JP4749658B2 - Colored resin film for color filter and method for producing the same, evaluation method for colored resin film for color filter, and color filter - Google Patents

Description

【０１００】
＜着色樹脂組成物の調製＞
上記から得られた各色の顔料分散液の各々２００質量部当たりにつき、下記組成をそれぞれ攪拌機にて均一に混合し、各色用のカラーフィルター用着色樹脂組成物を調製した。
【０１０１】
〔組成〕
・ベンジルメタアクリレート／メタアクリル酸共重合体 ３３質量部
（アルカリ可溶性樹脂、共重合モル比＝７０／３０、重量平均分子量 ３万）
・ジペンタエリスリトールペンタアクリレート（モノマー） ３６質量部
・プロピレングリコールモノメチルエチルアセテート（溶剤） １１０質量部
・エチル−３−エトキシプロピオネート（溶剤） ４４質量部
・ハロメチルトリアジン系開始剤 ４質量部
（光重合開始剤、商品名：ＴＡＺ１０７、みどり化学（株）製）
【０１０２】
《カラーフィルター用着色樹脂被膜の形成》
上記から得られた三色のカラーフィルター用着色樹脂組成物をそれぞれ別個に、アルカリ洗浄済みのガラス基板１０ｃｍ×１０ｃｍ（商品名：１７３７、コーニング（株）製）表面に均一になるようスピンコートを用いて塗布して光硬化性塗布膜を形成した。尚、スピンコートは、塗布後に塗布膜の表面温度１１０℃×１２０秒の条件で加熱処理した際に、着色樹脂被膜の膜厚が１．０μｍになるように塗布回転数を調節した。
【０１０３】
次いで、得られた光硬化性塗布膜を、ホットプレート上で１１０℃×１２０秒の条件で加熱処理（プリベーク）した。その後、２．５ＫＷの超高圧水銀灯を用いて、光硬化性塗布膜上の全面に２００ｍＪ／ｃｍ²の露光量で照射し、光硬化処理を行った。更に、有機系現像液（商品名：ＣＤ−２０００、富士フイルムアーチ（株）製）の４０％水溶液を用いて露光済みの塗布膜を覆い、６０秒間静置した。その後、純水をシャワー状に散布して現像液を洗い流した。
以上のように、光硬化処理および現像処理を施した塗布膜をホットプレート上で２００℃・５分間の条件で加熱処理（ポストベーク）を施し、各色についてガラス基板上にサイズ９ｃｍ×９ｃｍの単色のカラーフィルター用着色樹脂被膜（１）〜（３）を形成した。
【０１０４】
《評価》
得られた単色のカラーフィルター用着色樹脂被膜を光学顕微鏡の観測レンズと光源との間に設置して光を観測レンズに向けて照射し、その透過光状態を倍率が１０００倍のデジタルカメラが設置された光学顕微鏡によって観察した。光学顕微鏡に設置されたデジタルカメラには１２８万画素のＣＣＤが搭載されており、透過光状態にある被膜表面を撮影した。撮影画像は８ビットのビットマップ形式でデジタル変換したデータ（デジタル画像）として保存した。尚、被膜表面の撮影は任意に選択した２０の領域に対して行った。
また、デジタル変換したデータは、撮影画像をＲＧＢの３原色それぞれの輝度を０〜２５５までの２５６階調の濃度分布として数値化して保存した。
【０１０５】
次いで、保存されたデジタル画像について、１つの格子サイズが実基板上の２μｍ四方に相当するように、格子状に区分し、一つの区画内での輝度を平均化した。本実施例においては、１２８万画素のデジタルカメラで光学１０００倍の画像を撮影したため、実基板上の２μｍは撮影画像上の２ｍｍとなり、ディスプレイ上における画像サイズが４５２ｍｍ×３５２ｍｍであったことから、一つの領域における総区画数は３９７７６個であった。
【０１０６】
各領域の全区画について、任意の１区画とそれに隣接する全ての隣接区画の平均輝度とを計測した。隣接区画の平均輝度との差が５以上の区画を有意差区画と認定し、全領域の有意差区画の平均総数と、全領域の有意差区画の平均総数が各領域の全区画数（３９７７６個）に対して占める割合とを算出した。結果を下記表２に示す。
【０１０７】
【表２】

【０１０８】
《カラーフィルターおよびＣＣＤデバイスの作製》
＜カラーフィルターの作製＞
下記組成を攪拌機で混合し、平坦化膜用レジスト液を調製した。
【０１０９】
〔組成〕
・ベンジルメタアクリレート／メタアクリル酸共重合体 １６５質量部
（共重合モル比＝７０／３０、重量平均分子量 ３万）
・ジペンタエリスリトールペンタアクリレート ６５質量部
・プロピレングリコールモノメチルエチルアセテート １３８質量部
・エチル−３−エトキシプロピオネート １２３質量部
・ハロメチルトリアジン系開始剤 ３質量部
（光重合開始剤、商品名：ＴＡＺ１０７、みどり化学（株）製）
【０１１０】
得られた平坦化用レジスト液を、フォトダイオードを形成した６インチシリコンウエハ上にスピンコートで均一に塗布した。尚、スピンコートは、塗布後に塗布膜の表面温度を１１０℃×１２０秒の条件でホットプレートを用いて加熱処理した際に膜厚が約２．０μｍになるように塗布回転数を調節した。
その後、２２０℃で１時間オーブン中に置いて、塗布膜を硬化させ、シリコンウエハ上に形成されたフォトダイオード表面を一様に覆うように、平坦化膜を形成した。
【０１１１】
次いで、各色についてＧ、Ｒ、Ｂの順に、平坦化膜上に上述のカラーフィルター用着色樹脂組成物を塗布、乾燥（プリベーク）、パターン露光、アルカリ現像、リンス、硬化乾燥（ポストベーク）を行って着色樹脂被膜を形成し、フォトダイオード付シリコンウエハ上にカラーフィルターを作製した。
【０１１２】
尚、パターン露光は、２μｍマスクパターンを介して、ｉ線ステッパー（商品名：ＦＰＡ−３０００ｉ５＋、キャノン（株）製）を用いて５００ｍＪ／ｃｍ²で行った。
また、アルカリ現像には、有機アルカリ製現像液（商品名：ＣＤ−２０００、富士フイルムアーチ（株）製）の４０質量％水溶液を用いて、室温にて６０秒間パドル現像を行った後、２０秒スピンシャワーにて純水でリンスを行い、さらに純水で水洗を行った。その後、水滴を高圧のエアーで飛ばし、基板を自然乾燥させてパターンを得た後、ホットプレート上で表面温度２００℃・５分間の条件でポストベーク処理を施した。
【０１１３】
以上のようにして得られたＣＣＤデバイスをデジタルカメラに搭載し、同一光源下でＫｏｄａｋ製グレースケール付きカラーチャートを撮影した画像をモニター上で観察したところ、ざらつきの少ない均一でなめらかな色の画像が得られた。
【０１１４】
［比較例１］
《カラーフィルター用着色樹脂被膜の形成》
実施例１における緑色用の顔料分散液（１）および青色用の顔料分散液（２）を、下記組成の緑色用の顔料分散液（４）および下記青色用の顔料分散液（５）に変更し、且つ、赤色用の顔料分散液３を用いなかった以外は実施例１と同様にして、緑色および青色用の着色樹脂被組成物（４）〜（５）および着色樹脂被膜（４）〜（５）を形成し、同様の評価を行った。結果を下記表３に示す。
【０１１５】
＜緑色用顔料分散液（４）の調製＞
実施例１の顔料分散液（１）の調製に用いた着色剤（ピグメント・グリーンＰＧ３６、ピグメント・グリーンＰＧ７、ピグメント・イエローＰＹ１３９）のそれぞれを別個に、実施例１で用いた分散剤、樹脂および溶剤と共にニーダーで均一に混練した。その後、各々の混練物を二本ロールで分散（乾式分散処理）し、得られた分散物に溶剤成分としてプロピレングリコールモノメチルエチルアセテートを加え、ホモジナイザーにて攪拌処理した。得られた混練組成物をビーズ分散機（商品名：ディスパーマット、ＧＥＴＺＭＡＮＮ製）にて微分散処理し、２．５μｍフィルターにて濾過して、ピグメント・グリーンＰＧ３６、ピグメント・グリーンＰＧ７、およびピグメント・イエローＰＹ１３９が単独で分散された３種の顔料分散液を得た。その後、これら３種の顔料分散液をホモジナイザーにて攪拌処理し、緑色用の顔料分散液（４）を得た。
尚、二本ロール、ホモジナイザー、ビーズ分散機での処理条件は、実施例１と同一の条件を採用した。
【０１１６】
＜青色用顔料分散液（５）の調製＞
緑色用顔料分散液（４）の調製と同様にして、実施例１の顔料分散液（２）で用いた２種の着色剤（ピグメント・ブルーＰＢ１５：６、ピグメント・バイオレットＰＶ２３）が単独で分散された顔料分散液を得た。その後、これら２種の顔料分散液をホモジナイザーにて攪拌処理し、青色用の顔料分散液（５）を得た。
【０１１７】
【表３】

【０１１８】
《カラーフィルターおよびＣＣＤデバイスの作製》
実施例１において着色樹脂組成物（１）を上記着色樹脂組成物（４）に変更した以外は実施例１と同様にして、カラーフィルターおよびＣＣＤデバイスを作製した。得られたＣＣＤデバイスをデジタルカメラに搭載し、同一光源下でＫｏｄａｋ製グレースケール付きカラーチャートを撮影した画像をモニター上で観察したところ、黒欠陥が認められ、且つ、ざらつき感のある画像が得られた。
【０１１９】
［比較例２］
実施例１において着色樹脂組成物（２）を上記着色樹脂組成物（５）に変更した以外は実施例１と同様にして、カラーフィルターおよびＣＣＤデバイスを作製した。得られたＣＣＤデバイスをデジタルカメラに搭載し、同一光源下でＫｏｄａｋ製グレースケール付きカラーチャートを撮影した画像をモニター上で観察したところ、黒欠陥が認められ、且つ、ざらつき感のある画像が得られた。
【０１２０】
【発明の効果】
本発明によれば、デバイス上の黒欠陥、ムラ、および再現画像のざらつきを低減させた固体撮像素子の製造に好適に用いることのできるカラーフィルタ用着色樹脂被膜およびこれを用いたカラーフィルター、並びに、カラーフィルター用着色樹脂被膜の評価方法を提供することができる。
【図面の簡単な説明】
【図１】 隣接画素を説明するための説明図である。
【符号の説明】
１，３，５ 有意差区画
２，４，６ 隣接区画[0001]
BACKGROUND OF THE INVENTION
  The present invention relates to a photosensitive colored resin composition suitable for producing a color filter used in a liquid crystal display element or a solid-state imaging element.And its manufacturing methodAnd an evaluation method thereof, and a color filter using the same.
