JP2020060645A

JP2020060645A - Coloring composition for color filter containing dark sub dye

Info

Publication number: JP2020060645A
Application number: JP2018190912A
Authority: JP
Inventors: 由植村; Yu Uemura
Original assignee: Sanyo Color Works Ltd
Current assignee: Sanyo Color Works Ltd
Priority date: 2018-10-09
Filing date: 2018-10-09
Publication date: 2020-04-16
Anticipated expiration: 2038-10-09
Also published as: JP7212921B2

Abstract

To provide a coloring composition for a color filter having a yellow or red color as a main pigment, in which deterioration in luminance is suppressed while a contrast ratio is improved.SOLUTION: A coloring composition for a color filter containing a main dye that is yellow or red and a sub dye that is darker than the main dye is prepared. When the low wavelength end of a transmission band of the main dye is x (nm), the sub dye is a dye having a transmittance of 75% or less in a wavelength range of x-80 (nm) or more and x (nm) or less.SELECTED DRAWING: Figure 3

Description

本発明は、
黄色又は赤色である主色素と、該主色素よりも濃色である副色素とを含有するカラーフィルタ用着色組成物であって、コントラスト比に優れるカラーフィルタ用着色組成物に関する。 The present invention
The present invention relates to a color filter coloring composition containing a yellow or red main dye and a sub-dye darker than the main dye, which is excellent in contrast ratio.

カラーフィルタは、ガラスのような透明基板表面に複数の異なる色相の微細な帯状のフィルタセグメントを平行又は交差して配置した構造、又は微細なフィルタセグメントを縦横一定の配列で配置した構造を有する。液晶ディスプレイ用カラーフィルタは、色度の調整、輝度の向上、及びコントラスト比（CR）の向上が主な技術課題となっている。 The color filter has a structure in which a plurality of fine band-shaped filter segments of different hues are arranged in parallel or intersecting on the surface of a transparent substrate such as glass, or a structure in which the fine filter segments are arranged in a fixed vertical and horizontal arrangement. For color filters for liquid crystal displays, adjustment of chromaticity, improvement of brightness, and improvement of contrast ratio (CR) are major technical issues.

一般的なカラーフィルタでは、透明基板上に光の3原色である青、緑及び赤のフィルタセグメントが配置されているが、単一の顔料だけでそれぞれ目的のカラーフィルタとしての分光スペクトルを得るのが困難な場合には、顔料を2種以上用いて分光スペクトルを調整することが多い。 In a general color filter, filter segments of three primary colors of light, blue, green and red, are arranged on a transparent substrate, but it is possible to obtain a spectrum as a target color filter with only a single pigment. If it is difficult to adjust, the spectrum is often adjusted by using two or more pigments.

また、このような光の3原色のフィルタセグメントが配置されているカラーフィルタにおいては、透過度（明度）又は色純度といった色特性の向上についての要求が高まっている。色特性については、各単色だけでなく、3色を点灯させて得られるホワイトについても各用途に応じた要求があり、色度、色温度（Ｋ）又は色差（Δ_UV）によって管理されている。 Further, in such a color filter in which filter segments of three primary colors of light are arranged, there is an increasing demand for improvement of color characteristics such as transmittance (lightness) or color purity. Regarding color characteristics, not only each single color but also white obtained by lighting three colors is required to meet each application, and is controlled by chromaticity, color temperature (K) or color difference (Δ _UV ). .

ホワイトの色特性は、各色での色度と明度により規定されることから、従来は、ホワイトの色温度（K）、色差（Δ_UV）を調整するために3色の色度を変更する必要があるが、ホワイトを目標の色温度（K）及び色差（Δ_UV）とするために、各色の色度の目標が達成できなくなっていた。 Since the color characteristics of white are defined by the chromaticity and lightness of each color, conventionally it is necessary to change the chromaticity of the three colors to adjust the white color temperature (K) and color difference (Δ _UV ). However, since white is set as the target color temperature (K) and color difference (Δ _UV ), the target of chromaticity of each color cannot be achieved.

特許文献１は、透明樹脂、その前駆体又はそれらの混合物からなる色素担体と、該色素担体に分散された赤色色素及び青色色素を含み、該青色色素がC. I. Pigment Blue 15、15:1、15:2、15:3、15:4、15:6、22、60、64の群からなるいずれかの青色顔料であって、かつ該青色色素の含有量が、色素の全量を基準として0.005〜10重量％であることを特徴とするカラーフィルタ用赤色着色組成物を開示している。この着色組成物は、カラー液晶表示装置のホワイトバランスについても良好な値を付与することができ、透過型・反射型のカラー液晶表示装置ならびに固体撮像素子の色分解用カラーフィルタとして好適とされている。 Patent Document 1 includes a transparent resin, a pigment carrier composed of a precursor thereof or a mixture thereof, and a red pigment and a blue pigment dispersed in the pigment carrier, and the blue pigment is CI Pigment Blue 15, 15: 1, 15 : 2, 15: 3, 15: 4, 15: 6, 22, 60, 64 any one of the blue pigments, and the content of the blue pigment is 0.005 ~ based on the total amount of the pigment. Disclosed is a red coloring composition for a color filter, which is 10% by weight. This coloring composition can give a good value for the white balance of a color liquid crystal display device, and is suitable as a color filter for color separation of a transmission / reflection type color liquid crystal display device and a solid-state imaging device. There is.

また、特許文献２は、緑の明度を調整することにより、3色の色度を変更することなくホワイトを目標の色温度（K)、色差（Δ_UV）に調整することが可能なカラーフィルタ用緑色着色組成物を開示している。特許文献２のカラーフィルタ用緑色着色組成物は、具体的には、透明樹脂、透明樹脂の前駆体又はそれらの混合物からなる色素担体と、該色素担体に分散された緑色色素と、紫色色素、赤色色素又は黒色色素とを含み、紫色色素、赤色色素又は黒色色素の含有量が、色素の全量を基準として0.67〜2.0重量％であることを特徴とするカラーフィルタ用緑色着色組成物である。 Further, Patent Document 2 is a color filter capable of adjusting white to a target color temperature (K) and a color difference (Δ _UV ) by adjusting the brightness of green without changing the chromaticity of the three colors. A green coloring composition for use is disclosed. The green coloring composition for a color filter of Patent Document 2, specifically, a pigment carrier made of a transparent resin, a precursor of a transparent resin or a mixture thereof, a green pigment dispersed in the pigment carrier, a purple pigment, A green coloring composition for a color filter, comprising a red pigment or a black pigment, and the content of the purple pigment, the red pigment or the black pigment is 0.67 to 2.0% by weight based on the total amount of the pigment.

さらに、特許文献３は、カーボンブラックや有機顔料の塗料樹脂に対する分散性を向上させるだけでは達成できなかった光の乱反射による白ボケ現象を改善することにより、有光沢の塗料全般に対する鮮映性を改善するための、角度非依存性の構造色を発現するカテコール系高分子黒色微粒子を有効成分として含んでなる、水性塗料に鮮映性を付与するための調製物を開示している。 Furthermore, Patent Document 3 improves the sharpness of glossy paints in general by improving the white blur phenomenon due to diffused reflection of light that could not be achieved only by improving the dispersibility of carbon black or organic pigment in the paint resin. Disclosed is a preparation for imparting sharpness to a water-based paint, which comprises, as an active ingredient, catechol-based polymer black fine particles expressing an angle-independent structural color for improvement.

特許第４５３８２２０号公報Japanese Patent No. 4538220 特許第４９１８２１１号公報Japanese Patent No. 4918211 特許第６１７６８６０号公報Japanese Patent No. 6176860

上述したように、カラーフィルタ用着色組成物について、明度調整又は色度調整のために赤色又は緑色色素に黒色色素のような濃色色素を混合する技術は公知であった。カラーフィルタ用黄色色素についてCRを向上させる場合、光の散乱を防止する必要があると考えられたが、黄色色素の場合には、従来技術と同様に濃色色素を混合すると、輝度が低下しやすいという別の問題が生じる。同様の問題は、カラーフィルタ用赤色色素についても存在する。 As described above, with respect to the coloring composition for a color filter, a technique of mixing a red or green pigment with a dark pigment such as a black pigment for the purpose of adjusting the lightness or the chromaticity has been known. It was thought that it was necessary to prevent light scattering when improving the CR of yellow dyes for color filters.However, in the case of yellow dyes, mixing dark-colored dyes in the same way as in the prior art reduced the brightness. Another problem of easiness arises. Similar problems also exist for red pigments for color filters.

本発明は、黄色又は赤色を主色素とするカラーフィルタ用着色組成物であって、CRを向上させつつ、輝度の低下が少ないカラーフィルタ用着色組成物の提供を目的とする。 It is an object of the present invention to provide a color filter coloring composition containing yellow or red as a main dye, which is capable of improving CR and reducing luminance less.

本発明者等は、上記課題を解決すべく鋭意検討を続けた結果、主色素よりも濃色である特定の副色素を混合することにより、カラーフィルタの輝度低下を抑制しつつ、CRを向上させ得ることを見出し、本発明を完成させるに至った。 The present inventors, as a result of continuing diligent studies to solve the above problems, by mixing a specific sub-dye that is darker than the main dye, while suppressing the decrease in brightness of the color filter, improve CR. The inventors have found that they can be achieved and have completed the present invention.

具体的に本発明は、
黄色又は赤色である主色素と、該主色素よりも濃色である副色素とを含有するカラーフィルタ用着色組成物であって、
前記副色素は、前記主色素の透過帯域の低波長端をx(nm)とした場合に、x-80 (nm)以上x (nm)以下の波長範囲における透過率が75％以下である、
カラーフィルタ用着色組成物に関する。 Specifically, the present invention is
A coloring composition for a color filter, containing a main dye that is yellow or red and a sub-dye that is darker than the main dye,
The sub-dye has a transmittance of 75% or less in the wavelength range of x-80 (nm) or more and x (nm) or less, where x (nm) is the low wavelength end of the transmission band of the main dye.
The present invention relates to a coloring composition for a color filter.

本発明者等は、主色素が黄色又は赤色であるカラーフィルタのCRを向上させるために、濃色の副色素を混合することを試みた。しかし、特許文献１に開示されている青色色素では十分な効果が得られなかった。また、特許文献２に開示されている黒色色素を0.67重量％程度添加した場合には、輝度が著しく低下してカラーフィルタとしての実用性が損なわれてしまった。 The present inventors have attempted to mix a dark-colored sub-dye in order to improve the CR of a color filter whose main dye is yellow or red. However, a sufficient effect was not obtained with the blue dye disclosed in Patent Document 1. Further, when about 0.67% by weight of the black dye disclosed in Patent Document 2 was added, the brightness was remarkably lowered and the practicality as a color filter was impaired.

しかし、本発明では、黄色又は赤色である主色素に対して、主色素よりも濃色である副色素を混合することにより、CRを向上させつつ、輝度の低下を抑制している。 However, in the present invention, by mixing the main dye that is yellow or red with the sub-dye that is darker than the main dye, the CR is improved and the decrease in brightness is suppressed.

ここで、本発明でいう濃色は、主色素の透過帯域の低波長端をx(nm)とした場合に、x-80 (nm)以上x (nm)以下の波長範囲における透過率が75％以下である色を意味する。透過帯域の低波長端とは、その色素の組成物をガラス板に塗布し、分光光度計により分光透過率曲線を求めたとき、透過帯域の低波長側における曲線接線とy=0の軸とが接する点（外挿透過端）を意味する。 Here, the dark color in the present invention has a transmittance of 75 in the wavelength range of x-80 (nm) or more and x (nm) or less, where x (nm) is the low wavelength end of the transmission band of the main dye. Means a color that is less than or equal to%. The low wavelength end of the transmission band, the composition of the dye is applied to a glass plate, when the spectral transmittance curve is obtained by a spectrophotometer, the curve tangent and y = 0 axis on the low wavelength side of the transmission band Means a point (extrapolated transparent end) where is touched.

