[0010]
The fine pattern forming ability such as 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, there is no residue, no loss of fine lines, no foreign matter remains, no surface roughness occurs, Performances such as high resolution, accurate shape after development, and uniform film thickness are required.
[0011]
A residue is a colored product that remains in a portion that should not remain after development, and is likely to occur when developability is poor due to a large amount of pigment or dispersant.
[0012]
Fine line defects are likely to occur when the adhesiveness is inferior due to a small amount of the curing component in the photosensitive coloring composition or a low affinity with the substrate. The foreign matter is generated due to, for example, a part of a pixel being missing when there are few curing components in the photosensitive coloring composition, or a colored piece produced by peeling development with few developing components. Surface roughness also occurs when there are few curing components in the photosensitive coloring composition.
[0013]
In order to improve resolution, the liquid crystal drive system has evolved, and the color filter has a pattern with many curved parts and corners, unlike the conventional stripe pattern. There is a need to.
[0014]
There is a problem that the shape after development becomes an inverted trapezoid (reverse tapered shape) when the photosensitive coloring composition has poor photosensitivity. If the post-development shape becomes an inverted trapezoid, the upper part of the pixel tends to be chipped due to water pressure during development, which causes the above-mentioned foreign matter. Further, when the reverse trapezoidal film has low heat resistance, a portion protruding in a comb shape may hang down due to heat and form a hole after post-baking. This hole not only degrades the display quality but also reduces the resolution. In addition, the liquid crystal is contaminated when heated and burst in the liquid crystal panel assembly.
[0015]
Film thickness uniformity is not a major problem at the individual pixel level. However, for the purpose of cost reduction, the substrate size has been steadily increasing and has been applied to the metric class. In that case, if the film thickness is different between the glass center and the edge, the color varies, resulting in a defective product.
[0016]
In order to form a fine pattern accurately, it is required to satisfy all the above-described elements. However, in general, increasing the solubility of the photosensitive coloring composition with a developer so as not to leave a residue tends to cause fine line defects, foreign matter, surface roughness, and the like, so 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 and the liquid crystal display device, but also greatly affect the display performance. As physical properties that affect 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 directly formed on the substrate of the color filter, but may be provided in an upper layer than the pixels and the black matrix. In the latter case, if the pixel hardness and elastic modulus are inferior, even if a spacer having a high hardness is formed, the base is deformed and the uniformity of the cell gap is impaired. For this reason, even a pixel is required to have high hardness and elastic modulus.
[0019]
Impurity elution from the pixel causes liquid crystal contamination. Since the liquid crystal does not perform the switching function only by mixing 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, conductive pigments are often included as impurities in pigments and dispersants used for pixels. Therefore, suppression of impurity elution from the pixel portion is required.
[0020]
By sufficiently containing a curing component in the photosensitive coloring composition, the post-curing physical properties of the pixel can be improved. However, if a large amount of a dispersant is blended in order to finely disperse the pigment in the photosensitive coloring composition and increase the transparency of the pixel, the concentration of the curing component will be lowered and the physical properties of the pixel cannot be improved. . If a large amount of a dispersant is used, the pigment concentration is also lowered, so that the color reproduction ability is also inferior.
[0021]
The binder resin of the photosensitive coloring composition forming the pixel of the color filter has performances from various viewpoints as described above, for example, original transparency, heat resistance (yellowing resistance), curability, developability, Affinity with the pigment, adhesion with the substrate, and the like are required.
[0022]
JP-A-10-31308 discloses a photosensitive coloring composition using a copolymer of a monomer having an N-substituted maleimide and an acid group as a binder resin. JP-A-10-300922 discloses a radiation-sensitive composition for color filters containing an alkali-soluble resin containing a copolymer of an N-substituted maleimide monomer and another copolymerizable monomer. Further, JP-A-11-15147 discloses a colored image forming material containing a polymer having a maleimide group in the skeleton. However, there is a problem that the maleimide monomer tends to remain at the end of the reaction and cannot fully exhibit its action such as decomposition and coloring. In addition, when forming a thin film layer or a fine pattern such as a color filter, the resin composition is applied onto the substrate by a spin coating method or the like. At this time, if the boiling point of the solvent is low, a uniform film is formed. Since it is difficult, a solvent having a high boiling point is used in consideration of a balance such as dryness. However, there is a room to devise so that the copolymer is sufficiently dissolved in such a solvent.
[0023]
In JP-A-10-60214, α, β-ethylenically unsaturated carboxylic acid 1 to 6% by mass, α, β-ethylenically unsaturated carboxylic acid ester 10 to 80% by mass and N-substituted maleimide 5 to 30% are disclosed. An acrylic resin composition for a color filter obtained by blending an acrylic resin obtained by polymerizing a monomer mixture containing mass% is disclosed. However, in order to make such a polymer a constituent of a photosensitive coloring composition capable of forming a thin film layer such as a color filter or a fine pattern, the solubility in alkaline water is improved, There was room for contrivance to achieve both heat resistance and hardness. That is, in the manufacture of color filters and the like, a resin composition is applied on a transparent substrate to form a coating film, and pattern exposure is performed through a mask as necessary, followed by development using alkaline water to remove unexposed portions. It will go through the process of removing the cured part, but if it is not sufficiently soluble in alkaline water, it will be difficult to form a clear pattern, and if the solubility in alkaline water is improved, heat resistance and hardness will not be sufficient. There was room to devise in order to manufacture higher quality color filters and the like.
[0024]
[Problems to be solved by the invention]
The present invention has been achieved in view of such circumstances, and its first object is to use a maleimide-based alkali-soluble copolymer that can be sufficiently dissolved in alkaline water as a binder, and to improve transparency and yellowing resistance. Providing a color filter with excellent display performance, with pixels that have excellent color characteristics such as residue, and pixels with excellent pattern forming ability such as residue problems and fine pattern accuracy, and post-curing physical properties such as hardness and elasticity There is to do.
[0025]
In addition, a second object of the present invention is to provide a color filter that is particularly excellent in color characteristics, pattern forming ability, and post-curing physical properties of a blue pixel.
[0026]
The third 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 and is excellent in color characteristics such as transparency and yellowing resistance, and more preferably, It is possible to form a colored coating film having excellent pattern forming ability such as problem and accuracy of fine pattern, and post-curing physical properties such as hardness and elasticity. Particularly, it forms a pixel pattern of a color filter, particularly preferably a blue pixel. It is in providing the photosensitive coloring composition suitable for.
[0027]
A fourth object of the present invention is a pigment dispersion composition suitable for preparing the above photosensitive coloring composition using a maleimide-based alkali-soluble copolymer having a pigment dispersion function as well as a function as an alkali-soluble binder. To provide things.
[0028]
A fifth object of the present invention is to provide a liquid crystal display device that is excellent in display performance using the color filter, and preferably excellent in transparency and color characteristics of blue pixels.
[0029]
[Means for Solving the Problems]
The pigment dispersion composition according to the present invention includes at least one pigment selected from the group consisting of a blue pigment and a phthalocyanine pigment, a maleimide alkali-soluble copolymer, a dispersant, and a solvent. In the composition, the maleimide-based alkali-soluble copolymer has a benzylmaleimide monomer unit that may have a substituent as an essential component.
[0030]
The maleimide-based alkali-soluble copolymer specified as described above not only functions as a binder component but also has excellent pigment dispersion performance, so that it is excellent in dispersibility by using it instead of a dispersant. In addition, a pigment dispersion composition containing little or no dispersant can be prepared. Since the usage-amount of a dispersing agent can be reduced, the film | membrane physical property of the photosensitive coloring composition prepared using this improves.
[0031]
When the acid value of the maleimide-based alkali-soluble copolymer is 50 to 200 mgKOH / g and the hydroxyl value is 10 to 150 mgKOH / g, the effect of improving the residue (background stain) after development is great. In particular, it is preferable because a large improvement effect is obtained in a high pigment concentration range.
In the pigment dispersion composition, the blending ratio of the dispersant (dispersant / pigment) with respect to the total amount of the pigment including a pigment selected from the group consisting of a blue pigment and a phthalocyanine pigment is 0.5 or less in terms of mass ratio. Is preferred.
[0032]
Next, the photosensitive coloring composition according to the present invention includes at least one pigment selected from the group consisting of a blue pigment and a phthalocyanine pigment, a maleimide alkali-soluble copolymer, a radical polymerizable compound, and a photopolymerization initiator. The maleimide-based alkali-soluble copolymer has a benzylmaleimide monomer unit that may have a substituent as an essential component.
[0033]
The photosensitive coloring composition of the present invention is applied to a color filter substrate and exposed to light, whereby the maleimide-based alkali-soluble copolymer has excellent physical properties and alkali developability, and a three-dimensional formed by a radically polymerizable compound. With the network structure, it is possible to form a cured film with excellent physical properties such as adhesion to the surface of the substrate (substrate surface), film strength, heat resistance, hot pure water resistance, chemical resistance, etc. When it is exposed and developed in the shape, an accurate pattern can be formed, and no residue remains in the removed portion during development.