[0002]
[Prior art]
Pigments and dyes are used as colorants for color filters. Usually, pigment is used by uniformly dispersing pigment particles in a photocurable resin composition for a color filter. On the other hand, the dye is used by being dissolved in the photocurable resin composition.
[0003]
Pigments are excellent in durability such as light resistance and heat resistance against dyes, and are widely used in color filters for liquid crystal display devices and color filters for image sensors used in solid-state image sensors such as CCD and CMOS. ing.
[0004]
In recent years, in order to meet the demand for improvement in resolution, the size of a pixel (pixel) of a color filter for a solid-state imaging device has been miniaturized, and a pixel of about 2 to 3 μm square is required. However, as the pixel size is reduced and a solid image pickup device is required to reproduce a fine image, the roughness of the reproduced image (roughness of the image) has gradually become a problem. This tendency is particularly seen in color filters using pigments. This is because the particle size of the pigment contained in the pigment-type color resist has a large influence on the device. For example, when a pigment having a coarse particle size is included, no light is received and no signal is output. May be caused. In addition, when there is a variation in the particle diameter in each pixel, the level of the output signal varies even when light of the same intensity is given to each pixel, and “unevenness” occurs between the pixels. Will occur. Further, when such unevenness occurs between adjacent pixels, the above-described “roughness” is generated, which becomes noticeable and the reproduced image based on the output signal becomes rough.
[0005]
The roughness of the reproduced image due to such pixel miniaturization is, for example, that even if the pixel has a size of about 5 to 6 μm square, even if it is a colored resin film for a color filter in which the roughness of the reproduced image does not matter. When the size is reduced to ˜3 μm square, the roughness of the reproduced image becomes remarkable, which may cause deterioration in image quality.
[0006]
In order to solve the above problem, there has been proposed a color filter coating material in which the uniformity of sensitivity of all pixels picked up by a solid-state image pickup device is improved (for example, see Patent Document 1). Such a color filter application product suppresses uneven density of a reproduced image by sharpening the distribution of the relative color density of the application product.
[0007]
On the other hand, a red color resist ink in which a diketopyrrolopyrrole pigment is dispersed together with a diketopyrrolopyrrole sulfonic acid derivative has been proposed for the purpose of obtaining a resist ink with a high level of lightness (see, for example, Patent Document 2). .) In such a red color resist ink, first, a diketopyrrolopyrrole pigment is dispersed together with a diketopyrrolopyrrolesulfonic acid derivative, and a fine particle treatment is performed so that the primary particle diameter is 100 nm or less. In the fine particle treatment, two types of pigments are dry-dispersed with three rolls, and then an organic solvent is added and wet-dispersed with a bead mill to obtain a dispersion of red pigments having an average particle size of 150 nm to 170 nm. .
[0008]
However, according to the above dispersion method, the content of the solvent component used in the dry dispersion is relatively high, and is used at about 25% by mass. Further, since the resin component or the like is not used during the dry dispersion, The particle size of the dispersion actually obtained is 100 nm or more.
[0009]
[Patent Document 1]
JP 2001-249213 A
[Patent Document 2]
JP 2000-160084 A
[0010]
[Problems to be solved by the invention]
[0011]
It is considered that the roughness of the reproduced image is caused by differences in optical characteristics such as luminance, optical density, and chromaticity between pixels. In particular, when a fine pixel such as a pixel of 3 μm or less is formed, the problem of roughness of the reproduced image becomes significant.
[0012]
  In order to solve the above problems, the present invention provides a colored resin film for a color filter that can be suitably used for manufacturing a solid-state imaging device with reduced black defects, unevenness, and roughness of a reproduced image on a device,Its manufacturing methodAnd a color filter using the same, and a method for evaluating a colored resin coating for a color filter.
[0013]
[Means for Solving the Problems]
The above problem is solved by the following means.
[0014]
  <1> A colored resin film for a color filter containing a colorant and having a thickness of 0.1 to 10 μm, wherein the surface of the film is divided into a grid to form a 2 μm square section, Each is subjected to a numerical process for attaching a luminance value obtained by quantifying the luminance of the section to 256 gradations of 0 to 255, and the luminance value given by the numerical processing and an average of all adjacent adjacent sections When the section having a difference from the luminance value of 5 or more is defined as a significant difference section, the total number of the significant difference sections is 10% or less of the total number of sections.Furthermore, the colorant is a pigment, and the pigment contains 75% by mass or more of pigment particles having an average particle diameter in the range of 0.01 ± 0.005 μm.This is a colored resin coating for a color filter.
[0015]
<2> A method for producing a colored resin film for a color filter, wherein a composition containing at least a colorant is applied to a substrate, wherein the resin film for a color filter has a thickness of 0.1 to 10 μm, and the surface of the film Are divided into a grid shape to form a 2 μm square section, and each of the sections is subjected to a numerical processing for attaching a luminance value in which the luminance of the section is numerically expressed in 256 gradations of 0 to 255, and the numerical value is applied. When the difference between the luminance value given by the process and the average luminance value of all adjacent adjacent areas is 5 or more is defined as a significant difference area, the total number of significant difference areas is the total number of areas. 10% or less, and the colorant is composed of two or more pigments, and after the two or more pigments are dispersed in a high viscosity state of 50000 mPa · s or more, a low viscosity state of 1000 mPa · s or less is further added. To disperse in A method of producing a color filter for the colored resin film and symptoms.
[0016]
  <3>The colored resin film for color filter according to <2>, wherein the two or more pigments are dispersed in a high viscosity state of 50,000 to 100,000 mPa · s, and further dispersed in a low viscosity state of 100 mPa · s or less. It is a manufacturing method.
[0017]
<4> A step of forming a 2 μm square section by dividing the surface of the colored resin film for a color filter containing a colorant into a lattice shape, and the brightness of the section in each of the sections is 256 floors from 0 to 255 A digitizing step of adding a numerical value to the key, and the difference between the luminance value of an arbitrary section and the average luminance value of all adjacent sections adjacent to the arbitrary section is 5 or more An evaluation method for a colored resin film for a color filter, comprising: an authorization step for authorizing a compartment as a significant difference compartment; and a counting step for counting the total number of the significant difference compartments.
[0018]
<5> The method for evaluating a colored resin film for a color filter according to <4>, further comprising a comparison step of comparing the total number of the significant difference sections counted in the counting step with the total number of sections. is there.
