JP4325215B2 - Colored resin composition, color filter, and liquid crystal display device - Google Patents

Description

【０１０６】
【表２】

【０１０７】
実施例１〜３及び比較例１〜２
＜着色樹脂組成物の調製＞
表３に示した各配合量の各成分と全量に対して３．６重量倍のジルコニアビーズ（直径０．５ｍｍ）とをペイントシェーカーに収納し、７時間分散処理を行ってインク状を呈する着色樹脂組成物を調製した。
【０１０８】
【表３】

【０１０９】
【化１】

【０１１０】
【化２】

【０１１１】
＜カラーフィルタの製造＞
縦３７０mm、横４７０mm、厚さ０．７mmのガラス基板（旭硝子社製「ＡＮ６３５」）にダイコータでインク状の黒色の着色樹脂組成物を塗布した。なお、ダイコータは、幅手３６０mmのステンレス製ダイコータを使用し、リップ間隔は２００μｍ、ガラス基板面とのギャップは１００μｍとした。塗布に際しては、乾燥膜厚で０．７μｍとなる様に塗布液の吐出量を調整した。その後、６０℃で１分間乾燥した後、１１０℃で２分間加熱乾燥した。その後、着色樹脂組成物の塗布膜上に、乾燥後の膜厚が１．５μｍになる様に、ポリビニルアルコール水溶液を塗布した後に乾燥して、酸素遮断層を形成した。
【０１１２】
次いで、幅３０μｍ、縦３３０μｍ、横１１０μｍのピッチで繰り返すブラックマトリクス用ネガフォトマスクを使用し、２ｋＷ高圧水銀灯により、３００ｍＪ／cm^２の露光量で露光処理を行った。その後、０．１重量％炭酸ナトリウム水溶液を使用し、液温度２３℃で現像処理を行った。次いで、３Ｋｇ／ｃｍ^２の水圧で３０秒間スプレー水洗処理を行い、ブラックマトリクスを形成した。その後、温度２００℃で、７分間の熱硬化処理を行った。
【０１１３】
次いで、赤色、緑色、青色の各色材を含有する液状の着色樹脂組成物を使用し、上記と同様の手順で、塗布、予備乾燥、加熱乾燥、露光、現像、水洗、熱硬化の各処理を行い、各色パターンを順次に形成し、カラーフィルタを得た。この際、乾燥膜厚が１．３μｍとなる様に、塗布液の液吐出量を調整した。露光量は、各色共５００ｍＪ／ｃｍ^２、現像処理は、０．１重量％炭酸ナトリウム水溶液を使用し、液温度２５℃で行った。現像後、１０Ｋｇ／ｃｍ^２の水圧で３０秒間スプレー水洗処理を行った。各色の最後に、２００℃、１５分間の熱硬化処理を行った。なお、現像機は、上記のブラックマトリクス形成に使用したものと同じものを使用した。この様にして、実施例１〜３、比較例１〜３の組成を有する着色樹脂組成物を使用し、１００枚ずつの樹脂ブラックマトリクス付きカラーフィルタを作製した。
【０１１４】
＜体積平均粒子径ｍｖの測定＞
実施例１〜３及び比較例１〜２の組成を有する着色樹脂組成物をそれぞれ、５０ｍｍ角のガラス基板に乾燥膜厚２．５μｍでスピンコート法により塗布し、６０分風乾した。その後、該着色樹脂組成物を形成する溶剤６．２５ｇに２３℃で３分間浸漬し、再分散させ、浸漬開始から１０分後に日機装（株）製「マイクロトラックＵＰＡ」にて、粒径分布を測定し、体積平均粒子径（ｍｖ１）を算出した。その結果を表４に示した。
【０１１５】
また、同時に該着色樹脂組成物０．１ｇを該溶剤１００ｇに２３℃で攪拌しながら徐々に滴下し、希釈液を作成した。希釈液作成１０分後に、上記と同様に粒径分布を測定し、体積平均粒子径（ｍｖ２）を算出した。その結果を表４に示した。
【０１１６】
【表４】