[0034]
The maleimide-based alkali-soluble copolymer has a particularly high affinity with phthalocyanine pigments. Therefore, when used in combination with phthalocyanine pigments, it has excellent transparency, color characteristics, ability to form fine patterns, and a film after curing. Physical properties can be obtained.
[0035]
Further, since the maleimide-based alkali-soluble copolymer is excellent in yellowing resistance as described above, it is very effective to be combined with a blue pigment that has a remarkable adverse color tone due to yellowing. The phthalocyanine blue pigment is particularly preferable because of its excellent affinity.
[0036]
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 the C light source colorimetric XYZ color system 2 ° field of view. .30, a cured film capable of displaying a color space in which the y coordinate is 0.05 ≦ y ≦ 0.30 and the stimulus value Y is 20 or more can be formed.
[0037]
Further, in a preferred embodiment, by using the photosensitive coloring composition, the film thickness after curing is 1.3 μm, and the C light source calorimetric XYZ color system 2 field of view before and after heating at 250 ° C. for 1 hour, When the stimulus value Y at y = 0.1400 is measured, a cured film can be formed in which the rate of change (Y2 / Y1) of the measured value Y2 after heating with respect to the measured value Y1 before heating is 97% or more.
[0038]
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.
[0039]
In a preferred embodiment, a cured film having a surface roughness (Ra) of 50 mm or less can be formed by the measurement method based on JIS B0601-1994 by using the photosensitive coloring composition.
[0040]
In a preferred embodiment, by using the photosensitive coloring composition, a cured film having a line width of 25 μm or less that causes defects when exposed and cured through a line and space mask can be formed.
[0041]
In a preferred embodiment, a cured film having a resolution of 24 μm or less when exposed and cured through a line and space mask can be formed by using the photosensitive coloring composition.
[0042]
In a preferred embodiment, a cured film having a rising angle of the cross section of 50 degrees or less with respect to the coated surface can be formed by using the photosensitive coloring composition.
[0043]
Next, the first color filter according to the present invention is characterized in that a pixel obtained by curing the photosensitive coloring composition is provided.
[0044]
The second color filter according to the present invention includes at least one 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. A color filter provided with pixels in which a pigment is dispersed, wherein the maleimide alkali-soluble copolymer has an essential benzyl maleimide monomer unit which may have a substituent. And
[0045]
The photosensitive coloring composition according to the present invention is very particularly suitable for forming a pattern of a pixel containing a blue pixel or a phthalocyanine pigment in a color filter, preferably a pattern of a blue pixel containing a phthalocyanine blue pigment. A high-performance and high-quality color filter is obtained.
[0046]
In a preferred embodiment, the blue pixel of the color filter has a cross-section in which the rising angle of the cross-section is 50 degrees or less with respect to the surface to be coated, or the ratio of the length of the upper base to the length of the lower base is less than 1. It is formed in a tapered shape having a shape.
[0047]
In a preferred embodiment, the blue pixel of the color filter has an x coordinate of 0.05 ≦ x in the C light source color measurement XYZ color system 2 ° field of view when color measurement is performed with a single pixel with a film thickness of 1.35 μm or less. It is possible to display a color space in which ≦ 0.30, the y coordinate is 0.05 ≦ y ≦ 0.30, and the stimulus value Y is 20 or more.
[0048]
Further, in a preferred embodiment, the blue pixel of the color filter has a film thickness of 1.3 μm, and before and after being heated at 250 ° C. for 1 hour, a single pixel C light source color measurement XYZ color system two-degree field of view, y When the stimulus value Y at 0.1400 is measured, the rate of change (Y2 / Y1) in the measured value Y2 after heating with respect to the measured value Y1 before heating is 97% or more.
[0049]
Furthermore, according to the present invention, there can be obtained 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 therebetween.
[0050]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in detail below.
[0051]
In the maleimide-based alkali-soluble copolymer used as the binder component of the photosensitive coloring composition in the present invention, as the benzyl maleimide monomer unit that may have a substituent that is an essential monomer unit, for example, Examples thereof include a benzyl maleimide monomer unit having no substituent and a benzyl maleimide monomer unit having a substituent in the benzyl group. Among them, a benzyl maleimide monomer unit having no substituent is preferable. In the case of having a substituent, the type and number of substituents, the position at which the substituent is bonded, and the like are not particularly limited as long as the effects of the present invention can be exhibited.
[0052]
The solubility of the maleimide-based alkali-soluble copolymer in alkaline water is preferably soluble in, for example, a 1% KOH aqueous solution. In this case, it is preferable that 20% by mass of the copolymer is added to 1% KOH aqueous solution and completely dissolved when stirred for 3 hours. In the 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. Moreover, it is preferable that the alkaline aqueous solution insoluble content with respect to 0.5% KOH aqueous solution is 10 mass% or less. More preferably, it is 5 mass% or less, More preferably, it is 3 mass% or less. The aqueous solution insoluble content of the maleimide-based alkali-soluble copolymer is, for example, an alkali test using a 50-μm thick film of the maleimide-based alkali-soluble copolymer in a solubility test in 200 ml of 0.5% KOH aqueous solution at 50 ° C. It can be evaluated by determining the amount of water-insoluble matter.
[0053]
The maleimide-based alkali-soluble copolymer has a benzylmaleimide monomer unit that may have a substituent as an essential component, and appropriately sets the type and ratio of the monomer unit, the molecular weight, etc. so as to be alkali-soluble. However, the preferred form is a benzylmaleimide monomer unit, (meth) acrylic acid monomer unit and (meth) acrylic acid ester monomer which may have a substituent. The form which has a unit as an essential is mentioned. These monomer units can be used alone or in combination of two or more.
[0054]
As a mass ratio of the monomer unit which comprises the said maleimide type | system | group alkali-soluble copolymer, the benzyl maleimide monomer unit which may have a substituent is 5-50 mass%, for example, (meth) acrylic acid single unit It is preferable that a monomer unit is 8-30 mass% and a (meth) acrylic acid ester monomer unit is 30-87 mass%. When the mass ratio of these monomer units is out of the above range, there is a possibility that the function and effect exhibited by each monomer unit in the present invention cannot be obtained. As a more preferable form of the above mass range, 10 to 45% by mass of a benzylmaleimide monomer unit which may have a substituent, 10 to 25% by mass of a (meth) acrylic acid monomer unit, and (meth) Acrylic acid ester monomer unit 30 to 80% by mass, most preferably, benzyl maleimide monomer unit 12 to 45% by mass which may have a substituent, (meth) acrylic acid monomer unit 15 to 25% by mass %, And (meth) acrylic acid ester monomer unit 35 to 70% by mass. In addition, the said mass range is based on 100 mass% of maleimide type | system | group alkali-soluble copolymers. The composition of the copolymer can be determined by, for example, a method of quantifying unreacted monomers by gas chromatography at the end of polymerization.
[0055]
In this invention, it has monomer units other than the benzyl maleimide monomer unit which may have the said substituent, a (meth) acrylic acid monomer unit, and a (meth) acrylic acid ester monomer unit. However, the total mass ratio of essential monomer units is preferably 50% by mass or more, for example. More preferably, it is 70 mass% or more, More preferably, it is 90 mass% or more.
[0056]
The maleimide alkali-soluble copolymer preferably has a monomer unit capable of imparting photocurability (crosslinkability) together with the essential monomer unit. That is, in order to give photocurable to the photosensitive coloring composition of the present invention, a photocurable component having sensitivity at an appropriately selected irradiation wavelength such as radiation such as ultraviolet rays 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, it is possible to improve the irradiation sensitivity of the photosensitive coloring composition. That is, since the photocuring property of the photosensitive coloring composition is excellent, it is possible to shorten the curing time for efficiency, and to improve the accuracy of the pattern shape after development.
[0057]
As the monomer unit capable of imparting photocurability, for example, a monomer unit having a copolymerizable unsaturated bond is preferred, whereby the maleimide-based alkali-soluble copolymer is copolymerized to the side chain. A saturated bond is introduced, and this unsaturated bond contributes to photocurability. In this case, the mass ratio of the monomer unit having an unsaturated bond in the maleimide-based alkali-soluble copolymer is, for example, 1-60 mass% when the maleimide-based alkali-soluble copolymer is 100 mass%. preferable. More preferably, it is 5-40 mass%.
[0058]
The method for producing the maleimide alkali-soluble copolymer is not particularly limited. For example, a benzyl maleimide monomer, a (meth) acrylic acid monomer, and a (meth) acryl which may have a substituent. It can be produced by copolymerizing a monomer component containing an acid ester monomer as an essential component. Thereby, 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 alkali-soluble copolymer is in the above range. Incidentally, in response to the fact that the maleimide-based alkali-soluble copolymer may have a monomer unit other than the essential monomer unit, the monomer 1 type or 2 other than the essential monomer. You may use the monomer component containing a seed | species or more.