前記主色素が黄色であり、
前記副色素がカーボンブラックである場合には、
前記カラーフィルタ用色素中の前記副色素濃度が0.004質量％以上0.167質量％以下であることが好ましい。 The main pigment is yellow,
When the sub-dye is carbon black,
The sub-dye concentration in the color filter dye is preferably 0.004 mass% or more and 0.167 mass% or less.

前記主色素が黄色であり、
前記副色素が茶色である場合には、
前記カラーフィルタ用色素中の副色素濃度が0.008質量％以上3.34質量％以下であることが好ましい。 The main pigment is yellow,
When the sub-dye is brown,
The sub-dye concentration in the color filter dye is preferably 0.008 mass% or more and 3.34 mass% or less.

前記主色素がC. I. Pigment Yellow 74、C. I. Pigment Yellow 138、C. I. Pigment Yellow 139、C. I. Pigment Yellow 150及びC. I. Pigment Yellow 185からなる群より選択される1種であり、
前記副色素がC. I. Pigment Brown 25であることがより好ましい。 The main pigment is one selected from the group consisting of CI Pigment Yellow 74, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150 and CI Pigment Yellow 185,
More preferably, the secondary dye is CI Pigment Brown 25.

前記主色素が赤色であるC. I. Pigment Red 254であり、
前記副色素がカーボンブラックであり、
前記カラーフィルタ用色素中の前記副色素濃度が0.08質量％以上0.668質量％以下であることも好ましい。 The main pigment is CI Pigment Red 254 which is red,
The sub-dye is carbon black,
It is also preferable that the sub-dye concentration in the color filter dye is 0.08 mass% or more and 0.668 mass% or less.

本発明によれば、黄色又は赤色のカラーフィルタにおいて、輝度の低下を抑制しつつ、CRを向上させることが可能となる。このような効果が得られる原理は確認されていないが、主顔料の散乱光がxからx-80の波長の間にあり、本発明の組成であれば、主顔料の散乱光を副顔料が吸収し、コントラスト比における、偏光板が直交の時（クロスニコル配置）の明度を抑えることができるため、高いコントラスト比を実現するものと推測される。 According to the present invention, it is possible to improve CR in a yellow or red color filter while suppressing a decrease in luminance. Although the principle that such an effect is obtained has not been confirmed, the scattered light of the main pigment is in the wavelength range from x to x-80, and with the composition of the present invention, the scattered light of the main pigment is converted to the sub-pigment. It is presumed that a high contrast ratio can be realized because the lightness can be suppressed and the brightness of the contrast ratio when the polarizing plates are orthogonal (crossed Nicol arrangement) can be suppressed.

C. I. Pigment Red 254及びCBの300nm〜800nmにおける透過率（％）を測定したグラフを示す。The graph which measured the transmittance | permeability (%) in 300 nm-800 nm of C. I. Pigment Red 254 and CB is shown. C. I. Pigment Red 269及びCBの300nm〜800nmにおける透過率（％）を測定したグラフを示す。The graph which measured the transmittance | permeability (%) in 300 nm-800 nm of C. I. Pigment Red 269 and CB is shown. 評価用組成物５（Y185）及び評価用組成物７ｂ（Y185/Br25）のヘイズスペクトル測定結果を示す。The haze spectrum measurement result of the composition 5 for evaluation (Y185) and the composition 7b for evaluation (Y185 / Br25) is shown.

本発明の実施形態について、適宜図面を参照しながら説明する。本発明は、以下の記載に限定されない。 Embodiments of the present invention will be described with reference to the drawings as appropriate. The present invention is not limited to the description below.

＜顔料誘導体Ａの調製＞
濃硫酸（98％）200重量部中にC. I. Pigment Red 255 15重量部、パラホルムアルデヒド1.6重量部及び4-アミノフタルイミド8.4重量部を添加し、85℃で5時間反応させた。次に、この溶液を1Lの氷水中に供給し、濾過及び水洗を行うことにより、4-アミノフタルイミドメチル基1個を導入した(4-アミノフタルイミドメチル) - C. I. Pigment Red 225を19.5重量部得た。 <Preparation of pigment derivative A>
To 200 parts by weight of concentrated sulfuric acid (98%), 15 parts by weight of CI Pigment Red 255, 1.6 parts by weight of paraformaldehyde and 8.4 parts by weight of 4-aminophthalimide were added and reacted at 85 ° C. for 5 hours. Next, this solution was supplied to 1 L of ice water, and filtered and washed with water to introduce one 4-aminophthalimidomethyl group (4-aminophthalimidomethyl)-19.5 parts by weight of CI Pigment Red 225 was obtained. It was

得られた(4-アミノフタルイミドメチル) - C. I. Pigment Red 255 10重量部を水100部中に分散させ、アミノ基1個と反応する量の塩化シアヌル3.6重量部を加えて30℃で1時間反応させた。次に、3.4重量部のオルタニル酸を加え、80℃で2時間反応させ、化学式１に示される顔料誘導体Ａを15.2重量部得た。顔料誘導体Ａの元素分析及び質量分析を行ったところ、化学式１においてn=0.6であった。 10 parts by weight of the obtained (4-aminophthalimidomethyl)-CI Pigment Red 255 is dispersed in 100 parts of water, 3.6 parts by weight of cyanuric chloride that reacts with one amino group is added, and the mixture is reacted at 30 ° C for 1 hour. Let Next, 3.4 parts by weight of orthanilic acid was added and reacted at 80 ° C. for 2 hours to obtain 15.2 parts by weight of the pigment derivative A represented by the chemical formula 1. When the elemental analysis and the mass analysis of the pigment derivative A were performed, n = 0.6 in the chemical formula 1.

＜顔料誘導体Ｂの製造＞
500mL四つ口フラスコに25％発煙硫酸500gとC. I. Pigment Yellow 138（BASF社製、Paliotol Yellow L0960HD）55.5g（80.0mmol）を入れ、60℃に加熱しながら5時間撹拌した。反応液を、水3Lに注加し、析出した黄色固体を吸引ろ過した。水12Lで洗浄して得られた黄色ペースト314g（不揮発分17％）を80℃で乾燥し、化学式２に示される顔料誘導体Ｂを54.0g得た。 <Production of Pigment Derivative B>
To a 500 mL four-necked flask, 500 g of 25% fuming sulfuric acid and 55.5 g (80.0 mmol) of CI Pigment Yellow 138 (Paliotol Yellow L0960HD manufactured by BASF) were placed, and the mixture was stirred for 5 hours while heating at 60 ° C. The reaction solution was poured into 3 L of water, and the precipitated yellow solid was suction filtered. 314 g of a yellow paste (nonvolatile matter 17%) obtained by washing with 12 L of water was dried at 80 ° C. to obtain 54.0 g of the pigment derivative B represented by the chemical formula 2.

＜Ａ／主顔料組成物（主色素組成物）の調製＞
［主顔料組成物１］
C. I. Pigment Red 254（BASF社製、Irgazin（登録商標）Red L3630）8.10重量部；顔料誘導体Ａ 0.90重量部；樹脂型分散剤（ビックケミ・ジャパン株式会社製、BYK LPN6919、固形分60.9％） 4.43重量部；分散樹脂（株式会社日本触媒製、アクリキュアー（登録商標）BX-Y-11、固形分38.1％） 7.09重量部；プロピレングリコールモノメチルエーテル（PM） 3.00重量部；プロピレングリコールモノメチルエーテルアセテート（PMA） 36.48重量部；及び直径0.5mmのジルコニアビーズ240重量部を内容量100mLのプラスチック容器に投入し、ペイントコンディショナーを用いて１時間分散処理を行った。分散処理物を2.5μmメッシュのフィルタを用いて濾過し、主顔料組成物１を得た。 <A/Preparation of Main Pigment Composition (Main Pigment Composition)>
[Main pigment composition 1]
CI Pigment Red 254 (manufactured by BASF, Irgazin (registered trademark) Red L3630) 8.10 parts by weight; pigment derivative A 0.90 parts by weight; resin type dispersant (BYK LPN6919, solid content 60.9%, manufactured by BYK Chem Japan KK) 4.43 parts by weight Parts; Dispersion resin (Nippon Shokubai Co., Ltd., Acrycure (registered trademark) BX-Y-11, solid content 38.1%) 7.09 parts by weight; propylene glycol monomethyl ether (PM) 3.00 parts by weight; propylene glycol monomethyl ether acetate (PMA) ) 36.48 parts by weight; and 240 parts by weight of zirconia beads having a diameter of 0.5 mm were placed in a plastic container having an internal volume of 100 mL, and dispersed for 1 hour using a paint conditioner. The dispersion-treated product was filtered using a 2.5 μm mesh filter to obtain a main pigment composition 1.

［主顔料組成物２］
（微細化工程）
C. I. Pigment Red 269（山陽色素社製、Permanent Carmine 3811）270.0重量部；顔料誘導体Ｂ 30.0重量部；無水硫酸ナトリウム3000.0重量部；及びエチレングリコール800.0重量部を双腕型ニーダー（モリヤマ製5LニーダーΣ型）に投入し、ニーダー内が40℃となるように温度調整しながら、7時間混練した。さらに分散樹脂（昭和電工株式会社製、リポキシSPCN-100、固形分28.5％）158.0重量部を投入し、40℃で2時間混練した。 [Main pigment composition 2]
(Miniaturization process)
CI Pigment Red 269 (manufactured by Sanyo Pigment Co., Ltd., Permanent Carmine 3811) 270.0 parts by weight; pigment derivative B 30.0 parts by weight; anhydrous sodium sulfate 3000.0 parts by weight; and ethylene glycol 800.0 parts by weight with a double-arm kneader (Moriyama 5L kneader Σ type) ) And kneading for 7 hours while adjusting the temperature so that the inside of the kneader becomes 40 ° C. Further, 158.0 parts by weight of a dispersion resin (manufactured by Showa Denko KK, Lipoxy SPCN-100, solid content 28.5%) was added, and the mixture was kneaded at 40 ° C. for 2 hours.

混練物を、イオン交換水6Lを貯水した温度調節可能なタンク内に移し、60℃で30分間撹拌後、35％塩酸でpHを2.3〜2.5に調節して１時間分散させた。分散液をヌッチェに移して濾紙を用いて濾過し、洗浄排水の電気伝導度が3μS/cm以下になるまでイオン交換水を用いて洗浄した。洗浄後の残渣を95℃で24時間乾燥させた。乾燥ブロックを粉砕機（協立理工株式会社製、小型粉砕機サンプルミルSK-M2）によって粉砕することで、微細化C. I. Pigment Red 269を得た。 The kneaded product was transferred into a temperature-controllable tank containing 6 L of ion-exchanged water, stirred at 60 ° C. for 30 minutes, adjusted to pH 2.3 to 2.5 with 35% hydrochloric acid, and dispersed for 1 hour. The dispersion was transferred to a Nutsche, filtered using a filter paper, and washed with ion-exchanged water until the electric conductivity of the washing drainage was 3 μS / cm or less. The residue after washing was dried at 95 ° C for 24 hours. The dry block was crushed by a crusher (small crusher sample mill SK-M2 manufactured by Kyoritsu Riko Co., Ltd.) to obtain miniaturized C. I. Pigment Red 269.