【０１１７】
＜カラーフィルタの評価試験＞
得られたカラーフィルタにつき、異物欠陥発生の有無を測定し、その異物欠陥発生率を表５に示した。表５において、黒色、赤色、緑色、青色は、各色のインク状を呈する着色樹脂組成物（レジスト）を意味する。なお、異物欠陥とは、［（長径）^２＋（短径）^２］の平方根が６０μｍ以上のものを異物と定義し、各色レジストの凝集に起因する異物欠陥が認められたカラーフィルタの枚数を、全製造枚数（１００枚）で割った値を異物欠陥発生率と定義した。
【０１１８】
【表５】

【０１１９】
表１〜５より次のことが明らかである。
（１）本発明の着色樹脂組成物は、溶剤成分が請求項１および２を満たすため、これらの組成物を塗布して製造したカラーフィルタは、異物欠陥発生率が少ない（実施例１〜３参照）。
（２）これに対し、溶剤成分が請求項１および２の要件を満たさない着色樹脂組成物を塗布して製造したカラーフィルタは、異物欠陥発生率が高い（比較例１〜２参照）。
【０１２０】
【発明の効果】
本発明は、以上詳細に説明した通りであり、次の様な特別に有利な効果を奏し、その産業上の利用価値は極めて大である。
（１）本発明の着色樹脂組成物は、色材が高濃度であっても、基板表面に塗布する工程で、乾燥凝集し難く、異物の発生が少ない。
（２）ダイコート法によって本発明の着色樹脂組成物を基板表面に塗布する際、ダイリップに凝集塊が生じ難く、高品質の製品を高歩留りで得ることが出来る。
（３）本発明に係るカラーフィルタは、高品質であるため、これを使用したカラーディスプレー、液晶表示装置なども高品質である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a colored resin composition, a color filter, and a liquid crystal display device.
[0002]
[Prior art]
Conventionally, pigment dispersion methods, dyeing methods, electrodeposition methods, and printing methods are known as methods for producing color filters used in liquid crystal display devices and the like. From the viewpoint of spectral characteristics, durability, pattern shape and accuracy, a pigment dispersion method having excellent characteristics on average is most widely adopted.
[0003]
Hereinafter, the outline of the pigment dispersion method will be described. Usually, first, a black matrix is formed on a transparent support such as a glass substrate using a metal light-shielding film such as chromium or chromium oxide. Next, for example, a colored resin composition (color resist) in which a red pigment is dispersed is applied to the entire surface by spin coating or the like, and exposed through a mask. When development is performed after exposure, red pixels are obtained. The same method is adopted for the blue and green pixels, and three color pixels are formed.
[0004]
Between each pixel, the black matrix part is concave, so the surface is covered with a protective film of transparent resin such as epoxy resin or acrylic resin for smoothing. In some cases, it is not provided. Further, a transparent conductive film such as an ITO film is formed on the protective film by sputtering or vacuum deposition. In recent years, a pigment dispersion method is often employed when forming a black matrix. Specifically, a black matrix is created by applying, exposing and developing a colored resin composition (black resist) in which a black pigment is dispersed.
[0005]
The performance required for liquid crystal display devices has been diversified and sophisticated, in spite of recent technological innovation. In particular, color filters are required to have a wider color reproducibility than ever and to have a high transmittance. In order to achieve these requirements by the above-mentioned pigment dispersion method, a wide variety of new pigments have been developed, and colored resin compositions (color resists) containing these new pigments in high concentrations are becoming mainstream. . Further, not only the color resist but also the above-described black resist is required to have a thin coating film and a high light shielding property, and there is a tendency that a resist having a high pigment concentration is employed.
[0006]
On the other hand, various new technologies have been developed with respect to a method for manufacturing a color filter. Among the pixel forming processes, for example, with respect to the resist coating process, a method in which a resist is dropped on the center of the substrate and uniformized by a spin coating method has been the mainstream. However, as the size of the substrate has increased, the amount of resist used has increased, and restrictions on the spin coater equipment (motor capabilities, etc.) have increased. It has become.
[0007]