[0059]
Examples of the benzyl maleimide monomer that may have a substituent in the monomer unit include alkyl-substituted benzyl maleimides such as benzyl maleimide, p-methylbenzyl maleimide, and p-butylbenzyl maleimide; p-hydroxybenzyl Examples include phenolic hydroxyl group-substituted benzyl maleimides such as maleimide; benzyl maleimide monomers having a substituent on the benzyl group such as halogen-substituted benzyl maleimides such as o-chlorobenzyl maleimide, o-dichlorobenzyl maleimide, and p-dichlorobenzyl maleimide. It is done. Examples of the (meth) acrylic acid monomer include acrylic acid and methacrylic acid. Furthermore, as the (meth) acrylic acid ester monomer, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylic acid 2-ethylhexyl etc. are mentioned. “(Meth) acrylic acid” means that either acrylic acid or methacrylic acid may be used.
[0060]
The monomer other than the essential monomers is not particularly limited, and examples thereof include aromatic substituted maleimides such as phenylmaleimide, naphthylmaleimide, o-chlorophenylmaleimide; methylmaleimide, ethylmaleimide, propylmaleimide, isopropylmaleimide, and the like. Alkyl-substituted maleimides; aromatic vinyl monomers such as styrene, α-methylstyrene, p-methylstyrene, and p-chlorostyrene; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; unsaturated dicarboxylic acids such as maleic anhydride An acid anhydride etc. are mentioned.
[0061]
In the above production method, when the maleimide-based alkali-soluble copolymer itself is provided with photocurability, the maleimide-based alkali-soluble copolymer has a monomer unit having a copolymerizable unsaturated bond as a constituent element. In the case of preparing a copolymer having a carboxyl group by carrying out copolymerization using an unsaturated carboxylic acid, a compound having a functional group capable of binding to the carboxyl group and a copolymerizable unsaturated bond is prepared. Produced by a method of reacting or preparing a copolymer having a cyano group by copolymerization using a compound having a cyano group and a copolymerizable unsaturated bond, and then reacting with an unsaturated carboxylic acid. Is preferred.
[0062]
In the above case, for example, (meth) acrylic acid is preferably used as the unsaturated carboxylic acid. Examples of the compound having a functional group capable of binding to a carboxyl group and a copolymerizable unsaturated bond include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, α-ethyl glycidyl acrylate, crotonyl glycidyl ether, itaconic acid. Compounds having an oxirane ring and a copolymerizable unsaturated bond such as monoalkyl monoglycidyl ester; unsaturated alcohols such as allyl alcohol, 2-blanc-1-ol-freefuryl alcohol, oleyl alcohol, 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. Furthermore, as the compound having a cyano group and a copolymerizable unsaturated bond, for example, the above-described vinyl cyanide compound is preferably used.
[0063]
A preferred form for producing the maleimide-based alkali-soluble copolymer is, for example, a method of polymerizing monomer components using a radical polymerization initiator and, if necessary, a molecular weight regulator. In this case, the polymerization can be performed by bulk polymerization, solution polymerization, suspension polymerization, dispersion polymerization, emulsion polymerization, or a combination of these as appropriate. Among these, it is preferable to perform polymerization by solution polymerization. More preferably, the polymerization is performed by batch solution polymerization.
[0064]
When producing a 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 monomer to be copolymerized, the use ratio, etc. Good. For example, the solvent used for the polymerization by solution polymerization should be a liquid that does not hinder solution polymerization and can dissolve both the monomer component as a raw material and the maleimide-based alkali-soluble copolymer to be produced. Examples thereof include, but are not limited to, for example, aliphatic alcohols having 1 to 3 carbon atoms such as methanol, ethanol and glycol; cellosolvs such as cellosolve and butylcellosolve; carbitols such as carbitol and butylcarbitol; 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, dimethyl It can be used organic solvents having a polarity such as formamide. The solvent used for the polymerization by non-aqueous dispersion polymerization may be a liquid in which the monomer component as a raw material can be dissolved and the maleimide alkali-soluble copolymer to be formed is insoluble. For example, liquid hydrocarbons such as benzene, toluene, hexane, and cyclohexane, other nonpolar organic solvents, and the like can be used. These may be used alone or in combination of two or more. As a quantity of the solvent used for solution polymerization or non-aqueous dispersion polymerization, it is preferable to set it as 20-80 mass% among the total amount of all the monomers and a solvent, for example. If it is less than 20% by mass, there is a possibility that sufficient stirring cannot be performed due to thickening at the end of polymerization. If it exceeds 80% by mass, the molecular weight of the maleimide-based alkali-soluble copolymer to be produced becomes too small. There is a fear. More preferably, it is 30-70 mass%.
[0065]
As said radical polymerization initiator, 1 type (s) or 2 or more types, such as a well-known radical polymerization initiator, for example, a peroxide, an azo initiator, can be used. As a usage-amount of a polymerization initiator, it is preferable to use in the ratio of 0.001-5.0 mass% with respect to 100 mass% of all monomer components, for example, More preferably, it is 0.5-3.0. % By mass. Moreover, as a molecular weight regulator, 1 type (s) or 2 or more types, such as (alpha) -methylstyrene dimer and a mercaptan-type chain transfer agent, can be used, for example. Among these, a long chain alkyl mercaptan having 8 or more carbon atoms is preferable in terms of odor and little coloring.
[0066]
What is necessary is just to set suitably as polymerization temperature in copolymerization by the radical polymerization initiator etc. to be used, Although it does not specifically limit, For example, it is preferable to set it as 50-200 degreeC. When the temperature is lower than 50 ° C., it is necessary to use an initiator having a low decomposition temperature, which 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 undergo thermal polymerization before reaching the decomposition temperature of the initiator. Preferably, it is 80-150 degreeC.
[0067]
When producing a maleimide-based alkali-soluble copolymer by the above-described production method, the maleimide-based alkali-soluble copolymer may be separated and used after removing the volatile matter from the reaction solution after the completion of the polymerization reaction. You may use in a solution state, without isolate | separating a part. The method for separating the maleimide-based alkali-soluble copolymer is not particularly limited. For example, a method in which the reaction solution is heated under vacuum, a method in which the reaction solution is poured into a poor solvent, precipitated, and filtered are applied. be able to.
[0068]
Benzyl maleimide monomer that may have an unreacted substituent in the maleimide-based alkali-soluble copolymer, that is, benzyl maleimide monomer that may have a remaining substituent, It is preferable that it is 3 mass% or less with respect to 100 mass% of coalescence. If it exceeds 3% by mass, the thermal stability may be deteriorated or coloring may be caused. Moreover, since the benzyl maleimide monomer which may have a substituent is highly toxic, it is not preferable that the residual amount is large in this respect as well. More preferably, it is 1 mass% or less, Most preferably, it is 0.5 mass% or less.
[0069]
The remaining amount of monomer components other than the benzylmaleimide monomer which may have a substituent in the maleimide-based alkali-soluble copolymer is 5% with respect to 100% by mass of the maleimide-based alkali-soluble copolymer. % Or less is preferable. If the residual monomer exceeds 5% by mass, the thermal stability may be reduced or coloring may be caused. More preferably, it is 3 mass% or less, Most preferably, it is 1 mass% or less.
[0070]
The molecular weight of the maleimide 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, the heat resistance and thermal stability may be lowered, and if it exceeds 50,000, the solubility in alkaline water may be lowered. More preferably, it is 5000-35000, More preferably, it is 7000-32000. Moreover, it is preferable that ratio (Mw / Mn) of the mass average molecular weight and number average molecular weight measured by GPC (gel permeation chromatography) is 4.0 or less. If it exceeds 4.0, thermal stability and alkali water solubility may be reduced. More preferably, it is 3.0 or less, More preferably, it is 2.5 or less.
[0071]
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 with an unsaturated carboxylic acid, 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 the residue (soil) is affected not only by the acid value of the maleimide alkali-soluble copolymer but also by the hydroxyl value.
In the present invention, particularly in a high concentration region of the pigment (for example, when the solid content in the photosensitive coloring composition is 100%, the pigment mass is 15% or more, preferably 20% or more), Residues were likely to remain, but by setting the acid value and hydroxyl value of the maleimide-based alkali-soluble copolymer within the above ranges, the residue residue can be extremely reduced.
Specific examples of the maleimide alkali-soluble copolymer having an acid value and a hydroxyl value in the above range include a benzyl maleimide monomer optionally having a substituent, a (meth) acrylic acid ester monomer, and Benzyl, which is a copolymer obtained by reacting glycidyl (meth) acrylate as an unsaturated carboxylic acid for imparting photocurability after copolymerizing (meth) acrylic acid monomer, and constituting the main chain skeleton Maleimide monomer unit (A), (meth) acrylic acid ester monomer unit (B), (meth) acrylic acid monomer unit (C), and
The copolymerization ratio (A / B / C / D) of the unit (D) in which glycidyl (meth) acrylate is additionally introduced into the (meth) acrylic acid monomer unit is
(5-10 / 15-85 / 5-30 / 5-60), preferably (5-25 / 20-80 / 5-5-15 / 10-50), most preferably (5-25 / 30-70 / The thing in the range of 5-15 / 10-30) can be mentioned.