[0019]
  <6> Above<1>It is a color filter formed using the colored resin film for color filters.
[0020]
DETAILED DESCRIPTION OF THE INVENTION
<Colored resin film for color filter>
  The colored resin film for color filters of the present invention (hereinafter sometimes referred to as “colored resin film of the present invention”) contains a colorant and has a thickness of 0.1 to 10 μm. A coating is formed by dividing a coating surface into a grid shape to form 2 μm square sections, and each section is provided with a luminance value obtained by quantifying the brightness of the section in 256 gradations from 0 to 255. When the section having a difference between the brightness value given by the numerical processing and the average brightness value of all adjacent sections adjacent to the surrounding area is 5 or more is defined as a significant difference section Is less than 10% of the total number of sectionsFurthermore, the colorant is a pigment, and the pigment contains 75% by mass or more of pigment particles having an average particle diameter in the range of 0.01 ± 0.005 μm.It is characterized by that.
[0021]
In the colored resin coating of the present invention, since the total number of significant difference sections having a difference from the average luminance value of all adjacent sections of 5 or more is 10% or less of the total number of strokes, for example, for image sensors such as CCD and CMOS When used in this color filter, it is possible to reduce black spots and unevenness of each pixel, and to effectively suppress the roughness of the reproduced image.
[0022]
In the present invention, means for satisfying the condition that the total number of the specific sections is 10% or less of the total number of sections is not limited. For example, when the pigment is used as the colorant, the above conditions are such that the pigment particles contained in the colored resin composition for forming the colored resin film are fine particles having a particle diameter of about 0.01 μm, and the particle diameter Can be achieved by containing 75 mass% or more of pigment particles in the range of 0.01 ± 0.005 μm with respect to the mass of all pigment particles. In order to include the particle diameter of the pigment particles within the particle range, it is effective to disperse the pigment by a dispersion method described later.
[0023]
(Evaluation method of the present invention)
First, an evaluation method for specifying the colored resin film of the present invention will be described. The colored resin film of the present invention can be specified by, for example, the following evaluation method (hereinafter, sometimes referred to as “the evaluation method of the present invention”). In the evaluation method of the present invention, the surface of the colored resin film for a color filter containing a colorant is divided into a lattice shape to form a 2 μm square section, and the brightness of the section is set to 0 to each of the sections. When the difference between the numerical value process of attaching a numerical luminance value to 256 gradations of 255 and the luminance value of an arbitrary section and the average luminance value of all adjacent sections adjacent to the arbitrary section is 5 or more And an authorization step for authorizing the arbitrary partition as a significant difference partition, and a counting step for counting the total number of the significant difference partitions.
The evaluation method of the present invention is performed, for example, using a digital camera having an optical microscope, a CCD, and image capturing software for transmitting a colored resin film.
[0024]
The partition forming step is a step of dividing the surface of the colored resin coating into a lattice shape to form a 2 μm square partition. In the evaluation method of the present invention, since the section is divided into 2 μm squares, it is suitable as an evaluation method for an image sensor that requires minute pixels of 3 μm or less.
[0025]
The formation of the compartments in the compartment formation step is performed, for example, by the following method.
First, using a digital camera having an optical microscope and a CCD and image capturing software, a transmission image of the colored resin film is captured into a computer in a bitmap format of 8 bits per pixel. To capture the transmission image, a colored resin film is placed between the light source and the observation lens of the optical microscope, and the light is irradiated toward the observation lens, and the transparent resin surface image observed by the observation lens is digitally displayed. This is done by shooting with a camera. At this time, it is preferable to use an observation lens having a magnification of about 50 to 3000 times (preferably about 200 to 1500 times). A digital camera equipped with a CCD having effective pixels of about 3 to 5 million pixels (preferably about 128 to 5 million pixels) can be suitably used. A photographed image photographed by a digital camera is digitally converted into data in an 8-bit bitmap format and stored in a computer. The digital image saved in the 8-bit bitmap format is digitized and saved as a density distribution of 256 gradations from 0 to 255 for each of the RGB primary colors.
[0026]
Next, the stored digital image is divided into a lattice shape so that one lattice size corresponds to 2 μm square in actual size, thereby forming a partition. For example, when the surface of a resin film with an optical magnification of 1000 times is photographed with a 1.28 million pixel digital camera, 2 μm in actual size corresponds to 2 mm in the photographed image. For this reason, for example, when a section on the colored resin film to be actually evaluated is photographed with a digital camera via a 1000 × optical microscope, the photographed image size is 452 × 352 mm. If the photographed image is formed so as to have a size corresponding to 2 mm square on the digital screen, the total number of the formed spaces is 39776. In the evaluation method of the present invention, it is preferable to evaluate the entire region of the surface of the colored resin film. For example, a plurality of arbitrary regions (preferably 5 or more, more preferably 20 or more) are selected and evaluated. It is good also as evaluation of the whole colored resin film by doing.
[0027]
The digitizing step is a step of applying a digitizing process to each of the sections formed by the section forming step. The digitization process means a process of digitizing the luminance of the section into 256 gradations of 0 to 255 and attaching the value as a luminance value. Also, the digitization by the digitization process is performed by digitizing the average value of luminance in each section. In other words, when a 2 mm square section is formed on a digital image as described above, the average value of the brightness assigned when saved in an 8-bit bitmap format in one section is the brightness value of that section. And
[0028]
In the certification process, when attention is paid to an arbitrary section, the difference between the luminance value assigned to the arbitrary section and the average luminance value of all adjacent adjacent sections is calculated, and the difference is 5 or more. In this case, the arbitrary section is recognized as a “significant difference section”.
Here, “adjacent section” means a section adjacent to an arbitrary section. The adjacent section will be described with reference to FIG. For example, as shown in FIG. 1, when a section is adjacent to the surrounding eight sides like an arbitrary section 1, each of the eight sections is adjacent to the adjacent section 2 of the section 1 (located around the section 1. 8 sections indicated by diagonal lines). In addition, when an arbitrary section is located at the edge of the image as shown in FIG. 1, for example, when an adjacent section is adjacent in six directions like the arbitrary section 3 shown in FIG. Each of the six sections becomes an adjacent section 4 of the section 3 (six sections illustrated by diagonal lines arranged around the section 3). Further, when a section is adjacent to three sides like an arbitrary section 5, each of the three sections is indicated by an adjacent section 6 of the section 5 (hatched lines arranged around the section 3). 3 sections).
The average luminance value of the adjacent section is an average value of the luminance values assigned to each of the adjacent sections.
[0029]
The counting step is a step of counting the number of sections recognized as significant difference sections in the recognition step. The greater the number of significant difference sections, the greater the probability that blackout or roughness of the reproduced image will occur when a color filter formed using the colored resin film is mounted. For this reason, the performance of the colored resin coating film for color filters can be evaluated based on the number of significant difference sections counted in the counting step. As such evaluation, the total number of significant difference sections counted may be used as an absolute number, or may be compared with the total number of sections as described later. In the case where the total number of significant difference sections is used as an absolute number, for example, the number of significant difference sections allowed is used as a threshold value, and the colored resin coating is determined by whether or not the total number of significant difference sections exceeds the threshold value. Performance can be evaluated.
[0030]
As described above, the evaluation method of the present invention may further include a comparison step of comparing the total number of significant difference zones counted in the counting step with the total number of zones. In the comparison step, the total number of significant difference sections counted is compared with the total number of sections, and the performance of the colored resin coating can be evaluated based on the value. In the comparison step, the counted total number of significant difference sections and the total number of sections can be compared, and for example, the ratio of the total number of significant difference sections to the total number of sections can be calculated. In this case, the permissible value of the ratio of the total number of significant difference sections to the total number of sections is set as a threshold value, and the performance of the colored resin coating is evaluated based on whether or not the value calculated by the comparison step exceeds the threshold value. be able to.
[0031]
In the colored resin film of the present invention, the total number of the significant difference sections is 10% or less of the total number of sections. If the total number of significant difference sections exceeds 10% of the total number of sections, black spots and unevenness, roughness of reproduced images, etc. occur when used as a color filter for an image sensor or the like. The ratio of the total number of the significant difference sections to the total number of sections is preferably 7% or less, more preferably 5% or less, and particularly preferably 3% or less.
[0032]
The evaluation method of the present invention can be preferably implemented by a computer or the like. The evaluation method of the present invention is useful not only for performance evaluation of a colored resin film containing a pigment as a colorant, but also for performance evaluation of a colored resin film using a dye as a colorant.