微細化C. I. Pigment Red 269 36.23重量部；顔料誘導体Ｂ 3.50重量部；樹脂型分散剤（ビックケミ・ジャパン株式会社製、BYK LPN6919、固形分60.9％）12.48重量部、分散樹脂（綜研化学株式会社製、フォレット（登録商標）ZAH110、固形分35.0％）13.95重量部；プロピレングリコールモノメチルエーテル（PM） 23.33重量部：及びプロピレングリコールモノメチルエーテルアセテート（PMA）50.51重量部を内容量500mLの混合槽に投入し、ディスパーを用いて2000rpmで10分間撹拌し、予備分散を行った。得られた予備分散物に、直径0.8mmのジルコニアビーズ560重量部を添加し、2000rpmで60分間撹拌して本分散処理を行った。 Micronized CI Pigment Red 269 36.23 parts by weight; pigment derivative B 3.50 parts by weight; resin type dispersant (manufactured by BYK Chem Japan KK, BYK LPN6919, solid content 60.9%) 12.48 parts by weight, dispersion resin (manufactured by Soken Chemical Co., Ltd., Foret (registered trademark) ZAH110, solid content 35.0%) 13.95 parts by weight; propylene glycol monomethyl ether (PM) 23.33 parts by weight: and propylene glycol monomethyl ether acetate (PMA) 50.51 parts by weight are charged into a mixing tank having an internal capacity of 500 mL, Predispersion was performed by stirring at 2000 rpm for 10 minutes using a disper. 560 parts by weight of zirconia beads having a diameter of 0.8 mm was added to the obtained pre-dispersion, and the main dispersion treatment was performed by stirring at 2000 rpm for 60 minutes.

［主顔料組成物３］
（微細化工程）
C. I. Pigment Yellow 138（BASF社製、Paliotol Yellow L0960HD）200.0重量部；顔料誘導体Ｂ 10.0重量部；無水硫酸ナトリウム3000.0重量部；及びエチレングリコール750.0重量部を双腕型ニーダー（モリヤマ製5LニーダーΣ型）に投入し、ニーダー内が50℃となるように温度調整しながら、8時間混練した。さらに、分散樹脂（昭和電工株式会社製、リポキシSPCN-21、固形分37.7％）79.5重量部を投入し、50℃で1時間混練した。 [Main pigment composition 3]
(Miniaturization process)
CI Pigment Yellow 138 (manufactured by BASF, Paliotol Yellow L0960HD) 200.0 parts by weight; pigment derivative B 10.0 parts by weight; anhydrous sodium sulfate 3000.0 parts by weight; and ethylene glycol 750.0 parts by weight, double-arm kneader (Moriyama 5L kneader Σ type) And kneading for 8 hours while adjusting the temperature so that the inside of the kneader becomes 50 ° C. Furthermore, 79.5 parts by weight of a dispersion resin (manufactured by Showa Denko KK, Lipoxy SPCN-21, solid content 37.7%) was added, and the mixture was kneaded at 50 ° C. for 1 hour.

混練物を、イオン交換水12Lを貯水した温度調節可能なタンク内に移し、60℃で1時間分散させた。分散液をヌッチェに移して濾紙を用いて濾過し、洗浄排水の電気伝導度が3μS/cm以下になるまでイオン交換水を用いて洗浄した。洗浄後の残渣を60℃で20時間乾燥させた。乾燥ブロックを粉砕機（協立理工株式会社製、小型粉砕機サンプルミルSK-M2）によって粉砕することで、微細化C. I. Pigment Yellow 138顔料を得た。 The kneaded product was transferred to a temperature-controllable tank containing 12 L of ion-exchanged water and dispersed at 60 ° C. for 1 hour. The dispersion was transferred to a Nutsche, filtered using a filter paper, and washed with ion-exchanged water until the electric conductivity of the washing drainage was 3 μS / cm or less. The residue after washing was dried at 60 ° C for 20 hours. The dry block was crushed by a crusher (small crusher sample mill SK-M2 manufactured by Kyoritsu Riko Co., Ltd.) to obtain a miniaturized C.I. Pigment Yellow 138 pigment.

（分散工程）
微細化C. I. Pigment Yellow 138 39.12重量部；顔料誘導体Ｂ 3.78重量部；樹脂型分散剤（ビックケミ・ジャパン株式会社製、BYKLPN6919、固形分60.9％）26.06重量部；分散樹脂（株式会社日本触媒社製、アクリキュアー（登録商標）RD-Y-203；固形分40.2％）26.80重量部；及びプロピレングリコールモノメチルエーテルアセテート（PMA）82.99重量部を内容量500mLの混合槽に投入し、ディスパーを用いて2000rpmで10分間撹拌し、予備分散処理を行った。得られた予備分散物に、直径0.8mmのジルコニアビーズ720重量部を添加し、2000rpmで30分間撹拌して本分散処理を行った。 (Dispersion process)
Micronized CI Pigment Yellow 138 39.12 parts by weight; Pigment derivative B 3.78 parts by weight; Resin-type dispersant (manufactured by BYKPN Japan KK, BYKLPN6919, solid content 60.9%) 26.06 parts by weight; Dispersion resin (manufactured by Nippon Shokubai Co., Ltd., Acrycure (registered trademark) RD-Y-203; solid content 40.2%) 26.80 parts by weight; and propylene glycol monomethyl ether acetate (PMA) 82.99 parts by weight are charged into a mixing tank having an internal capacity of 500 mL, and a disper is used at 2000 rpm. After stirring for 10 minutes, preliminary dispersion treatment was performed. 720 parts by weight of zirconia beads having a diameter of 0.8 mm was added to the obtained pre-dispersion, and the main dispersion treatment was performed by stirring at 2000 rpm for 30 minutes.

その後、プロピレングリコールモノメチルエーテルアセテート（PMA）30.00重量部を添加し、2000rpmで10分間撹拌して希釈分散処理を行った。2.5μmメッシュのフィルタ（PALL社製、PALL HDC II Membrane Filter）を用いて濾過して得られた分散物180.0重量部に、直径0.05mmのジルコニアビーズ720重量部を添加し、2000rpmで60分間撹拌して二次分散処理を行った。 Then, 30.00 parts by weight of propylene glycol monomethyl ether acetate (PMA) was added, and the mixture was stirred at 2000 rpm for 10 minutes to carry out a dilution dispersion treatment. To 180.0 parts by weight of the dispersion obtained by filtration using a 2.5 μm mesh filter (PALL, PALL HDC II Membrane Filter), add 720 parts by weight of zirconia beads having a diameter of 0.05 mm, and stir at 2000 rpm for 60 minutes. Then, secondary dispersion processing was performed.

その後、プロピレングリコールモノメチルエーテルアセテート（PMA）90.00重量部を添加し、1500rpmで10分間撹拌して希釈分散処理を行った。2.5μmメッシュのフィルタ（PALL社製、PALL HDC II Membrane Filter）を用いて濾過し、主顔料組成物３を得た。 Then, 90.00 parts by weight of propylene glycol monomethyl ether acetate (PMA) was added, and the mixture was stirred at 1500 rpm for 10 minutes to carry out a dilution dispersion treatment. A main pigment composition 3 was obtained by filtering using a 2.5 μm mesh filter (PALL HDC II Membrane Filter, manufactured by PALL).

［主顔料組成物４］
（微細化工程）
C. I. Pigment Yellow 139（BASF社製、Irgaphor Yellow S2150CF）270.0重量部；顔料誘導体Ｂ 30.0重量部；無水硫酸ナトリウム3000.0重量部；及びジエチレングリコール860.0重量部を双腕型ニーダー（モリヤマ製5LニーダーΣ型）に投入し、ニーダー内が50℃となるように温度調整しながら、8時間混練した。さらに分散樹脂（昭和電工株式会社製、リポキシSPC-2000、固形分37.4％） 158.8重量部を投入し、50℃で1時間混練した。 [Main pigment composition 4]
(Miniaturization process)
CI Pigment Yellow 139 (BASF, Irgaphor Yellow S2150CF) 270.0 parts by weight; pigment derivative B 30.0 parts by weight; anhydrous sodium sulfate 3000.0 parts by weight; and diethylene glycol 860.0 parts by weight into a double-arm kneader (Moriyama 5L kneader Σ type) The mixture was charged and kneaded for 8 hours while adjusting the temperature so that the inside of the kneader became 50 ° C. Further, 158.8 parts by weight of a dispersion resin (manufactured by Showa Denko KK, Lipoxy SPC-2000, solid content 37.4%) was added, and the mixture was kneaded at 50 ° C. for 1 hour.

混練物を、イオン交換水12Lを貯水した温度調節可能なタンク内に移し、60℃で1時間分散させた。分散液をヌッチェに移して濾紙を用いて濾過し、洗浄排水の電気伝導度が3μS/cm以下になるまでイオン交換水を用いて洗浄した。洗浄後の残渣を80℃で24時間乾燥させた。乾燥ブロックを粉砕機（協立理工株式会社製、小型粉砕機サンプルミルSK-M2）によって粉砕することで、微細化C. I. Pigment Yellow 139を得た。 The kneaded product was transferred to a temperature-controllable tank containing 12 L of ion-exchanged water and dispersed at 60 ° C. for 1 hour. The dispersion was transferred to a Nutsche, filtered using a filter paper, and washed with ion-exchanged water until the electric conductivity of the washing drainage was 3 μS / cm or less. The residue after washing was dried at 80 ° C for 24 hours. The dry block was pulverized by a pulverizer (small pulverizer sample mill SK-M2 manufactured by Kyoritsu Riko Co., Ltd.) to obtain miniaturized C. I. Pigment Yellow 139.

（分散工程）
微細化C. I. Pigment Yellow 139 44.75重量部；顔料誘導体Ｂ 1.98重量部；樹脂型分散剤（ビックケミ・ジャパン株式会社製、BYKLPN6919、固形分61.2％）12.94重量部；分散樹脂（株式会社日本触媒社製、アクリキュアー（登録商標）RD-Y-507、固形分36.9％）18.24重量部；及びプロピレングリコールモノメチルエーテルアセテート（PMA）102.09重量部を内容量500mLの混合槽に投入し、ディスパーを用いて2000rpmで10分間撹拌し、予備分散処理を行った。得られた予備分散物に、直径0.5mmのジルコニアビーズ720重量部を添加し、2000rpmで60分間撹拌して本分散を行った。 (Dispersion process)
Micronized CI Pigment Yellow 139 44.75 parts by weight; Pigment derivative B 1.98 parts by weight; Resin type dispersant (BYKPN Japan Co., BYKLPN6919, solid content 61.2%) 12.94 parts by weight; Dispersion resin (Nippon Shokubai Co., Ltd., Acrycure (registered trademark) RD-Y-507, solid content 36.9%) 18.24 parts by weight; and propylene glycol monomethyl ether acetate (PMA) 102.09 parts by weight are charged into a mixing tank having an internal volume of 500 mL, and a disperser is used at 2000 rpm. After stirring for 10 minutes, preliminary dispersion treatment was performed. To the obtained preliminary dispersion, 720 parts by weight of zirconia beads having a diameter of 0.5 mm was added, and main dispersion was carried out by stirring at 2000 rpm for 60 minutes.

その後、樹脂型分散剤（ビックケミ・ジャパン株式会社製、BYK LPN6919、固形分60.9％）7.01重量部；及びプロピレングリコールモノメチルエーテルアセテート（PMA）32.99重量部を添加し、2000rpmで10分間撹拌して希釈分散処理を行った。2.5μmメッシュのフィルタ（PALL社製、PALL HDC II Membrane Filter）を用いて濾過して得られた分散物180.0重量部に、直径0.05mmのジルコニアビーズ720重量部を添加し、2000rpmで120分間撹拌して二次分散処理を行った。 Then, 7.01 parts by weight of a resin type dispersant (BYK LPN6919, solid content 60.9%, manufactured by BYK Chem Japan Co., Ltd.); and 32.99 parts by weight of propylene glycol monomethyl ether acetate (PMA) are added, and the mixture is stirred at 2000 rpm for 10 minutes for dilution. Dispersion processing was performed. 180.0 parts by weight of the dispersion obtained by filtration using a 2.5 μm mesh filter (PALL HDC II Membrane Filter) was added to 720 parts by weight of zirconia beads having a diameter of 0.05 mm, and stirred at 2000 rpm for 120 minutes. Then, secondary dispersion processing was performed.