[0072]
Since the binder component composed of such a maleimide-based alkali-soluble copolymer has excellent pigment dispersion performance, a pigment dispersion composition and a photosensitive coloring composition are prepared using the binder instead of a dispersant. be able to.
[0073]
A pigment dispersion composition can be prepared by blending the maleimide-based alkali-soluble copolymer with a pigment in a solvent and supplementing a dispersant as necessary.
[0074]
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 admixture of two or more.
[0075]
As the organic colorant, for example, dyes, organic pigments, natural pigments, and the like can be used. Specific examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists), that is, the following color index (C.I. ) Can be listed.
[0076]
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 C.I. 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 pigments such as C.I. Pigment Red 177; I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. C.I. Blue pigments such as CI Pigment Blue 15: 6; I. Violet pigments such as CI Pigment Violet 23:19; and green pigments such as Pigment Green 36.
[0077]
Examples of the inorganic colorant include inorganic pigments and extender pigments. Specific examples include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red rose ( Red iron oxide (III)), cadmium red, ultramarine blue, bitumen, chromium oxide green, cobalt green, amber, titanium black, synthetic iron black, carbon black and the like.
[0078]
The maleimide-based alkali-soluble copolymer used in the present invention is excellent in affinity with a phthalocyanine-based pigment used as a blue or green pigment. Examples of the phthalocyanine pigment include phthalocyanine blue pigments such as copper phthalocyanine.
[0079]
Further, the maleimide-based alkali-soluble copolymer used in the present invention is excellent in yellowing resistance during heating, and thus forms a blue coating film, particularly a blue pixel of a color filter, whose color characteristics are significantly deteriorated by yellowing. Very suitable as a binder component. Therefore, this 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 blue pigments. It is particularly preferable because of its excellent affinity.
[0080]
By blending the maleimide-based alkali-soluble copolymer in a proportion 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.
[0081]
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 regarded 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. A smaller amount of the dispersant is more preferable, but when used, the ratio of the pigment to the dispersant is generally set to 0.05 or more in order to make the dispersing action of the dispersant effective.
[0082]
The dispersant that can be used is not particularly limited. For example, cationic, anionic, nonionic, amphoteric, silicone, and fluorine-based surfactants can be used. Among these, polymeric surfactants (polymers) It is preferable to use a dispersant. Examples of the polymer surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, etc. Polyoxyethylene alkylphenyl ethers; polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid-modified polyesters; tertiary amine-modified polyurethanes.
[0083]
As a solvent (dispersion solvent) for preparing the pigment dispersion composition, an organic solvent is preferably used. As an organic solvent, in order to prepare the photosensitive coloring composition mentioned later, the organic solvent used as a dilution solvent can be used.
[0084]
The dispersion solvent is usually used in a proportion of 100 to 1000 parts by mass, preferably 200 to 900 parts by mass with respect to 100 parts by mass of the pigment.
[0085]
In the present invention, the pigment dispersion composition can be prepared by replacing part or all of the dispersant with the maleimide-based alkali-soluble copolymer in a conventionally known procedure for preparing a pigment dispersion composition. That is, the pigment, the maleimide-based alkali-soluble copolymer, and other components as necessary are mixed in a solvent in an arbitrary order, and kneader, roll mill, attritor, super mill, dissolver, homomixer, sand mill. A pigment dispersion composition can be prepared by dispersing using a known disperser such as the above.
[0086]
Specifically, a method in which a mixture of an organic pigment and a binder is added and dispersed in a solvent, a method in which a pigment and a binder are added and dispersed in a solvent; a liquid in which only a pigment is dispersed in a solvent; and a binder only in a solvent Examples thereof include a method of mixing the dispersed liquid or a method of adding a binder to a liquid in which only the pigment is dispersed in a solvent.
[0087]
In this way, a pigment dispersion composition having excellent pigment particle dispersibility is obtained. This pigment dispersion composition is used as a preliminary preparation for preparing a coating liquid excellent in pigment dispersibility. If a pigment or a pigment dispersant is directly added and mixed with a binder component in a diluent solvent, sufficient dispersibility may not be obtained. In contrast, the pigment dispersion composition according to the present invention is mixed with an additional amount of the binder and other components, or the pigment dispersion composition according to the present invention, the additional amount of the binder, and other components are mixed into the solid content. By adding to a solvent (dilution solvent) for adjusting the concentration, a coating liquid excellent in pigment dispersibility can be easily prepared.
[0088]
In the present invention, a photosensitive coloring composition containing one or more pigments and the maleimide-based alkali-soluble copolymer, radical polymerizable compound and photopolymerization initiator as essential binder components is prepared. Can do. The maleimide alkali-soluble copolymer, radical polymerizable compound and photopolymerization initiator may be used alone or in combination of two or more.
[0089]
The photosensitive coloring composition of the present invention is applied to a color filter substrate and exposed to light, whereby the maleimide-based alkali-soluble copolymer has excellent physical properties and alkali developability, and a three-dimensional formed by a radically polymerizable compound. With the network structure, it is possible to form a cured film with excellent physical properties such as adhesion to the surface of the substrate (substrate surface), film strength, heat resistance, hot pure water resistance, chemical resistance, etc. When it is exposed and developed in the shape, an accurate pattern can be formed, and no residue remains in the removed portion during development.
[0090]
As a compounding quantity of the said maleimide type | system | group alkali-soluble copolymer, it is preferable to set it as 5-80 mass% with respect to 100 mass% of photosensitive coloring compositions, for example. If it is less than 5% by mass, the viscosity becomes too low, and there is a fear that the coating film stability after coating and drying may not be sufficient. If it exceeds 80% by mass, the viscosity becomes too high and the fluidity decreases, There is a risk of inconvenience such as poor applicability. More preferably, it is 10-50 mass%.
[0091]
As a pigment mix | blended with the photosensitive coloring composition, the same thing as what can be mix | blended with the pigment dispersion liquid mentioned above can be used. Since the maleimide-based alkali-soluble copolymer used in the present invention has high affinity with the pigment, the pigment can be finely dispersed without reducing or using the dispersant in the photosensitive coloring composition. Since the pigment can be finely dispersed, the transparency of the colored cured film can be improved. Moreover, when the amount of the dispersant is reduced, the blending 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 can be improved by increasing the blending ratio of the pigment, and the ability to form a fine pattern and the film after curing can be increased by increasing the blending ratio of the binder component that contributes to curability and developability. Physical properties can be improved.
[0092]
The maleimide-based alkali-soluble copolymer has a particularly high affinity with phthalocyanine pigments. Therefore, when used in combination with phthalocyanine pigments, it has excellent transparency, color characteristics, ability to form fine patterns, and a film after curing. Physical properties can be obtained.
[0093]
Further, since the maleimide-based alkali-soluble copolymer is excellent in yellowing resistance as described above, it is very effective to be combined with a blue pigment that has a remarkable adverse color tone due to yellowing. The phthalocyanine blue pigment is particularly preferable because of its excellent affinity.
[0094]
As a compounding quantity of the said pigment, it is preferable to set it as 40-75 mass% with respect to 100 mass% of photosensitive coloring compositions, for example. If it is less than 40% by mass, the coloring power will not be sufficient, so there is a risk that it will be difficult to display a clear image, and if it exceeds 75% by mass, there is a risk of inconveniences such as insufficient light transmittance of the colored film. is there. More preferably, it is 45-70 mass%.
[0095]
In order to disperse the pigment uniformly and stably, the photosensitive coloring composition may contain one or more dispersants. As such a dispersing agent, the same thing as what can be mix | blended with the pigment dispersion liquid mentioned above 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 the case.
[0096]
The radically polymerizable compound is not particularly limited as long as it is a compound capable of generating a crosslink by light irradiation and curing the photosensitive coloring composition. For example, three ethylenically unsaturated bonds are contained in one molecule. It is preferable to use the photopolymerizable compound (trifunctional or higher functional photopolymerizable compound) as described above. In addition, a bifunctional photopolymerizable compound or the like can be used. As the tri- or higher functional photopolymerizable compound, for example, poly (meth) acrylates of trihydric or higher polyhydric alcohols or their dicarboxylic acid-modified products 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 Etc. Among these, it is preferable to use dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate. “(Meth) acrylate” means that either acrylate or methacrylate may be used.