[0033]
<Colored resin film for color filter>
Next, each component etc. which comprise the colored resin film of this invention are demonstrated. The colored resin film of the present invention contains at least a colorant and has a thickness of 0.1 to 10 μm. The colored resin film of the present invention can improve the performance of an image sensor using this because even when a fine pixel of about 3 μm or less is formed, there is little blackout or roughness of a reproduced image. As thickness of the colored resin film of this invention, 0.5-7 micrometers is preferable, More preferably, it is 0.5-2.0 micrometers.
[0034]
The colored resin film of the present invention can be formed by applying and drying a colored resin composition (hereinafter sometimes referred to as “composition in the present invention”) on a substrate. The composition in the present invention contains at least a colorant and, as necessary, an alkali-soluble resin, a photosensitive polymerization component, a photopolymerization initiator, a solvent, and other components as long as the effects of the present invention are not impaired. To do.
[0035]
(Coloring agent)
  As the colorant, various conventionally known dyes and pigments can be used singly or in combination. In particular, as the colored resin film of the present invention, in order to satisfy the condition that the total number of the above-mentioned special pixels is 10% or less with respect to the total number of all pixels, two or more kinds of pigments are used.UseFurthermore, it is particularly preferable that these pigments are dispersed by a dispersion method described later.
[0036]
-Pigment-
As the pigment, conventionally known various inorganic pigments or organic pigments can be used. Moreover, considering that it is preferable that the pigment has a high transmittance, whether it is an inorganic pigment or an organic pigment, it is preferable to use a pigment as fine as possible. Considering handling properties, the pigment particle diameter is preferably 0.01 μm to 0.1 μm, more preferably 0.01 μm to 0.05 μm, and the particle diameter is 0.01 μm. It is particularly preferable that the pigment particles in the range of ± 0.005 μm are contained in an amount of 75% by mass or more based on the total mass of the pigment particles. In order to achieve such particle size distribution, it is preferable to disperse the pigment by a dispersion method described later.
[0037]
The inorganic pigment is a metal compound represented by a metal oxide, a metal complex salt or the like, specifically, metal oxide such as aluminum, iron, cobalt, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, etc. And composite oxides of the above metals.
[0038]
As the organic pigment,
C.I.Pigment Yellow 11, 24, 31, 53, 83, 93, 99, 108, 109, 110, 138, 139, 147, 150, 151, 154, 155, 167, 180, 185, 199,;
C.I.Pigment Orange 36, 38, 43, 71;
C.I.Pigment Red 81, 105, 122, 149, 150, 155, 171, 175, 176, 177,209, 220, 224, 242, 254, 255, 264, 270;
C.I.Pigment Violet 19, 23, 32, 39;
C.I.Pigment Blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;
C.I.Pigment Green 7, 36, 37;
C.I.Pigment Brown 25, 28;
Etc.
[0039]
Although the following can be mentioned as a pigment which can be preferably used in this invention, This invention is not limited to these.
[0040]
C.I.Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185,
C.I.Pigment Orange 36, 71,
C.I.Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264,
C.I.Pigment Violet 19, 23, 32,
C.I.Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,
[0041]
The above organic pigments may be used alone or in various combinations in order to increase color purity. Specific examples of red pigments include anthraquinone pigments, perylene pigments, diketopyrrolopyrrole pigments alone or at least one of them and disazo yellow pigments, isoindoline yellow pigments, quinophthalone yellow pigments or perylenes. A combination with a red pigment can be used. For example, as an anthraquinone pigment, C.I. I. Pigment Red 177 and perylene pigments include C.I. I. Pigment red 155, C.I. I. Pigment Red 224 and diketopyrrolopyrrole pigments include C.I. I. Pigment red 254, and C.I. I. Pigment yellow 83 or C.I. I. A combination with Pigment Yellow 139 is preferred. The mass ratio of the red pigment to the yellow pigment is preferably 100: 5 to 100: 50, more preferably 100: 10 to 100: 30. When the mass ratio is within such a range, the light transmittance can be suppressed and the color purity can be improved, and further, it is possible to prevent the main wavelength from becoming shorter than the NTSC target hue. In the case of a combination of red pigments, it can be adjusted in accordance with the chromaticity.
[0042]
As the green pigment, a halogenated phthalocyanine pigment alone or a combination with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindoline yellow pigment can be used. For example, C.I. I. Pigment Green 7, 36, 37 and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180 or C.I. I. Mixing with Pigment Yellow 185 is preferred. The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 150, more preferably 100: 30 to 100: 120. When the mass ratio is within such a range, the light transmittance of 400 nm to 450 nm can be suppressed and the color purity can be improved, and further, the main wavelength can be prevented from deviating from the NTSC target hue due to the longer wavelength. it can.
[0043]
As the blue pigment, a phthalocyanine pigment alone or a combination with a dioxazine purple pigment can be used. Examples of the combination include C.I. I. Pigment blue 15: 6 and C.I. I. Mixing with pigment violet 23 is preferred. The mass ratio of the blue pigment to the violet pigment is preferably 100: 0 to 100: 30, more preferably 100: 10 or less.
[0044]
Furthermore, by using a powdered processed pigment in which the above pigment is finely dispersed in an acrylic resin, a maleic acid resin, a vinyl chloride-vinyl acetate copolymer, an ethyl cellulose resin, or the like, a pigment-containing photosensitive material having good dispersibility and dispersion stability. Resin can be obtained.
[0045]
As described above, in order to form the colored resin film of the present invention, a method using a pigment having finely divided pigment particles and a sharp particle size distribution is suitable. Specifically, a method using a pigment composed of pigment particles having an average particle diameter of about 0.01 μm and a particle diameter of 75% by mass or more in the range of 0.01 ± 0.005 μm is preferable. In order to adjust the particle size distribution of the pigment within the above range, the pigment dispersion method is particularly important. The method for dispersing the pigment will be described later.
[0046]
In the present invention, processed pigments previously treated with an acrylic resin, vinyl chloride-vinyl acetate resin, maleic acid resin, ethyl cellulose resin, nitrocellulose resin or the like can also be suitably used. In the present invention, the processed pigment treated with the above-mentioned various resins is preferably a powder, paste, pellet, or paste in which the resin and the pigment are uniformly dispersed.
[0047]
-Dye-
In the present invention, when the colorant is a dye, it is uniformly dissolved in the composition to obtain the composition in the present invention.
There is no restriction | limiting in particular as said dye, A well-known dye can be used for conventional color filters. Examples of the dye include JP-A 64-90403, JP-A 64-91102, JP-A-1-94301, JP-A-6-11614, Japanese Patent No. 2592207, US Pat. 808,501, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP JP-A-6-51115, JP-A-6-194828, JP-A-8-2111599, JP-A-4-249549, JP-A-10-123316, JP-A-11-302283, JP-A-7- No. 286107, JP-A No. 2001-4823, JP-A No. 8-15522, JP-A No. 8-29771, JP-A No. 8-146215, JP-A-11-343437, JP-A-8-62416, JP-A-2002-14220, JP-A-2002-14221, JP-A-2002-14222, JP-A-2002-14223, JP-A-8. The dyes disclosed in JP-A No. 302224, JP-A-8-73758, JP-A-8-179120, JP-A-8-151531, and the like can be used.
[0048]
The chemical structures of the above dyes include pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole. Examples include azomethine series, xanthene series, phthalocyanine series, benzopyran series, and indigo series.
[0049]
In the case of a resist system that performs water or alkali development, from the viewpoint of completely removing the binder and / or dye by development, an acid dye and / or a derivative thereof can be preferably used. Dyes, acid mordant dyes, azoic dyes, disperse dyes, oil-soluble dyes, food dyes, and / or derivatives thereof can also be usefully used.
[0050]
The acidic dye is not particularly limited as long as it has an acidic group such as sulfonic acid or carboxylic acid, but is soluble in an organic solvent or a developer, salt-forming with a basic compound, absorbance, other in the composition. It can be appropriately selected in consideration of all the required performance such as interaction with the above components, light resistance, heat resistance and the like.
[0051]
Specific examples of the acidic dye are listed below, but the present invention is not limited thereto.
Specific examples of the acid dye include, for example, acid alizarin violet N; acid blue 1,7,9,15,18,23,25,27,29,40,45,62,70,74,80,83, 86, 87, 90, 92, 103, 112, 113, 120, 129, 138, 147, 158, 171, 182, 192, 243, 324: 1; acid chroma violet K; acid Fuchsin; acid green 1, 3, 5, 9, 16, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95; acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266, 274; acid violet 6B, 7, 9, 17, 19; acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116, 184, 243; Food Yellow 3; and derivatives of these dyes.