その後、プロピレングリコールモノメチルエーテルアセテート（PMA）90.00重量部を添加し、2000rpmで10分間撹拌して希釈分散処理を行った。2.5μmメッシュのフィルタ（PALL社製、PALL HDC II Membrane Filter）を用いて希釈分散物を濾過し、主顔料組成物４を得た。 Then, 90.00 parts by weight of propylene glycol monomethyl ether acetate (PMA) was added, and the mixture was stirred at 2000 rpm for 10 minutes to carry out a dilution dispersion treatment. The diluted dispersion was filtered using a 2.5 μm mesh filter (PALL HDC II Membrane Filter manufactured by PALL) to obtain a main pigment composition 4.

［主顔料組成物５］
（微細化工程）
C. I. Pigment Yellow 185（BASF社製、Paliotol Yellow D 1155）270.0重量部；顔料誘導体Ｂ 30.0重量部；無水硫酸ナトリウム3000.0重量部；エチレングリコール 680.0重量部；及びジエチルアミノプロピルアミン 11重量部を、双腕型ニーダー（モリヤマ製5LニーダーΣ型）に投入し、ニーダー内が45℃となるように温度調整しながら8時間混練した。次に、分散樹脂（綜研化学株式会社製、フォレット（登録商標）ZAH110、固形分35.0％） 128.6重量部を投入し、45℃で1時間混練した。 [Main pigment composition 5]
(Miniaturization process)
CI Pigment Yellow 185 (BASF Paliotol Yellow D 1155) 270.0 parts by weight; Pigment derivative B 30.0 parts by weight; anhydrous sodium sulfate 3000.0 parts by weight; ethylene glycol 680.0 parts by weight; and diethylaminopropylamine 11 parts by weight The mixture was put into a kneader (5L kneader Σ type manufactured by Moriyama) and kneaded for 8 hours while adjusting the temperature so that the temperature inside the kneader was 45 ° C. Next, 128.6 parts by weight of a dispersion resin (Foret (registered trademark) ZAH110, solid content 35.0%, manufactured by Soken Kagaku Co., Ltd.) was added, and the mixture was kneaded at 45 ° C. for 1 hour.

混練物を、イオン交換水12Lを貯水した温度調節可能なタンク内に移し、60℃で30分間撹拌した後、35％塩酸でpHを2.3〜2.5に調節して1時間分散させた。分散液をヌッチェに移して濾紙を用いて濾過し、洗浄排水の電気伝導度が3μS/cm以下になるまでイオン交換水を用いて洗浄した。洗浄後の残渣を80℃で24時間乾燥させた。乾燥ブロックを粉砕機（協立理工株式会社製、小型粉砕機サンプルミルSK-M2）によって粉砕することで、微細化C. I. Pigment Yellow 185を得た。 The kneaded product was transferred into a temperature-controllable tank containing 12 L of ion-exchanged water, stirred at 60 ° C. for 30 minutes, adjusted to pH 2.3 to 2.5 with 35% hydrochloric acid, and dispersed for 1 hour. The dispersion was transferred to a Nutsche, filtered using a filter paper, and washed with ion-exchanged water until the electric conductivity of the washing drainage was 3 μS / cm or less. The residue after washing was dried at 80 ° C for 24 hours. The dry block was crushed by a crusher (small crusher sample mill SK-M2 manufactured by Kyoritsu Riko Co., Ltd.) to obtain a miniaturized C. I. Pigment Yellow 185.

（分散工程）
微細化C. I. Pigment Yellow 185 37.26重量部；顔料誘導体Ｂ 3.60重量部；樹脂型分散剤（ビックケミ・ジャパン株式会社製、BYK LPN6919、固形分60.9％）60.67重量部；分散樹脂（綜研化学株式会社製、フォレット（登録商標）ZAH110、固形分35.0％） 27.25重量部；及びプロピレングリコールモノメチルエーテルアセテート（PMA） 71.22重量部を内容量500mLの混合槽に投入し、ディスパーを用いて2000rpmで10分間撹拌し、予備分散処理を行った。得られた予備分散物に、直径0.8mmのジルコニアビーズ800重量部を添加し、2000rpmで30分間撹拌して本分散処理を行った。 (Dispersion process)
Micronized CI Pigment Yellow 185 37.26 parts by weight; pigment derivative B 3.60 parts by weight; resin type dispersant (manufactured by BYK Japan KK, BYK LPN6919, solid content 60.9%) 60.67 parts by weight; dispersion resin (manufactured by Soken Chemical Co., Ltd., Foret (registered trademark) ZAH110, solid content 35.0%) 27.25 parts by weight; and propylene glycol monomethyl ether acetate (PMA) 71.22 parts by weight were charged into a mixing tank having an internal capacity of 500 mL, and stirred at 2000 rpm for 10 minutes using a disper, Pre-dispersion processing was performed. To the obtained pre-dispersion, 800 parts by weight of zirconia beads having a diameter of 0.8 mm was added and stirred at 2000 rpm for 30 minutes for main dispersion treatment.

その後、プロピレングリコールモノメチルエーテルアセテート（PMA）25.00重量部を添加し、2000rpmで10分間撹拌して希釈分散処理を行った。2.5μmメッシュのフィルタ（PALL社製、PALL HDC II Membrane Filter）を用いて濾過して得られた分散物185.0重量部に、直径0.1mmのジルコニアビーズ740重量部を添加し、2000rpmで60分間撹拌して二次分散処理を行った。 Then, 25.00 parts by weight of propylene glycol monomethyl ether acetate (PMA) was added, and the mixture was stirred at 2000 rpm for 10 minutes to carry out a dilution dispersion treatment. To 185.0 parts by weight of the dispersion obtained by filtration using a 2.5 μm mesh filter (PALL HDC II Membrane Filter), add 740 parts by weight of zirconia beads having a diameter of 0.1 mm, and stir at 2000 rpm for 60 minutes. Then, secondary dispersion processing was performed.

その後、プロピレングリコールモノメチルエーテルアセテート（PMA）61.67重量部を添加し、1500rpmで10分間撹拌して希釈分散処理を行った。2.5μmメッシュのフィルタ（PALL社製、PALL HDC II Membrane Filter）を用いて希釈分散物を濾過し、主顔料組成物５を得た。 Then, 61.67 parts by weight of propylene glycol monomethyl ether acetate (PMA) was added, and the mixture was stirred at 1500 rpm for 10 minutes to carry out a dilution dispersion treatment. The diluted dispersion was filtered using a 2.5 μm mesh filter (PALL HDC II Membrane Filter, manufactured by PALL) to obtain a main pigment composition 5.

［主顔料組成物６］
主顔料組成物４の分散処理時に使用する微細化C. I. Pigment Yellow 139 44.75重量部のうち、1.98重量部をC.I.Pigment Brown 25（Clariant社製、Hostaperm（登録商標）Brown HFR-01）で置き換えて使用すること以外、すべて主顔料組成物４と同様に操作することにより、主顔料組成物６を得た。 [Main pigment composition 6]
Of the 44.75 parts by weight of the finely divided CI Pigment Yellow 139 used in the dispersion treatment of the main pigment composition 4, 1.98 parts by weight are replaced with CI Pigment Brown 25 (Clariant, Hostaperm (registered trademark) Brown HFR-01). Other than the above, the same operations as in the main pigment composition 4 were carried out to obtain a main pigment composition 6.

［主顔料組成物７］
C.I.Pigment Yellow 150（ランクセス社製、Levascreen Yellow G04） 34.56重量部；顔料誘導体Ｂ 1.44重量部；樹脂型分散剤（ビックケミ・ジャパン株式会社製、BYKLPN6919、固形分60.9％）20.69重量部；分散樹脂（株式会社日本触媒製、アクリキュアー（登録商標）BX-Y-11、固形分38.3％）28.20重量部；プロピレングリコールモノメチルエーテル（PM）7.50重量部；及びプロピレングリコールモノメチルエーテルアセテート（PMA）57.61重量部を内容量500mLの混合槽に投入し、ディスパーを用いて2000rpmで10分間撹拌し、予備分散処理を行った。得られた予備分散物に、直径0.8mmのジルコニアビーズ600重量部を添加し、2000rpmで30分間撹拌して本分散処理を行った。 [Main pigment composition 7]
CIPigment Yellow 150 (Levascreen Yellow G04 manufactured by LANXESS) 34.56 parts by weight; Pigment derivative B 1.44 parts by weight; Resin type dispersant (BYKLPN6919, solid content 60.9%, manufactured by BYK Chem Japan KK) 20.69 parts by weight; Dispersion resin (stock) Made by Nippon Shokubai Co., Ltd., Acrycure (registered trademark) BX-Y-11, solid content 38.3%) 28.20 parts by weight; propylene glycol monomethyl ether (PM) 7.50 parts by weight; and propylene glycol monomethyl ether acetate (PMA) 57.61 parts by weight. The mixture was put into a mixing tank having an inner volume of 500 mL, stirred at 2000 rpm for 10 minutes using a disper, and subjected to a preliminary dispersion treatment. 600 parts by weight of zirconia beads having a diameter of 0.8 mm were added to the obtained pre-dispersion, and the dispersion treatment was performed by stirring at 2000 rpm for 30 minutes.

その後、プロピレングリコールモノメチルエーテルアセテート（PMA）30.00重量部を添加し、1500rpmで10分間撹拌して希釈分散処理を行った。2.5μmメッシュのフィルタ（PALL社製、PALL HDC II Membrane Filter）を用いて濾過して得られた分散物150.0重量部に、直径0.05mmのジルコニアビーズ600重量部を添加し、2000rpmで40分間撹拌して二次分散処理を行った。 Then, 30.00 parts by weight of propylene glycol monomethyl ether acetate (PMA) was added, and the mixture was stirred at 1500 rpm for 10 minutes to carry out a dilution dispersion treatment. To 150.0 parts by weight of the dispersion obtained by filtration using a 2.5 μm mesh filter (PALL HDC II Membrane Filter), add 600 parts by weight of zirconia beads having a diameter of 0.05 mm, and stir at 2000 rpm for 40 minutes. Then, secondary dispersion processing was performed.

その後、プロピレングリコールモノメチルエーテルアセテート（PMA）100.00重量部を添加し、1500rpmで10分間撹拌して希釈分散処理を行った。2.5μmメッシュのフィルタ（PALL社製、PALL HDC II Membrane Filter）を用いて希釈分散物を濾過し、主顔料組成物７を得た。 Then, 100.00 parts by weight of propylene glycol monomethyl ether acetate (PMA) was added, and the mixture was stirred at 1500 rpm for 10 minutes to carry out a dilution dispersion treatment. The diluted dispersion was filtered using a 2.5 μm mesh filter (PALL HDC II Membrane Filter, manufactured by PALL) to obtain Main Pigment Composition 7.