[0097]
As a compounding quantity of the said radically polymerizable compound, it is preferable to set it as 5-70 mass% with respect to 100 mass% of photosensitive coloring compositions, for example. If it is less than 5% by mass, there is a possibility that unexposed portions will be lost during development. If it exceeds 70% by mass, the viscosity becomes too low and the coating film stability after coating and drying becomes insufficient. And there is a risk of inconvenience such as impairing the suitability of development. More preferably, it is 10-40 mass%.
[0098]
In the photosensitive coloring composition of the present invention, one or more monofunctional photopolymerizable monomers and the like as a reaction diluent can be blended as necessary together with the radical polymerizable compound. Specific examples of such a compound include (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and the like.
[0099]
The photopolymerization initiator is not particularly limited as long as it is a compound that can generate active species such as radicals, cations, and anions by radiation having a wavelength of 365 nm or less, and can initiate the polymerization reaction of the above-described radical polymerizable compound. Although it is not a thing, it is preferable that it is a thing with high solubility to 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; xanthone and thioxanthone derivatives; chlorosulfonyl Halogen-containing compounds such as chloromethyl polynuclear aromatic compounds, chloromethyl heterocyclic compounds, chloromethyl benzophenones; triazines; imidazolines; fluorenones; haloalkanes; redox couples of photoreductive dyes and reducing agents; Organic sulfur compounds; peroxides and the like. Among these, it is preferable to use triazines and imidazolines.
[0100]
As a compounding quantity of the said photoinitiator, it is preferable to set it as 0.05-20 mass% with respect to 100 mass% of photosensitive coloring compositions, for example. If it is less than 0.05% by mass, the curability of the coating film formed from the photosensitive coloring composition may not be sufficient, and if it exceeds 20% by mass, the unexposed part will be lost during development. Or the coating film may turn yellow after post-baking. More preferably, it is 2 to 15% by mass.
[0101]
The photosensitive coloring composition of the present invention may contain one or more components other than the above-described essential components as necessary, for example, a sensitizer; heat that reacts with an acid by heating and cures. It is preferable to contain a curable resin.
[0102]
When the sensitizer is contained, the sensitivity of the photosensitive coloring composition can be improved. As such a sensitizer, a styryl compound or a coumarin compound is preferably used. Specifically, as the styryl 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.
[0103]
As a compounding quantity of the said sensitizer, it is preferable to set it as 0.01-50 mass% with respect to 100 mass% of photosensitive coloring compositions, for example.
[0104]
When a thermosetting resin that cures by reacting with an acid by heating is contained, a photosensitive coloring composition is applied to the surface of the substrate, and a cured pattern is formed by exposing and developing in a desired pattern. Then, 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, so that the alkali resistance is improved and the thermosetting resin is used. The physical properties of the cured pattern are improved by the crosslinking reaction. As a result, the heat resistance, adhesion, warm 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.
[0105]
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, a bisphenol A type epoxy resin or a bisphenol F type epoxy resin. 1 type (s) or 2 or more types, such as a phenol novolac type epoxy resin and a cresol novolac type epoxy resin.
[0106]
As a compounding quantity of the said thermosetting resin, it is preferable to set it as 1-20 mass% with respect to 100 mass% of photosensitive coloring compositions, for example. If it is less than 1% by mass, there is a possibility that sufficient alkali resistance may not be imparted to the coating film formed by curing the photosensitive coloring composition, and if it exceeds 20% by mass, There is a risk of inconveniences such as deterioration in storage stability and developability. More preferably, it is 3 to 15% by mass.
[0107]
Various additives other than those described above can be blended in the photosensitive coloring composition of the present invention as necessary. Examples of such an additive include silane coupling agents such as vinyl silane, acrylic silane, and epoxy silane. By adding such an additive, adhesion to a substrate and other adjacent coating layers is exemplified. Can be improved.
[0108]
The method for producing the photosensitive coloring composition of the present invention is not particularly limited. For example, the pigment, the maleimide-based alkali-soluble copolymer, the radical polymerizable compound, the photopolymerization initiator, and, if necessary, the above-described essential components It can be produced by a method in which things other than the components are mixed or added to a solvent and stirred to dissolve and disperse uniformly. It is also possible to produce a photosensitive coloring composition using the above-described pigment dispersant. In such a production method, the mixing order and the like are not particularly limited. Examples of the 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.
[0109]
Although the usage form of the photosensitive coloring composition of the present invention is not particularly limited, it is usually diluted with a solvent in consideration of coating and applicability. As such a solvent, it is preferable to use a solvent that dissolves a maleimide-based alkali-soluble copolymer, a radical polymerizable compound, a photopolymerization initiator, and the like, has a high boiling point, and good spin coating properties. For example, alcohol solvents such as methyl alcohol, ethyl alcohol, N-propyl alcohol and i-propyl alcohol; cellosolv solvents such as methoxy alcohol and ethoxy alcohol; carbitol solvents such as methoxyethoxyethanol and ethoxyethoxyethanol; ethyl acetate Ester solvents such as 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; Examples include unsaturated hydrocarbon solvents such as benzene, toluene, xylene and naphthalene; organic solvents such as saturated hydrocarbon solvents such as N-heptane, N-hexane and N-octane. Can be used. Among these, it is preferable to use 3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, or the like.
[0110]
The amount of the solvent used is appropriately adjusted depending on the dissolved state of the compounding components, coating properties, and the like, but it is usually preferable that the solid concentration is 5 to 50% by mass.
[0111]
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 this invention is apply | coated to the surface of to-be-coated bodies, such as a board | substrate, and ionizing radiation, such as an ultraviolet-ray and an electron beam, is irradiated and hardened | cured to the formed coating film. When the coating film is irradiated with ionizing radiation, active species are first generated from the photopolymerization initiator by the action of ionizing radiation in the coating film, and the crosslinking reaction of the radical polymerizable compound is initiated by the action of the active species. The film is cured.
[0112]
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, and the predetermined pattern is exposed and developed. Since the maleimide-based alkali-soluble copolymer has a carboxyl group, the coating film can remove unexposed portions where the radically polymerizable compound is not cross-linked by alkali development. A cured film can be formed.
[0113]
The coating film is exposed and cured, developed as necessary, and then further cured by heating to obtain a cured film. When an ethylenically unsaturated bond derived from a radical polymerizable compound remains in the exposure-cured coating film, the crosslinking reaction can be further advanced by a heating step. Further, when the coating film contains a thermosetting resin such as a bifunctional epoxy resin, it reacts with the carboxyl group of the maleimide alkali-soluble copolymer remaining in the coating film. , While consuming the carboxyl group, it causes cross-linking. As a result, the heat resistance, adhesion, hot pure water resistance, and chemical resistance (particularly alkali resistance) of the cured film are improved.
[0114]
The colored cured film formed using the photosensitive coloring 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.
[0115]
Regarding color characteristics, particularly when a blue cured film is formed, bright pixels with high transparency can be formed. Specifically, the photosensitive coloring composition was applied onto a glass substrate by spin coating, dried at 80 ° C. for 3 minutes, and 100 mJ / cm. ² After the exposure with this irradiation amount, it can be heated at 230 ° C. for 30 minutes to form a blue cured film. The blue cured film thus obtained has a thickness of 1.35 μm or less, and when the color is measured with a single pixel, the x coordinate is 0.05 ≦ 0.05 in the C light source color measurement XYZ color system 2 degree visual field. A color space in the range of x ≦ 0.30, y coordinate 0.05 ≦ y ≦ 0.30, and stimulus value Y of 20.0 or more, preferably 21.0 or more can be displayed.
[0116]
The color filter is manufactured through a heating process involving high temperature such as post-baking or polyimide alignment film formation. If the color layer forming material turns yellow in such a heating process, it causes wavelength absorption near 400 nm. The color characteristics of the layer are deteriorated, and among the colors, the color tone deterioration and the luminance decrease of the blue pixel are most remarkable. On the other hand, since the photosensitive coloring composition according to the present invention uses a maleimide-based alkali-soluble copolymer having high heat resistance, it is difficult to cause yellowing and forms a blue cured film having high heat resistance regarding color tone. be able to.
[0117]
Specifically, the photosensitive coloring composition of the present invention is applied onto a glass substrate by spin coating, dried at 80 ° C. for 3 minutes, and 100 mJ / cm. ² After the exposure with the irradiation amount, a blue cured film having a film thickness of about 1.3 μm can be formed by heating at 230 ° C. for 30 minutes. Assuming a heating process for producing a color filter on this blue cured film, a heat resistance test is performed by heating at 250 ° C. for 1 hour, and before and after the heat resistance test, the C light source color measurement XYZ color system 2 field of view, y When the stimulus value Y value at 0.1400 is measured, the change rate (Y2 / Y1) of the measured value Y2 after the test with respect to the measured value Y1 before the test can be maintained at 97% or more.
[0118]
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. Yes.