In general, a technique of applying a resist by a die coating method is used, for example, in the manufacture of a flexible disk or the like, and is usually suitably used when a coating liquid such as a resist is continuously applied to a medium such as a polymer film. In the case of single-wafer coating such as a color filter, the resist coating method is intermittent coating, and the tip of the die lip is repeatedly wetted and dried. When a color resist or a black resist in which a high concentration of pigment is dispersed is dried at the tip of the die lip, the pigment concentration increases rapidly, which may cause agglomeration of the pigment. These agglomerates adhere to the tip of the die lip, peel off from the tip of the lip when the resist is discharged again, and move onto the substrate. These agglomerates are not easily removed in the subsequent process and remain on the substrate until the end. Such an agglomerate becomes a pixel defect of the color filter and causes a quality defect. This failure phenomenon is considered to be one of the phenomena that must be avoided because the product yield decreases with frequent occurrence.
[0008]
In order to solve the above-mentioned problems and prevent the adhesion of foreign substances, a dry film formed from the colored resin composition is immersed in a solvent of 10 times or more by weight as a solvent of the colored resin composition. In this case, a method using a solvent that dissolves the dried film within 5 minutes has been proposed (for example, see Patent Document 1). This method seems to be effective because the dried material at the tip of the die coat nozzle is easy to dissolve, but in reality, fine particles of a size close to the visual limit of several tens of μm in diameter become a problem as a foreign matter defect. Even in the case of a colored resin composition that uses a solvent that appears to be dissolved visually, it is often impossible to prevent the adhesion of foreign substances in actual production.
[0009]
[Patent Document 1]
JP 2002-23352 A
[0010]
[Problems to be solved by the invention]
The object of the present invention is to solve the above-mentioned problems in the prior art, and even when a high-concentration resist is used as a coating solution, it is possible to suppress the generation of dry agglomerates at the tip of the die lip, and foreign matter on the substrate An object of the present invention is to provide a colored resin composition, a color filter, and a liquid crystal display device that can minimize adhesion and obtain a high-quality product.
[0011]
[Means for Solving the Problems]
In the die coating method in which intermittent coating is performed, the inventors of the present invention solve the above-described problems caused by agglomerates by redispersing the agglomerates formed at the tip of the die lip in a coating solution in the next coating operation. As a result of paying attention to the above, the volume average particle size (mv1) obtained when the dried film of the coating solution is dispersed is reduced to a certain value or the volume average particle size (mv1) is compared. The volume average particle diameter (mv1) ratio with respect to the volume average particle diameter (mv2) obtained when the coating liquid is diluted is reduced to a certain value or less (in other words, the volume is increased by drying the coating liquid). The present inventors have obtained the knowledge that the above-mentioned object can be easily achieved if conditions such that the average particle diameter is not greatly changed are satisfied, and the present invention has been completed.
[0012]
The present invention has been completed based on the above findings, and the first gist of the present invention contains a coloring material, a binder resin, its monomer, a solvent, and a polymer dispersant and is used in a die coating method. A colored resin composition for a color filter, wherein the binder resin is an acrylic resin containing a monomer having a carboxyl group or a phenolic hydroxyl group in the side chain or main chain, and the solid component concentration relative to the entire colored resin composition Is 15 to 40% by weight, and as a solvent, Containing alcohols and / or alkyl alcohol ethers and alkyl alcohol ether acetate having a boiling point higher than these, It exists in the coloring resin composition characterized by using the solvent from which the volume average particle diameter (mv1) prescribed | regulated to the following (a) becomes 200 nm or less.