［主顔料組成物８］
（微細化工程）
C. I. Pigment Yellow 180(クラリアント社製、Toner Yellow HG）300.0重量部；及び無水硫酸ナトリウム3000.0重量部；エチレングリコール 780.0重量部を双腕型ニーダー（モリヤマ製5LニーダーΣ型）に投入し、ニーダー内が50℃となるように温度調整しながら、8時間混練した。次に、分散樹脂（昭和電工株式会社製、リポキシSPC-2000、固形分37.4％） 120.3重量部を投入し、50℃で1時間混練した。 [Main pigment composition 8]
(Miniaturization process)
CI Pigment Yellow 180 (Clariant, Toner Yellow HG) 300.0 parts by weight; and anhydrous sodium sulfate 3000.0 parts by weight; ethylene glycol 780.0 parts by weight are charged into a double-arm kneader (Moriyama 5L kneader Σ type), and the inside of the kneader is The mixture was kneaded for 8 hours while adjusting the temperature so as to be 50 ° C. Next, 120.3 parts by weight of a dispersion resin (manufactured by Showa Denko KK, Lipoxy SPC-2000, solid content 37.4%) was added, and the mixture was kneaded at 50 ° C. for 1 hour.

混練物を、イオン交換水12Lを貯水した温度調節可能なタンク内に移し、60℃で30分間撹拌後、35％塩酸でpHを2.3〜2.5に調節して1時間分散した。分散液をヌッチェに移して濾紙を用いて濾過し、洗浄排水の電気伝導度が3μS/cm以下になるまでイオン交換水を用いて洗浄した。洗浄後の残渣を80℃で24時間乾燥させた。乾燥ブロックを粉砕機（協立理工株式会社製、小型粉砕機サンプルミルSK-M2）によって粉砕することで、微細化C. I. Pigment Yellow 180を得た。 The kneaded product was transferred to a temperature-controllable tank containing 12 L of ion-exchanged water, stirred at 60 ° C. for 30 minutes, adjusted to pH 2.3 to 2.5 with 35% hydrochloric acid, and dispersed for 1 hour. The dispersion was transferred to a Nutsche, filtered using a filter paper, and washed with ion-exchanged water until the electric conductivity of the washing drainage was 3 μS / cm or less. The residue after washing was dried at 80 ° C for 24 hours. The dried block was crushed by a crusher (small crusher sample mill SK-M2 manufactured by Kyoritsu Riko Co., Ltd.) to obtain a miniaturized C. I. Pigment Yellow 180.

（分散工程）
微細化C. I. Pigment Yellow 180 31.46重量部；顔料誘導体Ｂ 3.04重量部；樹脂型分散剤（ビックケミ・ジャパン株式会社製、BYK LPN-22956、固形分44.4％）27.21重量部；分散樹脂（綜研化学株式会社製、フォレット（登録商標）ZAH-110、固形分59.6％）18.46重量部；及びプロピレングリコールモノメチルエーテルアセテート（PMA）79.82重量部を内容量500mLの混合槽に投入し、ディスパーを用いて2000rpmで10分間撹拌し、予備分散処理を行った。得られた予備分散物に、直径0.8mmのジルコニアビーズ640重量部を添加し、2000rpmで30分間撹拌して本分散を行った。 (Dispersion process)
Fine CI Pigment Yellow 180 31.46 parts by weight; pigment derivative B 3.04 parts by weight; resin type dispersant (BYK LPN-22956, BYK LPN-22956, solid content 44.4%) 27.21 parts by weight; dispersion resin (Soken Chemical Co., Ltd.) Foret (registered trademark) ZAH-110, solid content 59.6%) 18.46 parts by weight; and propylene glycol monomethyl ether acetate (PMA) 79.82 parts by weight are charged into a mixing tank having an internal capacity of 500 mL, and a disper is used at 10 at 2000 rpm. After stirring for a minute, preliminary dispersion treatment was performed. To the obtained pre-dispersion, 640 parts by weight of zirconia beads having a diameter of 0.8 mm was added, and main dispersion was performed by stirring at 2000 rpm for 30 minutes.

その後、プロピレングリコールモノメチルエーテルアセテート（PMA）30.00重量部を添加し、2000rpmで10分間撹拌して希釈分散処理を行った。2.5μmメッシュのフィルタ（PALL社製、PALL HDC II Membrane Filter）を用いて濾過して得られた分散物160.0重量部に、直径0.05mmのジルコニアビーズ640重量部を添加し、2000rpmで60分間撹拌して二次分散処理を行った。 Then, 30.00 parts by weight of propylene glycol monomethyl ether acetate (PMA) was added, and the mixture was stirred at 2000 rpm for 10 minutes to carry out a dilution dispersion treatment. To 160.0 parts by weight of a dispersion obtained by filtration using a 2.5 μm mesh filter (PALL HDC II Membrane Filter), add 640 parts by weight of zirconia beads having a diameter of 0.05 mm, and stir at 2000 rpm for 60 minutes. Then, secondary dispersion processing was performed.

その後、プロピレングリコールモノメチルエーテルアセテート（PMA）53.33重量部を添加し、1500rpmで10分間撹拌して希釈分散を行った。2.5μmメッシュのフィルタ（PALL社製、PALL HDC II Membrane Filter）を用いて希釈分散物を濾過し、主顔料組成物８を得た。 Then, 53.33 parts by weight of propylene glycol monomethyl ether acetate (PMA) was added, and the mixture was stirred at 1500 rpm for 10 minutes to carry out dilution dispersion. The diluted dispersion was filtered using a 2.5 μm mesh filter (PALL HDC II Membrane Filter, manufactured by PALL) to obtain a main pigment composition 8.

［主顔料組成物９］
C. I. Pigment Yellow 17（山陽色素社製、Pigment Yellow 1750）4.80重量部；顔料誘導体Ｂ 1.20重量部；樹脂型分散剤（ビックケミ・ジャパン株式会社製、BYK LPN6919、固形分60.9％）13.48重量部；分散樹脂（昭和電工株式会社製、リポキシSPC-2000、固形分37.4％）11.23重量部；プロピレングリコールモノメチルエーテル（PM）6.00重量部；プロピレングリコールモノメチルエーテルアセテート（PMA）23.29重量部；及び直径0.5mmのジルコニアビーズ240重量部を内容量100mLのプラスチック容器に投入し、ペイントコンディショナーを用いて1時間分散処理を行った。分散処理物を2.5μmメッシュのフィルタを用いて濾過し、主顔料組成物９を得た。 [Main pigment composition 9]
CI Pigment Yellow 17 (manufactured by Sanyo Pigment Co., Pigment Yellow 1750) 4.80 parts by weight; pigment derivative B 1.20 parts by weight; resin type dispersant (BYK LPN6919, solid content 60.9%) 13.48 parts by weight; dispersion Resin (manufactured by Showa Denko KK, Lipoxy SPC-2000, solid content 37.4%) 11.23 parts by weight; propylene glycol monomethyl ether (PM) 6.00 parts by weight; propylene glycol monomethyl ether acetate (PMA) 23.29 parts by weight; and diameter 0.5 mm 240 parts by weight of zirconia beads were placed in a plastic container having an internal volume of 100 mL, and dispersed for 1 hour using a paint conditioner. The dispersion-treated product was filtered using a 2.5 μm mesh filter to obtain a main pigment composition 9.

［主顔料組成物１０］
C. I. Pigment Yellow 17（山陽色素社製、Pigment Yellow 1750）4.80重量部の代わりに、C. I. Pigment Yellow 74（山陽色素社製、Pigment Yellow 7403）4.80重量部を使用すること以外、すべて主顔料組成物９と同様に操作することにより、主顔料組成物１０を得た。 [Main pigment composition 10]
CI Pigment Yellow 17 (Sanyo Pigment Co., Pigment Yellow 1750) 4.80 parts by weight instead of CI Pigment Yellow 74 (Sanyo Pigment Co., Pigment Yellow 7403) 4.80 parts by weight. The main pigment composition 10 was obtained by operating in the same manner as.

＜Ｂ／副顔料組成物（副色素組成物）の調製＞
［副顔料組成物１］
C. I. Pigment Black 7（三菱化学社製、MCF88）30.00重量部；分散樹脂（綜研化学株式会社製、フォレット（登録商標）ZAH110、固形分35.0％）25.78重量部；樹脂型分散剤（BASF社製、EFKA PX4701、固形分40.0％）22.50重量部；及びプロピレングリコールモノメチルエーテルアセテート（PMA）71.72重量部を内容量500mLの混合槽に投入し、ディスパーを用いて2000rpmで10分間撹拌し、予備分散処理を行った。得られた予備分散物に、直径0.8mmのジルコニアビーズ600重量部を添加し、2000rpmで30分間撹拌して本分散処理を行った。 <B / Preparation of Sub-Pigment Composition (Sub-Dye Composition)>
[Sub-pigment composition 1]
CI Pigment Black 7 (Mitsubishi Chemical Co., MCF88) 30.00 parts by weight; Dispersion resin (Soken Chemical Co., Ltd., Follet (registered trademark) ZAH110, solid content 35.0%) 25.78 parts by weight; Resin type dispersant (BASF Co., EFKA PX4701, solid content 40.0%) 22.50 parts by weight; and propylene glycol monomethyl ether acetate (PMA) 71.72 parts by weight are put into a mixing tank having an internal volume of 500 mL, and stirred for 10 minutes at 2000 rpm using a disper to carry out a preliminary dispersion treatment. went. 600 parts by weight of zirconia beads having a diameter of 0.8 mm were added to the obtained pre-dispersion, and the dispersion treatment was performed by stirring at 2000 rpm for 30 minutes.

2.5μmメッシュのフィルタ（PALL社製、PALL HDC II Membrane Filter）を用いて濾過して得られた分散物にプロピレングリコールモノメチルエーテルアセテート（PMA）を加えて固形分24.00％に調整した。分散物150.0重量部に直径0.1mmのジルコニアビーズ600重量部を添加し、2000rpmで60分間撹拌して二次分散処理を行った。 Propylene glycol monomethyl ether acetate (PMA) was added to the dispersion obtained by filtration using a 2.5 μm mesh filter (PALL HDC II Membrane Filter manufactured by PALL) to adjust the solid content to 24.00%. 600 parts by weight of zirconia beads having a diameter of 0.1 mm was added to 150.0 parts by weight of the dispersion, and the mixture was stirred at 2000 rpm for 60 minutes to carry out a secondary dispersion treatment.

その後、プロピレングリコールモノメチルエーテルアセテート（PMA）を加えて固形分19.20％になるように調整し、1000rpmで10分間撹拌して希釈分散処理を行った。希釈分散物を2.5μmメッシュのフィルタ（PALL社製、PALL HDC II Membrane Filter）を用いて濾過し、副顔料組成物１（黒色、顔料分12.00％）を得た。 Then, propylene glycol monomethyl ether acetate (PMA) was added to adjust the solid content to 19.20%, and the mixture was stirred at 1000 rpm for 10 minutes to carry out a dilution dispersion treatment. The diluted dispersion was filtered using a 2.5 μm mesh filter (PALL HDC II Membrane Filter, manufactured by PALL) to obtain a sub-pigment composition 1 (black, pigment content 12.00%).

［副顔料組成物２］
C. I. Pigment Red 179（DIC社製、Prrindo（商標登録）Maroon）1.80重量部；樹脂型分散剤（ビックケミ・ジャパン株式会社製、BYKLPN6919、固形分60.9％）4.43重量部；分散樹脂（綜研化学株式会社製、フォレット（登録商標）ZAH110、固形分35.0％）7.71重量部、プロピレングリコールモノメチルエーテル（PM）3.00重量部；プロピレングリコールモノメチルエーテルアセテート（PMA）43.06重量部；及び直径0.5mmのジルコニアビーズ240重量部を内容量100mLのプラスチック容器に投入し、ペイントコンディショナーを用いて1時間分散処理を行った。分散処理物を2.5μmメッシュのフィルタを用いて濾過し、副顔料組成物２（赤色、顔料分3.0％）を得た。 [Sub-pigment composition 2]
CI Pigment Red 179 (manufactured by DIC, Prrindo (registered trademark) Maroon) 1.80 parts by weight; resin type dispersant (manufactured by Big Chem Japan Co., BYKLPN6919, solid content 60.9%) 4.43 parts by weight; dispersion resin (Soken Chemical Co., Ltd.) Manufactured by Follet (registered trademark) ZAH110, solid content 35.0%) 7.71 parts by weight, propylene glycol monomethyl ether (PM) 3.00 parts by weight; propylene glycol monomethyl ether acetate (PMA) 43.06 parts by weight; and zirconia beads having a diameter of 0.5 mm 240 parts by weight Part was put into a plastic container having an internal volume of 100 mL, and the dispersion treatment was performed for 1 hour using a paint conditioner. The dispersion-treated product was filtered using a 2.5 μm mesh filter to obtain a sub-pigment composition 2 (red, pigment content 3.0%).