[0119]
In the negative resist development process, the uncured unexposed portion of the resist layer is dissolved by the alkali developer and leaves the substrate. However, as the development form, the portion to be removed is mainly large. There are a peelable type that peels off as a lump and a dissolved type that gradually dissolves and diffuses so that the dye dissolves in water. The former peeling type is a development form that is not preferred because a solid lump remains as a foreign substance and remains in the system and easily contaminates pixels of other colors. On the other hand, the photosensitive coloring composition of the present invention is the latter dissolution type and takes a preferable development form.
[0120]
Since the photosensitive coloring composition of the present invention has a shorter development time compared to the case of using an acrylic resin-based binder, the throughput is shortened accordingly, and the amount of developer used and the development line can be shortened. is there.
[0121]
In the developing process of the negative resist, the uncured unexposed portion of the resist layer is dissolved by the alkali developer and separated from the substrate, but the resist remains on the substrate without being sufficiently detached. There is a case. If a pixel is formed by applying and developing a resist of another color in a place where such a development residue remains, adverse effects such as a change in color characteristics and a decrease in smoothness are caused. On the other hand, since the photosensitive coloring composition of the present invention does not leave a residue in the dissolved portion during development, the quality of pixels other than blue is also improved.
[0122]
In general, if the residue is reduced, the solubility of the resist becomes too strong, resulting in problems such as surface roughness, poor adhesion and reduced resolution, and the accuracy of the pattern is impaired. A colored cured film produced using a product is accurately formed in a predetermined pattern without leaving a residue in a portion to be removed by development.
[0123]
Specifically, the colored cured film obtained can have a surface roughness (Ra) of 50 mm or less, preferably 30 mm or less, in a measurement method based on JIS B0601-1994.
[0124]
The colored cured film can have a line width of 25 μm or less, preferably 20 μm or less, which causes defects when a photosensitive colored composition coating film is exposed and cured through a line-and-space mask. Excellent in properties.
[0125]
The colored cured film may have a resolution of 24 μm or less, preferably 20 μm or less, when the coating film of the photosensitive colored composition is exposed and cured through a line and space mask.
[0126]
The photosensitive coloring composition of this invention is preferable also in the point that the cross-sectional shape of a cured film can be formed in a taper shape. When a colored resist is applied on the substrate and the coating film is developed, the cross-sectional shape of the resulting colored layer is such that the length of the lower base (contact surface with the substrate) is the upper base (surface facing the contact surface with the substrate). When the taper shape (trapezoidal shape) is larger than the length (ie (upper surface / lower surface) <1), when the cross-sectional shape is rectangular (ie (upper surface / lower surface) = 1), and the lower bottom of the cross-sectional shape May have a reverse tapered shape (reverse trapezoidal shape) that is smaller than the length of the upper base (that is, (upper surface / lower surface)> 1).
[0127]
When the cross-section of the colored layer is inversely tapered, when the ITO electrode layer is deposited on the colored layer, the ITO does not sufficiently wrap around the side surface of the colored layer, and the portion where the ITO layer cannot be formed is near the lower bottom. It is left and cannot conduct, or a large resistance value is partially generated, causing a problem in the electrode layer. Such a problem occurs when a color filter pixel pattern is formed using a colored resist. In addition, the reverse-tapered colored layer has corners that fall off during the various processes and falls off and adheres to other parts of the color filter, which causes soiling. Therefore, it is desirable that the colored layer pattern formed by applying, developing, and post-baking a resist on a substrate has a tapered shape (trapezoidal shape) in cross section. In response to this demand, when the photosensitive coloring composition of the present invention is used, a blue layer pattern having a tapered shape (substantially trapezoidal shape, (upper surface / lower surface) <1) is formed. Alternatively, soiling can be prevented.
[0128]
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 coated surface. it can. Alternatively, the cross-sectional shape of the colored cured film can be such that the ratio of the length of the upper base to the length of the lower base is less than 1.
[0129]
Regarding the contrast, when the blue cured film is formed using the photosensitive coloring composition of the present invention, the contrast ratio can be 2,000 or more.
[0130]
Regarding the 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, warm pure water resistance, chemical resistance, and impurity elution. .
[0131]
For example, regarding the hardness, the photosensitive coloring composition of the present invention is applied onto a glass substrate by spin coating, and 100 mJ / cm. ² When a coating film having a film thickness of 5 μm is formed by heating at 200 ° C. for 30 minutes after exposure at a dose of 1, the surface hardness of the coating film is measured under conditions where the surface temperature is 180 ° C. and the maximum load is 20 mN. Universal hardness (test load / surface area of Vickers indenter under test load) at 200 N / mm ² This can be done. Regarding universal hardness, material testing technology vol. 43, no. 2 (1998) p. 72 and can be evaluated according to the German standard DIN 50359-1.
[0132]
Using such a photosensitive coloring composition, a colored coating film containing a blue colored cured film or a phthalocyanine pigment can be formed in various fields. This photosensitive coloring composition is particularly suitable for forming a pattern of pixels containing a blue pixel or 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.
[0133]
The color filter essentially includes a transparent substrate and a colored layer formed on the transparent substrate, and further maintains a distance between the protective film covering the colored layer and / or the electrode substrate facing the transparent layer as necessary. In order to do so, a spacer provided at a position overlapping the non-display portion on the transparent substrate is provided. In the present invention, such a color filter pixel pattern, particularly a blue pixel, is formed using the photosensitive coloring composition.
[0134]
As a form of the color filter, (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 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. In addition, a transparent electrode for driving liquid crystal may be formed on the protective film as necessary. The method for forming the black matrix is not particularly limited, and 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. Moreover, you may form by chromium vapor deposition etc.
[0135]
The colored layer is usually arranged in a desired form such as an island type in which red, green, and blue pixel patterns are arranged in a mosaic type, a stripe type, a triangle type, a four-pixel arrangement type, and a "<" shape. Thus, the black matrix is provided between the colored patterns and in a predetermined area outside the colored layer forming area.
[0136]
In the present invention, at least one of the pixel patterns constituting such a colored layer, in particular, a blue pixel pattern is prepared using the photosensitive coloring composition. For example, the above-mentioned photosensitive coloring composition is applied to one surface side of a transparent substrate, exposed by irradiating with radiation such as ultraviolet rays through a photomask, and after being developed with an alkali, it is heated and cured in a clean oven or the like to form a colored layer. Can be formed. The thickness of the colored layer is usually preferably about 1.5 μm.
[0137]
As a method for forming the protective film, for example, a coating liquid of a transparent photosensitive coloring composition can be applied and formed by a method such as a spin coater, a roll coater, a spray, or printing. When using a spin coater, the number of revolutions is set within a range of 500 to 1500 revolutions / minute. The coating film of the photosensitive coloring composition is exposed by irradiating ionizing radiation through a photomask, and after alkali development, it is heated and cured in a clean oven or the like to form a protective film. The thickness of the protective film is usually preferably about 2 μm.
[0138]
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. The film is formed by a general method such as a vacuum deposition method or 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 about 20 to 500 nm, for example. More preferably, it is about 100 to 300 nm.
[0139]
The spacer is preferably a columnar spacer having a height corresponding to the cell gap. For example, the spacer is preferably provided on the transparent electrode, the colored layer, or the protective film in accordance with the region where the black matrix layer is formed. As a method of forming columnar spacers on a transparent electrode or the like, for example, a coating liquid of a transparent photosensitive coloring composition is applied by a method such as spin coater, roll coater, spray, printing, etc., and radiation through a photomask It can be formed by exposure by irradiation, alkali development, and heat curing in a clean oven or the like. The rotational speed of the spin coater may be set within a range of 500 to 1500 revolutions / minute, as in the case of forming the protective film. The thickness (height) of the columnar spacer is preferably about 5 μm, for example.
[0140]
A liquid crystal display device in which the color filter and the electrode substrate thus produced are opposed to each other and a liquid crystal compound is sealed between them 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, and filling the gap portion with a liquid crystal compound and sealing. The liquid crystal compound used in the liquid crystal display device of the present invention is not particularly limited. Moreover, it does not specifically limit as an electrode substrate, What was manufactured by the normal method can be used.
[0141]
In such a liquid crystal display device, the effects of the photosensitive coloring composition are sufficiently exhibited, the basic performance is excellent, and the quality of the display image is excellent, so that a flat display such as a personal computer is used. The present invention can be suitably applied as a display device.
[0142]
【Example】
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by mass” and “%” means “% by mass”.
[0143]
Example 1
(1) Synthesis of benzylmaleimide resin
A 30 L polymerization tank was charged with 40.0 parts of diethylene glycol dimethyl ether (DMDG) as a solvent, heated to 90 ° C. under a nitrogen atmosphere, and then added dropwise with dropper system 6.16 parts of benzyl maleimide (BzMI), diethylene glycol dimethyl ether (DMDG). ) 6.16 parts, methyl methacrylate (MMA) 12.12 parts, methacrylic acid (MAA) 12.55 parts, dropping system 2, perbutyl O (PBO) (trade name, manufactured by NOF Corporation) 0.62 parts, As dropping system 3, 1.23 parts of n-dodecyl mercaptan (n-DM) was continuously supplied over 3 hours. Then, after maintaining 90 degreeC for 30 minutes, temperature was heated up to 105 degreeC and superposition | polymerization was continued for 3 hours. The unreacted monomer as measured by gas chromatography (GC) was 0.1% BzMI, 0.2% MMA, and 0.3% MAA.