[0052]
Among them, the acid dyes 23, 25, 29, 62, 80, 86, 87, 92, 138, 158, 182, 243, 324: 1; acid orange 8, 51, 56, 63, 74, Acid red1,4,8,34,37,42,52,57,80,97,114,143,145,151,183,217; acid violet 7; acid yellow 17,25,29,34,42, Preferred are dyes such as 72, 76, 99, 111, 112, 114, 116, 184, 243; acidgreen 25 and derivatives of these dyes.
Other than the above, azo, xanthene and phthalocyanine acid dyes are also preferred. I. Solvent Blue 44, 38; I. Acid dyes such as Solvent orange 45; Rhodamine B, Rhodamine 110 and derivatives of these dyes are also preferably used.
[0053]
Examples of the acid dye derivative include inorganic salts of acidic dyes having an acidic group such as sulfonic acid and carboxylic acid, salts of acidic dyes and nitrogen-containing compounds, sulfonamides of acidic dyes, and the like. The acidic dye derivative is not particularly limited as long as it can be dissolved as a composition solution, but is soluble in organic solvents and developers, absorbance, interaction with other components in the curable composition, It can be appropriately selected in consideration of all required performance such as light resistance and heat resistance.
[0054]
The colorant content in the total solid content of the composition in the present invention is not particularly limited, but is preferably 30 to 60% by mass. If the amount of the colorant is too small, an appropriate chromaticity as a color filter may not be obtained. On the other hand, when the amount of the colorant is too large, photocuring does not proceed sufficiently and the strength as a film may be reduced, or the development latitude during alkali development may be narrowed.
[0055]
In the present invention, conventionally known pigment dispersants and surfactants can be added for the purpose of improving the dispersibility of the pigment. As these dispersants, many kinds of compounds are used. For example, phthalocyanine derivatives (commercially available products: EFKA-745 (manufactured by Efka)), Solsperse 5000 (manufactured by Geneca); organosiloxane polymer KP341 (Shin-Etsu Chemical) (Product)), (meth) acrylic acid type (co) polymer polyflow No.75, No.90, No.95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), etc. Cationic surfactants of: polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan Fatty acid Nonionic surfactants such as Lu; anionic surfactants such as W004, W005, W017 (manufactured by Yusho Co., Ltd.); EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, Polymer dispersing agents such as EFKA polymer 401, EFKA polymer 450 (manufactured by Morishita Sangyo Co., Ltd.), disperse aid 6, disperse aid 8, disperse aid 15, disperse aid 9100 (manufactured by San Nopco) Various Solsperse dispersants (manufactured by Geneca) such as Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000; Adeka Pluronic L31, F38, L42, L44, L61, L64, F68 , L72, P9 , F77, P84, F87, P94, L101, P103, F108, L121, P-123 (manufactured by Asahi Denka Co.) and Isonetto S-20 (manufactured by Sanyo Chemical Co.) and the like.
[0056]
(Alkali-soluble resin)
As said alkali-soluble resin, the organic high molecular polymer which has a water-soluble atomic group in a part of side chain can be used. The alkali-soluble resin is a linear organic high molecular polymer that is compatible with the monomer, and is organic solvent and alkali-soluble (preferably one that can be developed with a weak alkaline aqueous solution). Examples of the alkali-soluble resin include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-sho 59-53836, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer as described in JP-A-59-71048, There are partially esterified maleic acid copolymers, and acidic cellulose derivatives having a carboxylic acid in the side chain are also included.
[0057]
As the alkali-soluble resin, those obtained by adding an acid anhydride to a polymer having a hydroxyl group are also useful. In particular, among these, specifically, a benzyl (meth) acrylate / (meth) acrylic acid copolymer and a multi-component copolymer of benzyl (meth) acrylate / (meth) acrylic acid / and other monomers are preferable.
[0058]
The alkali-soluble resin includes at least (i) at least one acid component monomer selected from maleic anhydride (MAA), acrylic acid (AA), methacrylic acid (MA), and fumaric acid (FA), and (ii) It is possible to use a copolymer (hereinafter sometimes referred to as “copolymer A”) composed of ()) alkylpolyoxyethylene (meth) acrylate and (iii) benzyl (meth) acrylate.
[0059]
As the combination of the copolymer A, (i) acid component monomer, (ii) alkylpolyoxyethylene (meth) acrylate (Acr (EO)_n: CH_Three(OC₂H_Four)_nOCOC (CH_Three) = CHR), and (iii) the composition mass ratio of benzyl (meth) acrylate (BzMA) is preferably 10-25 / 5 to 25 / 50-85, more preferably 15-20 / 5 to 20 / 60-80. Is preferred. The polystyrene-reduced mass average molecular weight (Mw) by GPC of the copolymer is preferably 3,000 to 50,000, more preferably 5,000 to 30,000.
[0060]
(I) When the compositional mass ratio of the acid component monomer is within the above range, alkali solubility and solubility in a solvent are unlikely to decrease. And (ii) alkyl polyoxyethylene (meth) acrylate (Acr (EO)_n: CH_Three(OC₂H_Four)_nOCOC (CH_Three) = CHR) is within the above range, the liquid of the composition in the present invention tends to spread on the substrate, and the dispersibility of the colorant is not easily lowered. Can do.
(Iii) When the composition mass ratio of benzyl (meth) acrylate (BzMA) is in the above range, the dispersion stability of the colorant, the solubility in the composition, and the alkali development suitability of the coating film are unlikely to decrease.
[0061]
The above (ii) alkyl polyoxyethylene (meth) acrylate (Acr (EO)_n: CH_Three(OC₂H_Four)_nOCOC (CH_Three) = CHR) polyoxyethylene (EO)_n2 to 15 is preferable, 2 to 10 is more preferable, and 4 to 10 is particularly preferable. When the above repeating number n is in the above range, a development residue is less likely to occur after development with an alkaline developer, the fluidity of the composition as a coating solution can be prevented, and coating unevenness can be prevented. It is possible to prevent the thickness uniformity and the liquid-saving property from decreasing.
[0062]
Examples of the alkali-soluble resin include a copolymer (i) (meth) acrylic acid and (ii) benzyl methacrylate (hereinafter sometimes referred to as “copolymer B1”), or (i) (meta ) A copolymer comprising acrylic acid, (ii) benzyl methacrylate, and (iii) hydroxyethyl (meth) acrylate (hereinafter sometimes referred to as “copolymer B2”) can be used.
In the present invention, the copolymer B1 and the copolymer B2 are effective in the dispersion stability of the colorant. Further, when the kneading and dispersing treatment is carried out in the production of the composition in the present invention, the copolymers B1 and B2 give a strong shearing force to the colorant aggregate to promote the dispersion, followed by the copolymer B1 and B2. The dispersion stability of the colorant in the composition finally obtained through the fine dispersion treatment can be enhanced.
[0063]
The said polymer can be used in mixture of arbitrary quantity, and 30-85 mass% is preferable with respect to solid content mass of the composition in this invention from viewpoints of the image intensity | strength etc. which are formed.
[0064]
(Photosensitive polymerization component)
Next, the photosensitive polymerization component will be described.
As the photosensitive polymerization component, a compound having an ethylenically unsaturated group having at least one addition-polymerizable ethylene group and having a boiling point of 100 ° C. or higher under normal pressure is preferable. Acrylate compounds are more preferred.
[0065]
Examples of the compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C. or higher at normal pressure include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meta ) Monofunctional acrylates and methacrylates such as acrylates; polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra ( (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, Poly (meth) of penta (erythritol) or di (pentaerythritol) obtained by adding (meth) acrylate after adding ethylene oxide or propylene oxide to polyfunctional alcohols such as ly (acryloyloxyethyl) isocyanurate, glycerin or trimethylolethane Acrylates, urethane acrylates as described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, JP-A-48-64183, JP-B-49 -Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid described in JP-B No. 43191 and JP-B-52-30490 I can do it. Furthermore, the Japan Adhesion Association Vol. 20, No. 7, pages 300 to 308, those introduced as photocurable monomers and oligomers can also be used.
[0066]
A compound obtained by adding ethylene oxide or propylene oxide to the polyfunctional alcohol and then (meth) acrylated is described in JP-A-10-62986 as general formulas (1) and (2) together with specific examples thereof. These can also be used as photosensitive polymerization components.
[0067]
Among these, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and a structure in which these acryloyl groups are interposed via ethylene glycol or propylene glycol residues are preferable. These oligomer types are also used. These photosensitive polymerization components can be used alone or in combination of two or more.