［副顔料分散体３］
C. I. Pigment Red 179（DIC社製、Prrindo（商標登録）Maroon）1.80重量部の代わりに、C. I. Pigment Brown 25（Clariant社製、Hostaperm（登録商標）Brown HFR-01）1.80重量部を使用すること以外、すべて副顔料組成物２と同様に操作することにより、副顔料組成物３（褐色、顔料分3.0％）を得た。 [Sub pigment dispersion 3]
CI Pigment Red 179 (DIC, Prrindo (registered trademark) Maroon) 1.80 parts by weight instead of CI Pigment Brown 25 (Clariant, Hostaperm (registered trademark) Brown HFR-01) 1.80 parts by weight Then, all the same operations as in the sub-pigment composition 2 were carried out to obtain a sub-pigment composition 3 (brown, pigment content 3.0%).

［副顔料分散体４］
C. I. Pigment Red 179（DIC社製、Prrindo（商標登録）Maroon）1.80重量部の代わりにC. I. Pigment Red 57（東京化成工業社製、Brilliant Carmine 6B）1.80重量部を使用すること以外、すべて副顔料組成物２と同様に操作することにより、副顔料組成物４（赤色、顔料分3.0％）を得た。 [Sub pigment dispersion 4]
CI Pigment Red 179 (DIC, Prrindo (registered trademark) Maroon) 1.80 parts by weight Instead of CI Pigment Red 57 (Tokyo Kasei Kogyo Co., Brilliant Carmine 6B) 1.80 parts by weight, all sub-pigment compositions By operating in the same manner as in Item 2, Sub-Pigment Composition 4 (red, pigment content 3.0%) was obtained.

＜Ｃ／評価用組成物の調製＞
カラーフィルタ用着色組成物としての機能を確認するため、主顔料組成物と副顔料組成物を組み合わせ、以下に示されるような評価用組成物（カラーフィルタ用着色組成物）を調製した。 <C / Preparation of composition for evaluation>
In order to confirm the function as the color filter coloring composition, the main pigment composition and the sub-pigment composition were combined to prepare an evaluation composition (color filter coloring composition) as shown below.

［評価用組成物１］
主顔料組成物１を評価用組成物１とした。 [Evaluation composition 1]
The main pigment composition 1 was used as an evaluation composition 1.

［評価組成物１ａ］
主顔料組成物１の9.90重量部と、副顔料組成物１の0.10重量部とを混合し、評価用組成物１ａとした。 [Evaluation composition 1a]
9.90 parts by weight of the main pigment composition 1 and 0.10 parts by weight of the auxiliary pigment composition 1 were mixed to obtain a composition for evaluation 1a.

［評価組成物１ｂ］
主顔料組成物１の5.00重量部と、評価用組成物１ａの5.00重量部とを混合し、評価用組成物１ｂとした。 [Evaluation composition 1b]
5.00 parts by weight of the main pigment composition 1 and 5.00 parts by weight of the evaluation composition 1a were mixed to obtain an evaluation composition 1b.

［評価組成物１ｃ］
主顔料組成物１の8.00重量部と、評価用組成物１ｂの2.00重量部とを混合し、評価用組成物１ｃとした。 [Evaluation composition 1c]
8.00 parts by weight of the main pigment composition 1 and 2.00 parts by weight of the evaluation composition 1b were mixed to obtain an evaluation composition 1c.

［評価組成物１ｄ］
主顔料組成物１の9.00重量部と、評価用組成物１ｃの1.00重量部とを混合し、評価用組成物１ｄとした。 [Evaluation composition 1d]
9.00 parts by weight of the main pigment composition 1 and 1.00 parts by weight of the evaluation composition 1c were mixed to obtain an evaluation composition 1d.

［評価用組成物２］
主顔料組成物２を評価用組成物２とした。 [Evaluation composition 2]
The main pigment composition 2 was used as a composition 2 for evaluation.

［評価用組成物２ａ］
主顔料組成物２の4.90重量部と、副顔料組成物１の0.10重量部を混合し、評価用組成物２ａとした。 [Evaluation composition 2a]
4.90 parts by weight of the main pigment composition 2 and 0.10 parts by weight of the auxiliary pigment composition 1 were mixed to obtain a composition for evaluation 2a.

［評価用組成物３］
主顔料組成物３を評価用組成物３とした。 [Evaluation composition 3]
The main pigment composition 3 was used as a composition 3 for evaluation.

［評価用組成物３ａ］
主顔料組成物３の9.90重量部と、副顔料組成物１の0.10重量部を混合し、評価用組成物３ａとした。 [Evaluation composition 3a]
9.90 parts by weight of the main pigment composition 3 and 0.10 parts by weight of the auxiliary pigment composition 1 were mixed to obtain a composition for evaluation 3a.

［評価組成物３ｂ］
主顔料組成物３の9.00重量部と、評価用組成物３ａの1.00重量部とを混合し、評価用組成物３ｂとした。 [Evaluation composition 3b]
9.00 parts by weight of the main pigment composition 3 and 1.00 parts by weight of the evaluation composition 3a were mixed to obtain an evaluation composition 3b.

［評価組成物３ｃ］
主顔料組成物３の5.00重量部と、評価用組成物３ｂの5.00重量部とを混合し、評価用組成物３ｃとした。 [Evaluation composition 3c]
5.00 parts by weight of the main pigment composition 3 and 5.00 parts by weight of the evaluation composition 3b were mixed to obtain an evaluation composition 3c.

［評価用組成物４］
主顔料組成物４を評価用組成物４とした。 [Evaluation composition 4]
The main pigment composition 4 was used as an evaluation composition 4.

［評価用組成物４ａ］
主顔料組成物４の10.00重量部と、副顔料組成物１の0.24重量部を混合し、評価用組成物４ａとした。 [Evaluation composition 4a]
10.00 parts by weight of the main pigment composition 4 and 0.24 parts by weight of the auxiliary pigment composition 1 were mixed to obtain an evaluation composition 4a.

［評価用組成物４ｂ］
主顔料組成物４の5.00重量部と、評価用組成物４ａの2.50重量部とを混合し、評価用組成物４ｂとした。 [Evaluation composition 4b]
5.00 parts by weight of the main pigment composition 4 and 2.50 parts by weight of the evaluation composition 4a were mixed to obtain an evaluation composition 4b.

［評価用組成物５］
主顔料組成物５を評価用組成物５とした。 [Evaluation composition 5]
The main pigment composition 5 was used as an evaluation composition 5.

［評価用組成物５ａ］
主顔料組成物５の9.90重量部と、副顔料組成物１の0.10重量部を混合し、評価用組成物５ａとした。 [Evaluation composition 5a]
9.90 parts by weight of the main pigment composition 5 and 0.10 parts by weight of the auxiliary pigment composition 1 were mixed to obtain an evaluation composition 5a.

［評価用組成物５ｂ］
主顔料組成物５の5.00重量部と、評価用組成物５ａの5.00重量部とを混合し、評価用組成物５ｂとした。 [Evaluation composition 5b]
5.00 parts by weight of the main pigment composition 5 and 5.00 parts by weight of the evaluation composition 5a were mixed to obtain an evaluation composition 5b.

［評価用組成物５ｃ］
主顔料組成物５の8.00重量部と、評価用組成物５ｂの2.00重量部とを混合し、評価用組成物５ｃとした。 [Evaluation composition 5c]
8.00 parts by weight of the main pigment composition 5 and 2.00 parts by weight of the evaluation composition 5b were mixed to obtain an evaluation composition 5c.

［評価用組成物６ａ］
主顔料組成物５の9.20重量部と、副顔料組成物２の0.80重量部を混合し、評価用組成物６ａとした。 [Evaluation composition 6a]
9.20 parts by weight of the main pigment composition 5 and 0.80 parts by weight of the auxiliary pigment composition 2 were mixed to obtain a composition for evaluation 6a.

［評価用組成物６ｂ］
主顔料組成物５の5.00重量部と、評価用組成物６ａの5.00重量部とを混合し、評価用組成物６ｂとした。 [Evaluation composition 6b]
5.00 parts by weight of the main pigment composition 5 and 5.00 parts by weight of the evaluation composition 6a were mixed to obtain an evaluation composition 6b.

［評価用組成物６ｃ］
主顔料組成物５の5.00重量部と、評価用組成物６ｂの5.00重量部とを混合し、評価用組成物６ｃとした。 [Evaluation composition 6c]
5.00 parts by weight of the main pigment composition 5 and 5.00 parts by weight of the evaluation composition 6b were mixed to obtain an evaluation composition 6c.

［評価用組成物７ａ］
主顔料組成物５の4.60重量部と、副顔料組成物３の0.40重量部を混合し、評価用組成物７ａとした。 [Evaluation composition 7a]
4.60 parts by weight of the main pigment composition 5 and 0.40 parts by weight of the auxiliary pigment composition 3 were mixed to obtain a composition for evaluation 7a.

［評価用組成物７ｂ］
主顔料組成物５の9.60重量部と、副顔料組成物３の5.00重量部とを混合し、評価用組成物７ｂとした。 [Evaluation composition 7b]
9.60 parts by weight of the main pigment composition 5 and 5.00 parts by weight of the auxiliary pigment composition 3 were mixed to obtain a composition for evaluation 7b.

［評価用組成物７ｃ］
主顔料組成物５の5.00重量部と、評価用組成物８ｂの5.00重量部とを混合し、評価用組成物７ｃとした。 [Evaluation composition 7c]
5.00 parts by weight of the main pigment composition 5 and 5.00 parts by weight of the evaluation composition 8b were mixed to obtain an evaluation composition 7c.

［評価用組成物７ｄ］
主顔料組成物５の8.00重量部と、評価用組成物８ｃの2.00重量部とを混合し、評価用組成物７ｄとした。 [Evaluation composition 7d]
8.00 parts by weight of the main pigment composition 5 and 2.00 parts by weight of the evaluation composition 8c were mixed to obtain an evaluation composition 7d.

［評価用組成物７ｅ］
主顔料組成物５の9.00重量部と、評価用組成物８ｄの1.00重量部とを混合し、評価用組成物７ｅとした。 [Evaluation composition 7e]
9.00 parts by weight of the main pigment composition 5 and 1.00 parts by weight of the evaluation composition 8d were mixed to obtain an evaluation composition 7e.

［評価用組成物８ａ］
主顔料組成物５の9.20重量部と、副顔料組成物４の0.80重量部を混合し、評価用組成物８ａとした。 [Evaluation composition 8a]
9.20 parts by weight of the main pigment composition 5 and 0.80 parts by weight of the auxiliary pigment composition 4 were mixed to obtain an evaluation composition 8a.

［評価用組成物９ａ］
主顔料組成物６の9.20重量部と、副顔料組成物３の0.80重量部を混合し、評価用組成物９ａとした。 [Evaluation composition 9a]
9.20 parts by weight of the main pigment composition 6 and 0.80 parts by weight of the auxiliary pigment composition 3 were mixed to obtain an evaluation composition 9a.