[0144]
Next, 12.73 parts of glycidyl methacrylate (GMA), 0.13 part of triethylamine as a catalyst, and 2,2′-methylenebis (4-methyl-6-tert-butylphenol) as a polymerization inhibitor (trade name Antage) W400 (manufactured by Kawaguchi Chemical Industry Co., Ltd.) was added, and the reaction was continued for 8 hours while 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, unreacted GMA was not detected. After adding and diluting 7.5 parts of DMDG, it cooled and the benzyl maleimide resin solution 1 was obtained.
[0145]
(2) Preparation of blue pigment dispersion composition
The benzyl maleimide resin solution 1 together with the pigment and the dispersant was mixed in the following amount, and the beads were dispersed with 0.3 mm zirconia beads for 3 hours using a paint shaker to obtain a blue pigment dispersion composition 1. The resulting blue pigment dispersion composition 1 had a solid content mass ratio (pigment / dispersant / benzylmaleimide resin) of the pigment, dispersant and benzylmaleimide resin of 1 / 0.2 / 0.4.
[0146]
<Composition of Blue Pigment Dispersion Composition 1>
Pigment Blue 15: 6 (copper phthalocyanine-based 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)
Benzylmaleimide resin solution 1 (BzMI / MMA / MAA / GMA-MAA copolymer, solid content 44.4% by mass): 11.56 parts by mass
Propylene glycol monomethyl ether acetate: 69.79 parts by mass
(3) Preparation of blue resist
A blue resist 1 was prepared by blending the benzyl maleimide resin solution 1 and other components into the blue pigment dispersion composition 1 in the following amounts. The obtained blue resist 1 is composed of benzyl maleimide resin as a main polymer, dipentaerythritol pentaacrylate as a monomer (trade name Sartomer SR399E, manufactured by Nippon Kayaku Co., Ltd.), and masses of solid contents of initiators 1 and 2 The ratio (benzylmaleimide resin / dipentaerythritol pentaacrylate / initiator 1 and 2 total) was 35/45/35.
[0147]
<Composition of blue resist 1>
Blue pigment dispersion composition 1: 34.3 parts by mass
Benzylmaleimide resin solution 1 (BzMI / MMA / MAA / GMA-MAA copolymer, solid content 44.4% 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 Pharmaceutical): 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 of the blue pigment dispersion composition 1 excluding the benzyl maleimide resin solution 1 was used.
[0148]
Further, in Example 1, instead of the benzylmaleimide resin solution 1, the same amount of acrylic resin (trade name B-7500, manufactured by Shin-Nakamura Chemical Co., Ltd.) was used to prepare a blue resist C1 as a comparative example.
[0149]
(Analysis and evaluation)
The benzyl maleimide 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 amounts charged.
[0150]
Table 2 shows the results of evaluation by the methods described below using the blue pigment dispersion compositions and blue resists obtained in Examples and Comparative Examples.
[0151]
[Table 1]

[0152]
[Table 2]

[0153]
(1) Analysis method of benzylmaleimide resin solution 1
<Unreacted monomer and copolymer composition>
It was determined by quantifying the unreacted monomer at the end of the polymerization by gas chromatography.
[0154]
<Solid content>
A resin solution (0.3 g) was precisely weighed on an aluminum dish and vacuum-dried at 140 ° C. for 5 hours, and the volatile content was removed.
[0155]
<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, titrated with 0.1N KOH aqueous solution using thymol blue as an indicator, and the acid value per 1 g of the solid content was determined from the concentration of the solid content.
[0156]
<Viscosity>
Place the resin solution in a 300 ml tall beaker, hold it in a constant temperature water bath at 25 ± 0.2 ° C, adjust the temperature to 25 ± 0.5 ° C, and use a B-type digital viscometer (DVM-B type manufactured by Toki Sangyo) In rotor No. The viscosity was measured at 3, 6 rpm.
[0157]
<Moisture content>
A new Karl Fischer titration solvent, Hayashi-Solvent CE (dehydrated solvent) was used, 1 g of the sample was dissolved in 30 g of the titration solvent, and the moisture content was measured with a Karl Fischer measurement device (MKS-3P, manufactured by Kyoto Electronics Industry Co., Ltd.). .
[0158]
<Double bond amount>
The resin solution was vacuum-dried at 70 ° C. for 5 hours to volatilize the solvent, and then 200 MHz 1H NMR (Gemini 2000 / 200BB manufactured by Varian Technologies Japan Limited) was measured using DMSO-d6 as the solvent and chloroform as the internal standard substance. It calculated | required from the absorption intensity of the double bond.
[0159]
<Weight average molecular weight (Mw)>
The weight average molecular weight was measured with Shodex GPC System-21H (Polystyrene) using polystyrene as a standard substance and THF as an eluent.
[0160]
<Glass transition point (Tg)>
Using a DSC8230 (trade name) manufactured by Rigaku Denki Co., Ltd., the polymer alone was measured under a nitrogen stream at a heating rate of 10 ° C./min.
[0161]
<1% KOH solubility>
The polymer solution was diluted with tetrahydrofuran (THF), precipitated in a large amount of hexane, filtered and dried, and the polymer alone was separated, put into 20% of 1% KOH aqueous solution, and stirred for 3 hours. After stirring, if there was any insoluble matter, it was filtered and the amount of insoluble matter was measured and evaluated according to the following criteria.
A: Complete dissolution,
○: Slightly turbid or insoluble content is 10% or less,
Δ: Insoluble content is 10% to 50%,
×: Insoluble content is 50% or more
<Solubility of propylene glycol monomethyl ether acetate (PGMEA) and 3-methoxybutyl acetate (methace)>
Each solvent was added to the precipitated and dissolved polymer so as to be 20%, heated to 60 ° C. and stirred for 3 hours, and then allowed to cool to room temperature. When there was an insoluble matter, it was filtered, the amount of insoluble matter was measured, and evaluated according to the following criteria.
A: Complete dissolution,
○: Slightly turbid or insoluble content is 10% or less,
Δ: Insoluble content is 10% to 50%,
×: Insoluble content is 50% or more
<380 nm transmittance>
The copolymer solution is diluted with diethylene glycol dimethyl ether (DMDG) to a polymer concentration of 20%, and a coating film is formed on a glass substrate using a spin coater. At room temperature for 30 minutes, at 90 ° C. for 30 minutes, at 200 ° C. Heat drying for 30 minutes to form a 2 μm thick coating film. Then, it heated at 250 degreeC for 1 hour, and measured the light transmittance in the range of 380-780 nm.
[0162]
(2) Blue pigment dispersion composition and blue resist evaluation method
(2-1) Pigment dispersibility
The 50% average pigment particle size of the blue pigment dispersion composition was measured using a Nikkiso Co., Ltd. laser Doppler scattered light analysis particle size analyzer (Microtrac 934UPA).
[0163]
(2-2) Development form, development time, spectral characteristics, heat resistance, pattern cross-sectional shape
A blue resist was spin-coated on a glass substrate that had been cleaned with alkali, and then dried at room temperature for 3 minutes and further on a hot plate at 80 ° C. for 3 minutes to form a coating film having a thickness of 1.3 μm. This coating is 100 mJ / cm ² The film was exposed to a mask, spin-developed, and the developer was indirectly liquid for 60 seconds, washed with pure water, and the patterned substrate was baked in an oven at 230 ° C. for 30 minutes. During this development process, whether the development form was a dissolution type or a peeling type was observed, and the development time was measured.
[0164]
Next, the obtained blue-patterned substrate was subjected to brightness Y defined in JIS Z8701 by using a C light source defined by the International Commission on Illumination and using a microspectrophotometer (OSP SP-100) manufactured by Olympus Optical Industry Co., Ltd. The value was measured.
[0165]
Thereafter, the substrate with the blue pattern is heated in an oven at 250 ° C. for 1 hour, the brightness Y value is measured by the same method, and the rate of change in the Y value before and after the test is determined based on the Y value before the heat resistance test. Calculated.
[0166]
Moreover, while observing the cross-sectional shape of the colored layer of the board | substrate with a blue pattern obtained in the stage after baking at 230 degreeC for 30 minutes with SEM (scanning electron microscope), using the SEM photograph, The ratio of the length of the upper base to the length of the lower base was calculated.
[0167]
(2-3) Development residue
A blue resist solution was spin-coated on a glass substrate on which chromium was vapor-deposited on the back surface, and then dried on a hot plate at 80 ° C. for 3 minutes at room temperature to form a coating film having a thickness of 1.3 μm. This coating film was spin-developed, and the developer was indirectly liquid for 60 seconds, followed by washing with pure water.