The amount of the photosensitive polymerization component used is preferably 20 to 200 mass%, more preferably 50 to 120 mass%, based on the total solid content of the composition in the present invention, from the viewpoint of sufficient curing.
[0068]
(Photopolymerization initiator)
As said photoinitiator, the photoinitiator activated by irradiation of light, a radiation, active electromagnetic waves, etc. can be used. As the photopolymerization initiator, at least one trihalomethyl compound can be used, and the following materials can also be combined.
Examples of materials that can be used in combination with the above trihalomethyl compound include the picinal polyketoaldonyl compounds disclosed in US Pat. No. 2,367,660, US Pat. Nos. 2,367,661 and 2 Α-carbonyl compounds disclosed in US Pat. No. 2,367,670, acyloin ethers disclosed in US Pat. No. 2,448,828, and US Pat. No. 2,722,512. Aromatic substituted aromatic acyloin compounds, polynuclear quinone compounds disclosed in US Pat. Nos. 3,046,127 and 2,951,758, US Pat. No. 3,549,367 Triarylimidazole dimer / p-aminophenyl ketone combination disclosed in US Pat. No. 4,212,976 The oxadiazole compound etc. which are described in the gazette are mentioned. The amount of the trihalomethyl compound used is preferably about 0.2 to 20% by mass, more preferably 0.5 to 15% by mass in terms of the solid content ratio relative to the photosensitive polymerization component. 10-800 mass% is preferable with respect to the trihalomethyl compound, and, as for the ratio of the compound used in combination with the said trihalomethyl compound, 20-300 mass% is preferable.
[0069]
0.1-10.0 mass% is preferable with respect to the total solid of the composition in this invention, and, as for the usage-amount of the said photoinitiator, 0.5-5.0 mass% is more preferable. When the usage-amount of the said photoinitiator exists in said range, superposition | polymerization will advance easily and film | membrane intensity | strength can be raised.
[0070]
(solvent)
Examples of the solvent used when preparing the composition in the present invention include solvents such as esters, ethers, ketones, and aromatic hydrocarbons.
Examples of the esters include ethyl acetate, vinegar-n-butyl, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, Such as ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate 3-oxypropionic acid alkyl esters;
[0071]
Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, 2 -Methyl methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, 2-oxy-2 -Ethyl methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2- Oxobutanoic acid Le, ethyl 2-oxobutanoate, and the like.
[0072]
Examples of the ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate. , Propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate and the like.
[0073]
Examples of the ketones include methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone. Examples of the aromatic hydrocarbons include toluene and xylesi.
[0074]
Among these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl Carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate and the like are preferably used. These solvents may be used alone or in combination of two or more.
[0075]
(Other ingredients)
Various other additives such as dispersants, fillers, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, and the like are added to the composition of the present invention as necessary. I can do it.
[0076]
The dispersant can be added in order to improve the dispersibility of the pigment. As the dispersant, known ones can be appropriately selected and used, and examples thereof include a cationic surfactant, a fluorine surfactant, and a polymer dispersant.
[0077]
Further, the graft copolymer having a specific acid amide group-containing monomer and a quaternary ammonium salt monomer residue in the main chain described in JP-A-10-254133 has an excellent action of finely dispersing the pigment. Therefore, it can be used as the dispersant. By using the above-mentioned furaft copolymer, it is possible to finely disperse the pigment while reducing energy and time consumption, and the dispersed pigment may aggregate or settle even after a lapse of time. Long-term dispersion stability can be maintained.
[0078]
The said dispersing agent may be used independently and may be used in combination of 2 or more type.
The amount of the dispersant added in the composition of the present invention is usually preferably about 0.1 to 50 parts by mass with respect to 100 parts by mass of the pigment.
[0079]
In order to improve the storage stability of the composition in the present invention, a thermal polymerization inhibitor may be added. Furthermore, in the case where the alkali solubility in the unirradiated part is promoted and the developability of the composition in the present invention is further improved, the composition in the present invention has an organic carboxylic acid, preferably a low molecular weight of 1000 or less. Organic carboxylic acids can be added.
[0080]
(Method for producing colored resin film of the present invention)
The colored resin film of the present invention is prepared by first mixing a colorant, further an alkali-soluble resin used as necessary, a photosensitive polymerization component, a photopolymerization initiator, and other additives with a solvent, It can be formed by mixing and dispersing using a disperser (mixing and dispersing step), applying the obtained composition of the present invention to a substrate and drying.
In addition, it is preferable to use the method which consists of a kneading | mixing dispersion | distribution process and the fine dispersion | distribution process performed following it as a mixing dispersion | distribution process as mentioned above.
[0081]
-Preparation of composition in the present invention-
As described above, in order to form the colored resin film of the present invention, a method using a pigment having finely divided pigment particles and a sharp particle size distribution is suitable. Specifically, a method using a pigment constituted by including 75% by mass or more of pigment particles having an average particle size of about 0.01 μm and a particle size in the range of 0.01 ± 0.005 μm is preferable.
In order to adjust the particle size distribution of the pigment within the above range, the pigment dispersion method is particularly important. As such a dispersion method, for example, dry dispersion (kneading dispersion treatment) in which a high-viscosity state is dispersed using a roll mill such as a kneader or two-roll, and a relatively low-viscosity state using a three-roll or bead mill is used. Examples of the dispersion method include a combination of wet dispersion (fine dispersion treatment) for dispersion. In the dispersion method, it is also preferable to co-disperse two or more pigments, or not to use a solvent or to reduce the amount of use as much as possible during the kneading dispersion treatment, or to use various dispersants. Further, in order to relieve the solvent shock, it is preferable to add the resin component separately at the time of the kneading and dispersing treatment and at the time of the fine dispersing treatment (use in two divisions), and shift from the kneading and dispersing treatment to the fine dispersing treatment. In order to prevent reaggregation of the pigment particles, it is preferable to use a resin component having excellent solubility. Furthermore, it is also effective to use high hardness ceramics or beads with a small particle diameter for the beads of the bead mill used during the fine dispersion treatment. In addition, as said resin component, the above-mentioned alkali-soluble resin can be used, for example.
[0082]
In the present invention, in particular, two or more pigments are used, and two or more pigments are further dispersed in a high viscosity state of 50000 mPa · s or more, and then further dispersed in a low viscosity state of 1000 mPa · s or less. It is preferable to use a different colorant.
Generally, these pigments are supplied after drying by various methods after synthesis. Usually, it is dried from an aqueous medium and supplied as a powder. However, since water requires a large latent heat of vaporization for drying, a large amount of heat energy is given to dry it to form a powder. Therefore, the pigment usually forms an aggregate (secondary particle) in which primary particles are aggregated.
The preparation method of the composition according to the present invention which is preferable in the present invention will be described.
However, the present invention is not limited to this.
[0083]
In the above preparation method, first, the viscosity after kneading and dispersing the alkali-soluble resin in the colorant (pigment) is 50,000 mPa · s or more (preferably 50,000 to 100,000 mPa · s) so that the viscosity becomes relatively high. A kneading and dispersing treatment is applied to the above. Here, the kneading dispersion treatment may be high viscosity dispersion or dry dispersion.
[0084]
Then, if necessary, an alkali-soluble resin is additionally added to the dispersion after the kneading dispersion treatment so that the viscosity after the fine dispersion treatment is 1000 mPa · s or less (preferably 100 mPa · s or less). Apply fine dispersion. The fine dispersion treatment may be low viscosity dispersion or wet dispersion.
[0085]
In the kneading and dispersing treatment, the solvent ratio is preferably 0 to 20% by mass with respect to the dispersion. Thus, when the dispersion is performed without using much solvent, the surface of the pigment particles can promote the wetting with the constituent component mainly composed of the resin component of the vehicle. The solid / gas interface between the pigment particles and air can be converted to a solid / solution interface between the pigment particles and the vehicle solution. When the interface formed by the surfaces of the pigment particles is converted from air to a solution and mixed and stirred, the pigment can be dispersed to a fine state close to the primary particles.
[0086]
Thus, in order to highly disperse the pigment, it is effective to convert the interface formed by the pigment particle surface from air to a solution. Such conversion requires a strong shearing force or compressive force. For this reason, in the above kneading and dispersing treatment, it is preferable to use a kneading machine capable of exhibiting a strong shearing force and compressing force, and to use a material having a high viscosity as the material to be kneaded.
[0087]
In the fine dispersion treatment, it is preferable to mix and stir together with fine dispersion media such as glass or ceramic. Furthermore, it is preferable that the ratio of the solvent at the time of a fine dispersion process is 20-90 mass% of to-be-dispersed material. At the time of the fine dispersion treatment, it is necessary to uniformly and evenly distribute the pigment particles to a fine state, and therefore, a disperser capable of imparting impact force and shear force to the aggregated pigment particles; It is preferable to use a low-viscosity material.