［評価用組成物１０ａ］
主顔料組成物７の9.20重量部と、副顔料組成物３の0.80重量部を混合し、評価用組成物１０ａとした。 [Evaluation composition 10a]
9.20 parts by weight of the main pigment composition 7 and 0.80 parts by weight of the auxiliary pigment composition 3 were mixed to obtain an evaluation composition 10a.

［評価用組成物１１ａ］
主顔料組成物８の9.20重量部と、副顔料組成物３の0.80重量部を混合し、評価用組成物１１ａとした。 [Evaluation composition 11a]
9.20 parts by weight of the main pigment composition 8 and 0.80 parts by weight of the auxiliary pigment composition 3 were mixed to obtain an evaluation composition 11a.

［評価用組成物１２ａ］
主顔料組成物９の9.20重量部と、副顔料組成物３の0.80重量部を混合し、評価用組成物１２ａとした。 [Evaluation composition 12a]
9.20 parts by weight of the main pigment composition 9 and 0.80 parts by weight of the auxiliary pigment composition 3 were mixed to prepare an evaluation composition 12a.

［評価用組成物１３ａ］
主顔料組成物１０の9.20重量部と、副顔料組成物３の0.80重量部を混合し、評価用組成物１３ａとした。 [Evaluation composition 13a]
9.20 parts by weight of the main pigment composition 10 and 0.80 parts by weight of the auxiliary pigment composition 3 were mixed to obtain a composition for evaluation 13a.

＜Ｄ／評価用塗布板の作製＞
各種評価組成物を、厚さ1mm、100mm角の無アルカリガラス基板上にスピンコーター（ミカサ株式会社製、スピンコーターMS-150A）を用いて、色度座標（x,y）のうち表１、表２又は表４において指定されたx又はｙの座標値が、指定の通りとなる回転数に合わせて製膜し、90℃恒温槽にて2分30秒間乾燥した。露光装置（株式会社三永電機製作所製、商品名：UVE-1001S型露光光源装置、YSH-100SA型超高圧水銀ランプ）を用いて60mJ/cm²の露光強度となるよう、紫外線を塗布板に照射し、235℃で30分間ポストベイクを実施し、評価用塗布板を得た。同様にして、表１、表２又は表４において指定されたx又はｙの座標値が評価用組成物と同じ値を持つ、副顔料を含まない評価用組成物１〜５の塗布板（対照物）を用意した。 <Preparation of D / coated plate for evaluation>
Each of the compositions for evaluation was placed on a non-alkali glass substrate having a thickness of 1 mm and a size of 100 mm by using a spin coater (Micasa Co., Ltd., spin coater MS-150A). The x or y coordinate value specified in Table 2 or Table 4 was formed into a film according to the number of rotations as specified, and the film was dried in a 90 ° C constant temperature bath for 2 minutes and 30 seconds. UV light is applied to the coated plate using an exposure device (manufactured by Sanei Denki Seisakusho Co., Ltd., trade name: UVE-1001S type exposure light source device, YSH-100SA type ultra-high pressure mercury lamp) so that the exposure intensity is 60 mJ / cm ^2. Irradiation and post-baking were performed at 235 ° C. for 30 minutes to obtain a coated plate for evaluation. Similarly, the coated plates of the evaluation compositions 1 to 5 containing no sub-pigment, in which the x or y coordinate value specified in Table 1, Table 2 or Table 4 has the same value as the evaluation composition (control). Things) were prepared.

＜Ｅ／輝度及び色度の測定方法＞
各評価用塗布板について、測色計（ミノルタ製CM-3700d）を用いて、輝度値（Yn）及び色度座標（xn,yn）を測定した。さらに、上記対照物との比較値（dY＝測定物のY値−対照物のY値、dx＝測定物のx値−対照物のx値、dy＝測定物のy値−対照物のy値）を算出した。 <E / luminance and chromaticity measurement method>
The luminance value (Yn) and chromaticity coordinates (xn, yn) of each evaluation coated plate were measured using a colorimeter (CM-3700d manufactured by Minolta). Furthermore, the comparison value with the above control (dY = Y value of the measurement product−Y value of the control product, dx = x value of the measurement product−x value of the control product, dy = y value of the measurement product−y of the control product) Value) was calculated.

＜Ｆ／コントラスト測定方法＞
各評価用塗布板を偏光板（株式会社ルケオ製、POLAX-38S）に挟み、ランプ（HF-LS-100WLCG）の上に設置し、偏光板がクロスニコル配置にある時の輝度（Ycn）及びパラレルニコル配置にある時の輝度（Ypn）を、色彩輝度計（コニカミノルタセンシング株式会社製、LS-100）で測定し、コントラスト比（CR）を算出した。さらに、対照物との比較値（CR％；測定物のCR/対照物のCR）を算出した。 <F / Contrast measurement method>
Each evaluation coated plate was sandwiched between polarizing plates (Lukeo Co., Ltd., POLAX-38S) and placed on the lamp (HF-LS-100WLCG), and the brightness (Ycn) and The luminance (Ypn) in the parallel Nicol arrangement was measured with a color luminance meter (LS-100, manufactured by Konica Minolta Sensing Co., Ltd.), and the contrast ratio (CR) was calculated. Further, a comparison value with the control product (CR%; CR of the measurement product / CR of the control product) was calculated.

＜Ｇ／分光透過スペクトル測定方法＞
主顔料組成物（主顔料分12〜15％）を評価色度付近となるような回転数で秒間スピンコート塗布して得られたガラス塗板と、副顔料組成物（副顔料分1％）を1000rpmで1分間スピンコート塗布して得られたガラス塗板を用意した。これらガラス塗板について、紫外可視近赤外吸収スペクトル測定装置（日本分光株式会社製、V-670）を用いて分光透過スペクトルを測定した。そして、主顔料組成物の分光透過スペクトルの外挿透過端（x nm）と、（x-80nm）の波長範囲における平均透過率を算出した。 <G / spectral transmission spectrum measuring method>
A glass coated plate obtained by spin-coating the main pigment composition (main pigment content 12 to 15%) at a rotation speed for about the evaluation chromaticity for a second and a sub-pigment composition (sub-pigment content 1%). A glass coated plate obtained by spin coating at 1000 rpm for 1 minute was prepared. The spectral transmission spectra of these glass coated plates were measured using an ultraviolet-visible near-infrared absorption spectrum measuring device (V-670, manufactured by JASCO Corporation). Then, the extrapolated transmission edge (x nm) of the spectral transmission spectrum of the main pigment composition and the average transmittance in the wavelength range of (x-80 nm) were calculated.

＜Ｈ／ヘイズスペクトル測定方法＞
プロピレングリコールモノメチルエーテルアセテート（PMA）を用い、評価用組成物を2倍希釈した試料を調製した。この試料を、厚さ1mm、100mm角の無アルカリガラス基板上に回転数1000rpmで1分間スピンコート塗布し、測定用ガラス塗板を作製した。積分球ユニット付き紫外可視近赤外吸収スペクトル測定装置（株式会社島津製作所製、SolidSpec-3700）を用いて、全光線透過率（Tt）及び拡散透過率（Td）のスペクトルデータを測定した。そして、各波長における透過率の比（Td/Tt）を計算することにより、ヘイズスペクトルを得た。 <Method of measuring H / haze spectrum>
Using propylene glycol monomethyl ether acetate (PMA), a 2-fold diluted composition for evaluation was used to prepare a sample. This sample was spin-coated on a 100 mm square alkali-free glass substrate having a thickness of 1 mm at a rotation speed of 1000 rpm for 1 minute to prepare a glass-coated plate for measurement. Spectral data of total light transmittance (Tt) and diffuse transmittance (Td) were measured using an ultraviolet-visible near-infrared absorption spectrum measuring device with an integrating sphere unit (SolidSpec-3700, manufactured by Shimadzu Corporation). Then, the haze spectrum was obtained by calculating the transmittance ratio (Td / Tt) at each wavelength.

評価用組成物１と１ａ〜１ｄはxが0.648；評価用組成物２と２ａはxが0.685；評価用組成物３と３ａ〜３ｂはyが0.500；評価用組成物４と４ａ〜４ｂはxが0.500；評価用組成物５と５ａ〜５ｃはxが0.460となるよう、それぞれ回転数が選択された。 X is 0.648 for the evaluation compositions 1 and 1a to 1d; x is 0.685 for the evaluation compositions 2 and 2a; y is 0.500 for the evaluation compositions 3 and 3a to 3b; and evaluation compositions 4 and 4a to 4b are x is 0.500; the rotational speeds of the compositions 5 for evaluation and 5a to 5c were selected so that x was 0.460.

表１は、評価用組成物１〜５ｃについて、主顔料、副顔料及び副顔料濃度(質量％)と、(dx,dy)、dY及びCR(％)の測定結果を示す。赤色顔料であるC. I. Pigment Red 254を主顔料とし、カーボンブラック(CB)を副顔料とする評価用組成物１ａ〜１ｄは、CBを含有しない評価用組成物と比較して、dx及びdyに殆ど変化が認められず、副顔料の混合によっても主顔料の色彩が影響されていないことが示された。CB濃度が0.8質量％の場合にはdY＜-2となった。CRは、CB濃度が0.08質量％以上であれば対照よりも10％以上向上した。 Table 1 shows the main pigment, the sub-pigment and the sub-pigment concentration (mass%), and the measurement results of (dx, dy), dY and CR (%) for the compositions 1 to 5c for evaluation. The evaluation compositions 1a to 1d containing CI Pigment Red 254, which is a red pigment, as a main pigment and carbon black (CB) as a sub-pigment were found to have almost no dx and dy as compared to the evaluation composition containing no CB. No change was observed, indicating that the color of the main pigment was not affected by the mixing of the sub-pigments. When the CB concentration was 0.8% by mass, dY <-2. CR was improved by 10% or more over the control when the CB concentration was 0.08% by mass or more.

赤色顔料であるC. I. Pigment Red 269を主顔料とした評価用組成物２は、CB濃度1.6質量％でもdx及びdyに殆ど変化が認められなかったが、dYは-4.33となった。この場合でも、CRは対照よりも17％向上した。 In the evaluation composition 2 containing C. I. Pigment Red 269, which is a red pigment, as the main pigment, almost no change was observed in dx and dy even when the CB concentration was 1.6% by mass, but dY was -4.33. Again, the CR was 17% better than the control.

図１は、C. I. Pigment Red 254及びCBの300nm〜800nmにおける透過率（％）を測定したグラフを示す。図２は、C. I. Pigment Red 269及びCBの300nm〜800nmにおける透過率（％）を測定したグラフを示す。図１より、主顔料であるC. I. Pigment Red 254の分光透過スペクトルの外挿透過端（x nm）は575nmであることが確認できる。同様に、図２より、主顔料であるC. I. Pigment Red 269の分光透過スペクトルの外挿透過端（x nm）は590nmであることが確認できる。 FIG. 1 is a graph showing the measured transmittance (%) of C. I. Pigment Red 254 and CB at 300 nm to 800 nm. FIG. 2 is a graph showing the measured transmittance (%) of C. I. Pigment Red 269 and CB at 300 nm to 800 nm. From FIG. 1, it can be confirmed that the extrapolated transmission edge (x nm) of the spectral transmission spectrum of C.I. Pigment Red 254, which is the main pigment, is 575 nm. Similarly, from FIG. 2, it can be confirmed that the extrapolated transmission edge (x nm) of the spectral transmission spectrum of C.I. Pigment Red 269, which is the main pigment, is 590 nm.