[0168]
After washing, the glass substrate was visually observed with a projector to confirm the presence or absence of residues. Further, the surface of the substrate was wiped off with a waste cloth with ethanol, and the presence or absence of a residue wiped on the waste cloth was confirmed.
[0169]
(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 (Toshiba Mellow 5D FL10EX-D-H color temperature 6500K) was used. It was turned on, and the luminance when the polarizing plate was orthogonal and parallel was measured with a luminance meter (SL-100 manufactured by Minolta). The contrast ratio can be derived from the following equation using the measured luminance value.
[0170]
Contrast ratio = parallel luminance (cd / m ² ) / Orthogonal luminance (cd / m) ² )
(2-5) Surface roughness, adhesion, resolution, cross peel test
Evaluation on plate making properties (surface roughness (Ra), adhesion and resolution by line and space, cross peel test) was performed. The curable resin composition 1 was applied and dried on a 10-cm glass substrate with a spin coater (Mikasa, model 1H-DX2) 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, 100 mJ / cm by a UV aligner (manufactured by Dainippon Screen, model MA 1200) equipped with a 2.0 kW super high pressure mercury lamp with a photomask placed at a distance of 100 μm from the coating film. ² Was irradiated with ultraviolet rays at an intensity of 405 nm (in terms of illuminance at 405 nm).
[0171]
After UV irradiation, a 0.05 wt% aqueous potassium hydroxide solution was applied to the coating film with a spin developing machine (Applied Process Technology, INK, MODEL: 915) for 60 seconds to dissolve and remove unexposed portions, and the remaining exposure. The part was developed by rinsing with pure water for 60 seconds. After development, the film in the exposed area was heated at 200 ° C. for 30 minutes by a clean oven (manufactured by Shinobu Research Institute, SCOV-250 Hy-So).
[0172]
The surface of the coating film after the alkali development treatment is subjected to AFM measurement using a scanning probe microscope (AS-7B) manufactured by Takano Co., Ltd., and the surface roughness (Ra) defined in JIS B0601-1994 (coating film) Surface smoothness) was determined and evaluated according to the following criteria.
[0173]
<Evaluation criteria for surface roughness>
A: Extremely smooth. (50mm or less)
○: Smooth. (Over 50Å, less than 100Å)
Δ: Roughness is observed on the surface. (100Å or more)
X: The surface is severely roughened and whitening of the coating film is observed.
[0174]
In addition, exposure is performed by the above method through a line-and-space mask, and the shape of the obtained relief pattern is observed with an optical microscope (manufactured by Olympus Optical Co., Ltd., MHL100). (Adhesion) and resolution were determined.
[0175]
Furthermore, after the cured colored layer was immersed in pure water at 80 ° C. for 30 minutes, a cross-cut peel test method was performed, and adhesion (heat-resistant pure water resistance) was evaluated according to the following criteria.
[0176]
<Evaluation criteria for cross peel test>
○: No peeling of the coating film.
(Triangle | delta): It peels in the coating film of less than 50%, and there exists a defect | deletion.
X: Peeled to 50% or more of the coating film, and there was a defect.
[0177]
(Example 2)
Except having changed the preparation amount as shown in Table 3, the same operation as Example 1 was performed and the benzyl maleimide resin solution 2 was obtained. The analysis values are shown in Table 3.
In Example 1, blue resist 2 was prepared using benzyl maleimide resin solution 2 in the same amount instead of benzyl maleimide resin solution 1.
(Example 3)
A benzylmaleimide resin solution 3 was obtained in the same manner as in Example 1 except that the amount charged was changed as shown in Table 3. The analytical values are shown in Table 1.
In Example 1, blue resist 3 was prepared using benzyl maleimide resin solution 3 in the same amount instead of benzyl maleimide resin solution 1.
[0178]
(Analysis and evaluation)
Table 4 shows the results of the following evaluations.
<Method for measuring hydroxyl value>
The hydroxyl value was determined according to JIS-K0070, and the hydroxyl value per gram of solid content was determined from the solid content concentration.
<Method for measuring acid value>
The acid value was measured by the same method as in Example 1.
<Development residue>
The same residue wiping test as in Example 1 was conducted and evaluated according to the following criteria. A: No residue (no coloring)
○: Lightly colored
Δ: deeply colored
×: Colored deeply (residue confirmation level)
[0179]
[Table 3]

[0180]
[Table 4]

[0181]
【The invention's effect】
As described above, according to the present invention, a photosensitive coloring composition containing a blue pigment or a phthalocyanine pigment, excellent in color characteristics, ability to form a fine pattern, and physical properties after curing, and a pigment used in the preparation thereof A dispersion composition is obtained. This photosensitive coloring composition is very suitable for forming color filter pixels, especially blue pixels, and is excellent in transparency and yellowing resistance, and forms a pixel pattern accurately without developing residue during development. It has excellent physical properties such as hardness and elasticity after curing.
[0182]
By forming a pixel of a color filter using such a photosensitive coloring composition, a color filter excellent in display performance and a display device excellent in display performance using the color filter, such as a liquid crystal display device or an organic EL A display device or the like is obtained.
[Brief description of the drawings]
FIG. 1 is a schematic cross-sectional view of an example of a liquid crystal panel.
FIG. 2 is a schematic cross-sectional view of another example of a liquid crystal panel.
[Explanation of symbols]
1. Color filter
2 ... Electrode substrate
3. Gap (L: Liquid crystal compound)
4 ... Sealing 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 ... Columnar spacer

Claims (24)

A pigment dispersion composition comprising at least one pigment selected from the group consisting of blue pigments and phthalocyanine pigments, a maleimide alkali-soluble copolymer, a dispersant, and a solvent, wherein the maleimide alkali The soluble copolymer has a benzyl maleimide monomer unit which may have a substituent as an essential component, and a pigment dispersion composition. 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. The mixing ratio of the dispersant (dispersant / pigment) with respect to the total amount of the pigment containing a pigment selected from the group consisting of a blue pigment and a phthalocyanine pigment is 0.5 or less in mass ratio. Or the pigment dispersion composition of 2. A photosensitive coloring composition comprising at least one pigment selected from the group consisting of a blue pigment and a phthalocyanine pigment, a maleimide alkali-soluble copolymer, a radical polymerizable compound, and a photopolymerization initiator, The said maleimide type | system | group alkali-soluble copolymer has the benzyl maleimide monomer unit which may have a substituent as an essential, The photosensitive coloring composition characterized by the above-mentioned. 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 calorimetric XYZ color system 2 ° visual field The photosensitive coloring composition according to claim 4, wherein a cured film capable of displaying a color space having a stimulation 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, y = 0.1400 before and after heating at 250 ° C. for 1 hour after setting the film thickness after curing, 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 with respect to the measured value Y1 can be 97% or more. 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 mm or less can be formed by a measurement method based on JIS B0601-1994. The photosensitive coloring composition according to claim 4, wherein a cured film having a line width of 25 μm or less that generates defects 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 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 obtained by curing the photosensitive coloring composition according to any one of claims 4 to 12. A color filter provided with a pixel in which at least one pigment selected from the group consisting of a blue pigment and a phthalocyanine pigment is dispersed in a matrix formed of a cured binder containing a maleimide alkali-soluble copolymer. The maleimide-based alkali-soluble copolymer has a benzylmaleimide monomer unit that may have a substituent as an essential component, and is a color filter. The color filter according to claim 13 or 14, wherein the pixel has a surface roughness (Ra) of 50 mm or less in a measurement method based on JIS B0601-1994. The color filter according to claim 13, wherein the pixel has a line width of 25 μm or less that causes a defect when exposed and cured through a line-and-space mask. The color filter according to claim 13, wherein the pixel has a resolution of 24 μm or less when exposed and cured through a line and space mask. The color filter according to claim 13, wherein the pixel has a rising angle of a cross section of 50 degrees or less with respect to a surface to be coated. 19. The color filter according to claim 13, wherein a ratio of the length of the upper base to the length of the lower base of the cross-sectional shape of the pixel is less than one. The color filter according to claim 13, wherein the pixel is a blue pixel. The blue pixel has a film thickness of 1.35 μm or less, and when the color is measured with a single pixel, the x coordinate is 0.05 ≦ x ≦ 0.30 and the y coordinate is 21. The color filter according to claim 20, wherein a color space having 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 film thickness of 1.3 μm, and before and after being heated at 250 ° C. for 1 hour, the stimulus value Y at the C light source color measurement XYZ color system 2 field of view, y = 0.1400 The color filter according to claim 20 or 21, wherein a rate of change (Y2 / Y1) of the measured value Y2 after heating with respect to the measured value Y1 before heating becomes 97% or more when measuring. The color filter according to claim 20, wherein the blue pixel has a contrast ratio of 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 them.

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