[0088]
For example, in the kneading and dispersing treatment for producing a color filter using the composition in the present invention, first, a coloring agent such as an organic pigment, a dispersing agent, a surface treating agent, and a minimum amount of solvent are kneaded. As the kneading machine, a two-roll, three-roll, ball mill, tron mill, disper, kneader, kneader, homogenizer, blender, single-screw or twin-screw extruder, etc. can be used, and they are dispersed while giving a strong shearing force. As the kneader, a two-roll mill is particularly preferable. Next, a solvent and, if necessary, an alkali-soluble resin are added, mainly using a vertical or horizontal sand grinder, ball mill, pin mill, slit mill, homogenizer, disper, ultrasonic disperser, etc. Disperse with beads made of glass or zirconia of particle size.
Details of kneading and dispersing are also described in “Paint Flow and Pigment Dispersion” by T.C. Patton (published by John Wiley and Sons, 1964).
[0089]
Next, the obtained composition of the present invention is applied to the substrate directly or via another layer by a coating method such as spin coating, slit coating, casting coating, roll coating, etc. Radiation-sensitive composition layer), exposing through a predetermined mask pattern, curing only the light-irradiated coating film portion, and developing with a developer, so that each color (3 colors or 4 colors) can be obtained. A color filter can be manufactured by forming a patterned film made of pixels. As radiation used at this time, ultraviolet rays such as g-line and i-line are particularly preferably used. The radiation referred to in the present invention is a broad concept including visible light, ultraviolet light, far ultraviolet light, X-rays and the like.
[0090]
Next, by performing an alkali development treatment, the light-irradiated portion is eluted in the alkaline aqueous solution by the exposure, and only the photocured portion remains. Any developer can be used as long as it dissolves the light-irradiated portion of the photosensitive layer but does not dissolve the light-irradiated portion.
Further, after the excess developer is washed away and dried, heat treatment (post-bake) is performed at a temperature of 50 ° C. to 240 ° C. Thus, the said process can be repeated sequentially for every color, and a cured film can be manufactured. Thereby, a color filter is obtained.
[0091]
-Board-
As the substrate, for example, non-alkali glass, soda glass, pyrex (R) glass, quartz glass used for liquid crystal display elements and the like, and those obtained by attaching a transparent conductive film to these, photoelectric conversion elements used for solid-state imaging devices, etc. Examples of the substrate include a silicon substrate. Furthermore, a plastic substrate is also possible. On these substrates, normally, black stripes for isolating each pixel may be formed.
[0092]
Drying (pre-baking) of the photosensitive colored resin composition layer of the present invention applied on the substrate can be performed at a temperature of 50 ° C. to 140 ° C. for 10 to 300 seconds using a hot plate, oven or the like.
[0093]
Any developer can be used as long as it dissolves the photosensitive colored resin composition of the present invention and does not dissolve the radiation irradiated portion. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used.
Examples of the organic solvent include the aforementioned solvents used in preparing the composition in the present invention. The development temperature is usually 20 ° C. to 30 ° C., and the development time is 20 to 90 seconds.
[0094]
Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, Concentration of an alkaline compound such as tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene, in a concentration of 0.001 to 10% by mass, preferably 0.01 to An alkaline aqueous solution dissolved so as to be 1% by mass is used. In addition, when using the developing solution which consists of such alkaline aqueous solution, generally it wash | cleans (rinse) with water after image development.
[0095]
Post-baking is heating after development to complete curing, and is usually performed at about 200 ° C. to 220 ° C. (hard baking).
This post-bake treatment is performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater, or the like so that the coating film after development is in the above-described condition. be able to.
[0096]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited by a following example.
[0097]
[Example 1]
<< Preparation of coloring composition for color filter >>
<Preparation of pigment dispersion>
For each color of green (G), blue (B), and red (R), each material shown in Table 1 below is uniformly kneaded with a kneader, and the kneaded product is then subjected to dry dispersion treatment (kneading dispersion treatment) with two rolls. did.
785 parts by mass of propylene glycol monomethyl ethyl acetate as a solvent component was added to the dispersion subjected to the dry dispersion treatment. Thereafter, the mixture was stirred with a homogenizer at 2000 rpm for 30 minutes to prepare a dispersion composition of each color of green (G), blue (B), and red (R) in which the pigment was uniformly dispersed. The obtained dispersion composition was finely dispersed with a bead disperser (trade name: Dispermat, manufactured by GETZMANN) using 0.3 mm zirconia beads.
[0098]
Then, it filtered with a 2.5 micrometer filter, and obtained the pigment dispersion liquid (1)-(3) of each color in which the pigment was disperse | distributed uniformly. For each pigment dispersion, the viscosity of the kneaded product (dispersion) at the time of the kneading dispersion treatment and the fine dispersion treatment, and the average particle diameter and the particle diameter of 0.01 ± 0.005 μm in each pigment dispersion liquid Table 1 shows the ratio of the pigment particles. The pigment particle size was measured by using MICROTRAC UPA 150 manufactured by Nikkiso Co., Ltd., and using each of the colored resin compositions diluted with propylene glycol monomethyl ethyl acetate as a sample.
[0099]
[Table 1]

[0100]
<Preparation of colored resin composition>
The following composition was uniformly mixed with a stirrer for each 200 parts by mass of the pigment dispersion of each color obtained from the above to prepare a colored resin composition for a color filter for each color.
[0101]
〔composition〕
・ 33 parts by mass of benzyl methacrylate / methacrylic acid copolymer
(Alkali-soluble resin, copolymerization molar ratio = 70/30, weight average molecular weight 30,000)
・ 36 parts by mass of dipentaerythritol pentaacrylate (monomer)
・ 110 parts by mass of propylene glycol monomethyl ethyl acetate (solvent)
・ 44 parts by mass of ethyl-3-ethoxypropionate (solvent)
・ Halomethyltriazine initiator 4 parts by mass
(Photopolymerization initiator, trade name: TAZ107, manufactured by Midori Chemical Co., Ltd.)
[0102]
<Formation of colored resin film for color filter>
The three colored resin compositions for color filters obtained from the above are individually spin-coated so as to be uniform on the surface of an alkali cleaned glass substrate 10 cm × 10 cm (trade name: 1737, manufactured by Corning). A photo-curable coating film was formed by application. In spin coating, the coating rotation speed was adjusted so that the thickness of the colored resin coating film was 1.0 μm when the coating film was heat-treated after application at a surface temperature of 110 ° C. × 120 seconds.
[0103]
Subsequently, the obtained photocurable coating film was heat-treated (prebaked) on a hot plate under conditions of 110 ° C. × 120 seconds. Then, using a 2.5 KW ultra high pressure mercury lamp, 200 mJ / cm over the entire surface of the photocurable coating film.²The photocuring process was performed by irradiating with the exposure amount. Further, the exposed coating film was covered with a 40% aqueous solution of an organic developer (trade name: CD-2000, manufactured by Fuji Film Arch Co., Ltd.) and allowed to stand for 60 seconds. Thereafter, pure water was sprayed in a shower to wash away the developer.
As described above, the coating film that has been subjected to the photo-curing treatment and the development treatment is subjected to heat treatment (post-baking) on a hot plate at 200 ° C. for 5 minutes, and each color is a single color of 9 cm × 9 cm on a glass substrate. The colored resin coatings (1) to (3) for color filters were formed.
[0104]
<Evaluation>
The obtained colored resin film for a single color filter is placed between the observation lens and the light source of the optical microscope to irradiate the light toward the observation lens, and a digital camera with a magnification of 1000 times installs the transmitted light state. Was observed with an optical microscope. A digital camera installed in the optical microscope is equipped with a CCD with 1.28 million pixels, and the surface of the coating film in a transmitted light state was photographed. The photographed image was stored as digitally converted data (digital image) in an 8-bit bitmap format. The film surface was photographed on 20 arbitrarily selected areas.
In addition, the digitally converted data was stored by digitizing the captured image as a density distribution of 256 gradations from 0 to 255 for each of the three primary colors of RGB.
[0105]
Next, the stored digital image was divided into a lattice shape so that one lattice size corresponds to 2 μm square on the actual substrate, and the luminance in one partition was averaged. In this example, since an image of 1000 times optical was captured with a 1.28 million pixel digital camera, 2 μm on the actual substrate was 2 mm on the captured image, and the image size on the display was 452 mm × 352 mm. The total number of sections in one area was 39976.