表２は、C. I. Pigment Red 254及びC. I. Pigment Red 269の透過帯域の低波長端X(nm)及びX-80(nm)と、副顔料としてのカーボンブラック(CB)のx-80 (nm)以上x (nm)以下の波長範囲における平均透過率を示す。副顔料であるCBは、平均透過率が59％と75％以下であった。 Table 2 shows low wavelength edges X (nm) and X-80 (nm) of the transmission band of CI Pigment Red 254 and CI Pigment Red 269, and x-80 (nm) or more of carbon black (CB) as a sub-pigment. The average transmittance in the wavelength range of x (nm) or less is shown. The secondary pigment CB had an average transmittance of 59% or less than 75%.

黄色顔料であるC. I. Pigment Yellow 138を主顔料とし、CBを副顔料とする評価用組成物３ａ〜３ｃについては、CB濃度0.0004質量％〜0.08質量％の範囲ではdx及びdyに殆ど変化が認められず、dY＞-2でありながら、CRは若干向上した。しかし、C. I. Pigment Yellow 139及び185を主顔料とした評価用組成物４ａ〜４ｂ、５ａ〜５ｃについては、CB濃度が0.4質量％以上になれば、CRは向上するがdY＜-4となり、主顔料である黄色の色彩に変化が生じた。 For the evaluation compositions 3a to 3c containing CI Pigment Yellow 138, which is a yellow pigment, as the main pigment and CB as the sub-pigment, almost no change was observed in dx and dy in the range of CB concentration 0.0004% by mass to 0.08% by mass. However, CR was slightly improved while dY> -2. However, for the evaluation compositions 4a-4b, 5a-5c using CI Pigment Yellow 139 and 185 as the main pigments, when the CB concentration is 0.4% by mass or more, the CR is improved but dY <-4. There was a change in the color of the yellow pigment.

副顔料の割合が増加すればCRが向上する反面、色彩が変化する蛍光があることが確認されたが、dY＜-2では色彩の変化が大きく、黄色又は赤色カラーフィルタへの利用が好ましくなくなる。副顔料濃度とdY又はCRとをプロットしたグラフから、dY=-2を限度とすると、主顔料が赤色の場合には、副顔料であるCBは0.668質量％以下とすることが好ましいと考察された。また、主顔料が黄色の場合には、副顔料であるCBは0.167質量％以下とすることが好ましいと考察された。 Although CR was improved when the ratio of the sub-pigment increased, it was confirmed that there was fluorescence with a change in color, but when dY <-2, the change in color was large, making it unsuitable for use in yellow or red color filters. . From the graph plotting the sub-pigment concentration and dY or CR, if dY = -2 is the limit, when the main pigment is red, it is considered that CB as the sub-pigment is preferably 0.668 mass% or less. It was Further, it was considered that when the main pigment is yellow, it is preferable that the content of CB as the sub-pigment is 0.167 mass% or less.

その一方、副顔料濃度が低すぎるとCR向上効果が得られない。対照よりもCRを最低3％向上させつつ、色彩への影響が小さい副顔料濃度範囲としては、(i) 赤色顔料を主顔料、CBを副顔料とする場合には、評価用組成物における副顔料濃度を0.08質量％以上0.668質量％以下とする；(ii) 黄色顔料を主顔料、CBを副顔料とする場合には、評価用組成物における副顔料濃度を0.004質量％以上0.167質量％以下とする：ことが好ましいと判断された。 On the other hand, if the auxiliary pigment concentration is too low, the CR improving effect cannot be obtained. While improving CR by at least 3% as compared with the control, the sub-pigment concentration range that has a small effect on color is as follows: (i) When the red pigment is the main pigment and CB is the sub-pigment, The pigment concentration is 0.08% by mass or more and 0.668% by mass or less; (ii) When the yellow pigment is the main pigment and CB is the auxiliary pigment, the auxiliary pigment concentration in the evaluation composition is 0.004% by mass or more and 0.167% by mass or less. Shall be: It was judged that it was preferable.

表３は、評価用組成物５〜５ｃ、６ａ〜６ｃ、７ａ〜７ｅ及び８ａについて、主顔料、副顔料及び副顔料濃度(質量％)と、(dx,dy)、dY及びCR(％)の測定結果を示す。いずれもxが0.460となる回転数が選択された。C. I. Pigment Yellow 135を主顔料とし、C. I. Pigment Red 179を副顔料として使用した場合、副顔料濃度0.4質量％ではdY＞-2であり、CRは対照よりも20％向上した。しかし、0.8質量％以上ではdY＜-2となり主顔料の色彩が変化した。また、副顔料としてC. I. Pigment Red 57を使用した場合、副顔料濃度1.6質量％でdY＜-2となり、CRも対照より14％低下した。 Table 3 shows the main pigment, the sub-pigment and the sub-pigment concentration (mass%), (dx, dy), dY and CR (%) for the compositions 5 to 5c, 6a to 6c, 7a to 7e and 8a for evaluation. The measurement result of is shown. In all cases, the rotation speed was selected so that x was 0.460. When C. I. Pigment Yellow 135 was used as the main pigment and C. I. Pigment Red 179 was used as the sub-pigment, dY> -2 at a sub-pigment concentration of 0.4% by mass, and CR was improved by 20% compared to the control. However, when 0.8% by mass or more, dY <-2 and the color of the main pigment changed. When C.I. Pigment Red 57 was used as the sub-pigment, dY <-2 was obtained at a sub-pigment concentration of 1.6% by mass, and CR was 14% lower than that of the control.

表４は、C. I. Pigment Yellow 139及びC. I. Pigment Yellow 185の透過帯域の低波長端X(nm)及びX-80(nm)と、副顔料としてのカーボンブラック(CB)、C. I. Pigment Red 179(R179)、C. I. Pigment Brown 25(Br25)及びC. I. Pigment Red 57(R57)のx-80 (nm)以上x (nm)以下の波長範囲における平均透過率を示す。主顔料と副顔料について、図１及び２と同様に300nm〜800nmにおける透過率（％）を測定したグラフから、x(nm)、x-80(nm)を求め、その波長内における平均透過率を算出した。C. I. Pigment Red 57のみ、平均透過率が75％超であり、その他は75％以下であった。 Table 4 shows low wavelength edges X (nm) and X-80 (nm) of the transmission bands of CI Pigment Yellow 139 and CI Pigment Yellow 185, carbon black (CB) as a sub-pigment, and CI Pigment Red 179 (R179). , CI Pigment Brown 25 (Br25) and CI Pigment Red 57 (R57) in the wavelength range from x-80 (nm) to x (nm). As for the main pigment and the sub-pigment, x (nm) and x-80 (nm) were calculated from the graph of transmittance (%) measured at 300 nm to 800 nm as in FIGS. 1 and 2, and the average transmittance within that wavelength was obtained. Was calculated. Only C. I. Pigment Red 57 had an average transmittance of more than 75%, and the others had 75% or less.

評価用組成物５と７ａはxが0.460；評価用組成物６と９ａはxが0.500；評価用組成物７と１０ａはxが0.445；評価用組成物８と１１ａはxが0.443；評価用組成物１２ａはxが0.467；評価用組成物１３ａはxが0.476となる回転数が、それぞれ選択された。評価用組成物９は、評価用組成物１２ａの対照とされる際にはxが0.467となる回転数が選択され、評価用組成物１３ａの対照とされる際にはxが0.476となる回転数が選択された。 X is 0.460 for the evaluation compositions 5 and 7a; x is 0.500 for the evaluation compositions 6 and 9a; x is 0.445 for the evaluation compositions 7 and 10a; x is 0.443 for the evaluation compositions 8 and 11a; The composition 12a was selected such that the x was 0.467; and the evaluation composition 13a was selected such that the x was 0.476. For the evaluation composition 9, a rotation number at which x is 0.467 is selected when it is used as a control of the evaluation composition 12a, and x is 0.476 when it is used as a control of the evaluation composition 13a. A number was selected.

表５は、黄色の主顔料6種類と、副顔料としてC. I. Pigment Brown 25とを含有する評価用組成物について、主顔料、副顔料及び副顔料濃度(質量％)と、(dx,dy)、dY及びCR(％)の測定結果を示す。C. I. Pigment Yellow 180及びC. I. Pigment Yellow 17を主顔料とする評価用組成物１２ａ及び１３ａは、他の黄色顔料を含有する評価用組成物と異なり、副顔料濃度1.6質量％以上ではdY＜-2となり、色彩が変化した。これら以外の評価用組成物は、C. I. Pigment Brown 25濃度3.33質量％以下で色彩の変化が小さく、CRは対照よりも向上した。 Table 5 shows a main pigment, a sub-pigment and a sub-pigment concentration (mass%), (dx, dy), for the evaluation composition containing 6 types of yellow main pigments and CI Pigment Brown 25 as a sub-pigment, The measurement results of dY and CR (%) are shown. The evaluation compositions 12a and 13a containing CI Pigment Yellow 180 and CI Pigment Yellow 17 as the main pigments, unlike the evaluation compositions containing other yellow pigments, had dY <-2 when the auxiliary pigment concentration was 1.6% by mass or more. , The color has changed. The compositions for evaluation other than these showed little change in color at C. I. Pigment Brown 25 concentration of 3.33% by mass or less, and CR was improved as compared with the control.

表３及び表５の結果から、主顔料が黄色（C. I. Pigment Yellow 180及びC. I. Pigment Yellow 17を除く）の場合には、副顔料であるC. I. Pigment Brown 25は0.0008質量％以上3.33質量％以下とすることが好ましいと考察された。 From the results of Tables 3 and 5, when the main pigment is yellow (excluding CI Pigment Yellow 180 and CI Pigment Yellow 17), CI Pigment Brown 25, which is a sub-pigment, is 0.0008 mass% or more and 3.33 mass% or less. Was considered preferable.

図３は、評価用組成物５（Y185）及び評価用組成物７ｂ（Y185/Br25）のヘイズスペクトル測定結果を示す。副顔料を含有しない評価用組成物５と比較して、副顔料であるC. I. Pigment Brown 25を含有する評価用組成物７ｂは、435nm及び468nmにおける散乱が抑制されていることが確認された。 FIG. 3 shows the haze spectrum measurement results of the evaluation composition 5 (Y185) and the evaluation composition 7b (Y185 / Br25). It was confirmed that scattering was suppressed at 435 nm and 468 nm in the evaluation composition 7b containing the sub-pigment C. I. Pigment Brown 25, as compared with the evaluation composition 5 containing no sub-pigment.

本発明のカラーフィルタ用着色組成物は、光学又は電子機器等の技術分野において有用である。 The coloring composition for a color filter of the present invention is useful in the technical field of optical or electronic devices.

Claims

A coloring composition for a color filter, containing a main dye that is yellow or red and a sub-dye that is darker than the main dye,
The sub-dye has a transmittance of 75% or less in the wavelength range of x-80 (nm) or more and x (nm) or less, where x (nm) is the low wavelength end of the transmission band of the main dye.
Coloring composition for color filter.

The main pigment is yellow,
The sub-dye is carbon black,
The sub-dye concentration in the color filter dye is 0.004 mass% or more and 0.167 mass% or less,
The coloring composition for a color filter according to claim 1.

The main pigment is yellow,
The sub-dye is brown,
The sub-dye concentration in the color filter dye is 0.008 mass% or more and 3.34 mass% or less,
The coloring composition for a color filter according to claim 1.

The main pigment is one selected from the group consisting of CI Pigment Yellow 74, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150 and CI Pigment Yellow 185,
The sub-dye is CI Pigment Brown 25,
The coloring composition for a color filter according to claim 3.

The main pigment is CI Pigment Red 254 which is red,
The sub-dye is carbon black,
The sub-dye concentration in the color filter dye is 0.08 mass% or more and 0.668 mass% or less,
The coloring composition for a color filter according to claim 1.