[0106]
For all the sections in each region, an arbitrary luminance and the average luminance of all adjacent sections adjacent to it were measured. A partition having a difference of 5 or more from the average brightness of adjacent partitions is recognized as a significant difference partition, and the average total number of significant difference partitions in all regions and the average total number of significant difference partitions in all regions are the total number of partitions in each region (39976). The ratio of the total to the total) was calculated. The results are shown in Table 2 below.
[0107]
[Table 2]

[0108]
<Production of color filter and CCD device>
<Production of color filter>
The following composition was mixed with a stirrer to prepare a planarizing film resist solution.
[0109]
〔composition〕
165 parts by mass of benzyl methacrylate / methacrylic acid copolymer
(Copolymerization molar ratio = 70/30, weight average molecular weight 30,000)
・ 65 parts by mass of dipentaerythritol pentaacrylate
・ Propylene glycol monomethyl ethyl acetate 138 parts by mass
-123 parts by mass of ethyl-3-ethoxypropionate
・ Halomethyltriazine initiator 3 parts by mass
(Photopolymerization initiator, trade name: TAZ107, manufactured by Midori Chemical Co., Ltd.)
[0110]
The obtained flattening resist solution was uniformly applied by spin coating onto a 6-inch silicon wafer on which photodiodes were formed. In spin coating, the coating rotation speed was adjusted so that the film thickness was about 2.0 μm when the surface temperature of the coating film was heated using a hot plate under the condition of 110 ° C. × 120 seconds after coating.
Then, it was placed in an oven at 220 ° C. for 1 hour to cure the coating film, and a planarizing film was formed so as to uniformly cover the surface of the photodiode formed on the silicon wafer.
[0111]
Next, the above-described colored resin composition for color filter is applied on the planarizing film in the order of G, R, and B for each color, followed by drying (pre-baking), pattern exposure, alkali development, rinsing, and curing drying (post-baking). A colored resin film was formed, and a color filter was produced on a silicon wafer with a photodiode.
[0112]
The pattern exposure is 500 mJ / cm using an i-line stepper (trade name: FPA-3000i5 +, manufactured by Canon Inc.) through a 2 μm mask pattern.²I went there.
For alkali development, a 40% by weight aqueous solution of an organic alkali developer (trade name: CD-2000, manufactured by Fuji Film Arch Co., Ltd.) is used for paddle development for 60 seconds at room temperature. The second spin shower was rinsed with pure water, and further washed with pure water. Thereafter, water droplets were blown off with high-pressure air, the substrate was naturally dried to obtain a pattern, and then post-baked on a hot plate at a surface temperature of 200 ° C. for 5 minutes.
[0113]
When the CCD device obtained as described above is mounted on a digital camera and an image obtained by photographing a color chart with Kodak's gray scale under the same light source is observed on a monitor, an image of uniform and smooth color with little roughness is obtained. was gotten.
[0114]
[Comparative Example 1]
<Formation of colored resin film for color filter>
The green pigment dispersion liquid (1) and the blue pigment dispersion liquid (2) in Example 1 were changed to a green pigment dispersion liquid (4) and a blue pigment dispersion liquid (5) described below. In addition, the green and blue colored resin compositions (4) to (5) and the colored resin coating (4) to 4 are the same as in Example 1 except that the pigment dispersion 3 for red is not used. (5) was formed and the same evaluation was performed. The results are shown in Table 3 below.
[0115]
<Preparation of green pigment dispersion (4)>
Each of the colorants (Pigment Green PG36, Pigment Green PG7, Pigment Yellow PY139) used in the preparation of the pigment dispersion (1) of Example 1 was separately used. It knead | mixed uniformly with the kneader with the solvent. Thereafter, each kneaded product was dispersed with two rolls (dry dispersion treatment), propylene glycol monomethyl ethyl acetate was added as a solvent component to the obtained dispersion, and the mixture was stirred with a homogenizer. The obtained kneaded composition was finely dispersed with a bead disperser (trade name: Dispermat, manufactured by GETZMANN), filtered with a 2.5 μm filter, and Pigment Green PG36, Pigment Green PG7, and Pigment Three types of pigment dispersions in which yellow PY139 was dispersed alone were obtained. Thereafter, these three types of pigment dispersions were stirred with a homogenizer to obtain a green pigment dispersion (4).
The processing conditions in the two-roll, homogenizer, and bead disperser were the same as those in Example 1.
[0116]
<Preparation of blue pigment dispersion (5)>
In the same manner as the preparation of the pigment dispersion for green (4), the two colorants (Pigment Blue PB15: 6, Pigment Violet PV23) used in the pigment dispersion (2) of Example 1 were dispersed alone. A pigment dispersion was obtained. Thereafter, these two pigment dispersions were stirred with a homogenizer to obtain a blue pigment dispersion (5).
[0117]
[Table 3]

[0118]
<Production of color filter and CCD device>
A color filter and a CCD device were produced in the same manner as in Example 1 except that the colored resin composition (1) was changed to the colored resin composition (4) in Example 1. When the obtained CCD device is mounted on a digital camera and an image obtained by photographing a color chart with Kodak gray scale under the same light source is observed on a monitor, an image with black defects and a rough feeling is obtained. It was.
[0119]
[Comparative Example 2]
A color filter and a CCD device were produced in the same manner as in Example 1 except that the colored resin composition (2) was changed to the colored resin composition (5) in Example 1. When the obtained CCD device is mounted on a digital camera and an image obtained by photographing a color chart with Kodak gray scale under the same light source is observed on a monitor, an image with black defects and a rough feeling is obtained. It was.
[0120]
【The invention's effect】
According to the present invention, a colored resin film for a color filter that can be suitably used for the manufacture of a solid-state imaging device with reduced black defects, unevenness, and roughness of a reproduced image on the device, a color filter using the same, and A method for evaluating a colored resin film for a color filter can be provided.
[Brief description of the drawings]
FIG. 1 is an explanatory diagram for explaining adjacent pixels.
[Explanation of symbols]
1,3,5 significant difference compartment
2, 4, 6 Adjacent compartments

Claims (6)

A colored resin film for a color filter containing a colorant and having a thickness of 0.1 to 10 μm, wherein the surface of the film is divided into a grid to form 2 μm square sections, and each of the sections has the above-mentioned A numerical value processing is performed to add a luminance value obtained by numerically dividing the luminance of the section into 256 gradations of 0 to 255, and the luminance value given by the numerical processing and the average luminance value of all adjacent adjacent areas when the difference is a significant difference partitioning in which the partitions 5 or more, the total number of significant difference compartment Ri der than 10% of the total number of compartments, further the colorant is a pigment, and said pigment Contains 75% by mass or more of pigment particles having an average particle diameter in the range of 0.01 ± 0.005 μm . A method for producing a colored resin film for a color filter, wherein a composition containing at least a colorant is applied to a substrate,
  The color filter resin film has a thickness of 0.1 to 10 μm, and the surface of the film is divided into a grid to form 2 μm square sections, and the brightness of the sections is set to 0 to 255 in each of the sections. The numerical value process which attaches | subjects the luminance value digitized to 256 gradations is performed, The difference of the luminance value attached | subjected by the said numerical value process and the average luminance value of all the adjacent divisions adjacent to the circumference is 5 or more When the section is a significant difference section, the total number of the significant difference sections is 10% or less of the total number of sections,
  The colorant comprises two or more pigments, and the two or more pigments are dispersed in a high viscosity state of 50000 mPa · s or more, and then further dispersed in a low viscosity state of 1000 mPa · s or less. A method for producing a colored resin film for a color filter. 3. The colored resin film for a color filter according to claim 2, wherein the two or more pigments are dispersed in a high viscosity state of 50,000 to 100,000 mPa · s and further dispersed in a low viscosity state of 100 mPa · s or less. Manufacturing method . A section forming step of forming a section of 2 μm square by dividing the surface of the colored resin film for a color filter containing a colorant into a lattice shape;
A quantification step of attaching a luminance value obtained by quantifying the luminance of the division to 256 gradations of 0 to 255 to each of the divisions;
A qualifying step of certifying the arbitrary section as a significant difference section when a difference between a luminance value of the arbitrary section and an average luminance value of all adjacent sections adjacent to the arbitrary section is 5 or more;
A counting step of counting the total number of the significant difference compartments;
A method for evaluating a colored resin film for a color filter, comprising:   The method for evaluating a colored resin film for a color filter according to claim 4, further comprising a comparison step of comparing the total number of the significant difference sections counted in the counting step with the total number of sections. A color filter formed using the colored resin film for a color filter according to claim 1 .

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