[0013]
A second gist of the present invention is a colored resin composition for a color filter, which contains a coloring material, a binder resin, a monomer thereof, a solvent, and a polymer dispersant, and is used in a die coating method. Is an acrylic resin containing a monomer having a carboxyl group or a phenolic hydroxyl group in the side chain or main chain, the solid component concentration relative to the entire colored resin composition is 15 to 40% by weight, and as a solvent, Containing alcohols and / or alkyl alcohol ethers and alkyl alcohol ether acetates having boiling points higher than these, A coloration characterized by using a solvent whose volume average particle diameter (mv1) specified in (a) is 1.5 times or less of the volume average particle diameter (mv2) specified in (b) below: Resists in resin composition.
[0014]
(A) Volume average particle diameter (mv1) in the redispersed liquid when the dried film formed by the colored resin composition is immersed in a solvent 1000 times by weight and redispersed.
(B) Volume average particle diameter (mv2) in the colored resin composition dilution when the colored resin composition is diluted with a solvent of 1000 times by weight or more
[0015]
The third gist of the present invention resides in a color filter formed by the die coating method using the above colored resin composition.
[0016]
The fourth gist of the present invention resides in a liquid crystal display device formed by using the above color filter.
[0017]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail. First, the colored resin composition of the present invention will be described. The colored resin composition of the present invention contains a coloring material, a binder resin, its monomer, and a solvent as essential components. In a preferred embodiment, it contains a photopolymerization initiator system, and further contains a thermal polymerization inhibitor, a plasticizer, and other additives as necessary.
[0018]
Examples of the color material include red, green, and blue dyes / pigments, yellow for toning, violet dyes / pigments, carbon black, and the like, and metal powders, white pigments, fluorescent pigments, and the like. The pigment may be either an inorganic pigment or an organic pigment.
[0019]
Examples of the inorganic pigment include barium sulfate, lead sulfate, titanium oxide, yellow lead, bengara, chromium oxide, carbon black, graphite, iron black, aniline black, cyanine black, and titanium black.
[0020]
Examples of organic pigments include the following. The numbers described below are C.I. I. (Color index) number (the same applies to dyes described later).
[0021]
Examples of yellow pigments include C.I. I. Pigment Yellow 1, 3, 4, 5, 6, 12, 13, 14, 16, 17, 18, 20, 24, 55, 65, 73, 74, 81, 83, 86, 87, 93, 94, 95, 97, 98, 100, 101, 108, 109, 110, 113, 116, 117, 120, 123, 125, 128, 129, 133, 137, 138, 139, 147, 148, 150, 151, 153, 154, 155, 156, 166, 168, 169, 170, 171, 172, 173, 175 and the like.
[0022]
Examples of orange pigments include C.I. I. Pigment orange 1, 2, 5, 13, 15, 16, 17, 18, 19, 31, 34, 36, 38, 40, 42, 43, 51, 52, 55, 59, 60, 61, 62, etc. It is done.
[0023]
Examples of red pigments include C.I. I. Pigment Red 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 15, 17, 18, 22, 23, 31, 37, 38, 41, 42, 48: 1, 48: 2, 48: 3, 49, 50, 52, 53, 54, 57, 58, 60, 63, 64, 68, 81, 88, 90, 97, 112, 114, 115, 122, 123, 133, 139, 144, 146, 147, 149, 150, 151, 166, 168, 170, 171, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 192, 194, 202, 207, 208, 209, 214, 215, 216, 217, 220, 221, 223, 224, 226, 227, 228, 240, 242, 243, 245, 246, 247, 254, etc.
[0024]
Examples of violet pigments include C.I. I. Pigment violet 1, 2, 3, 5, 19, 23, 29, 30, 31, 32, 33, 36, 37, 38, 39, 40, 43, 50 and the like.
[0025]
Examples of blue pigments include C.I. I. Pigment Blue 1, 17, 19, 22, 56, 60, 61, 64, and the like. Examples of green pigments include C.I. I. Pigment Green 2, 8, 10, etc. Examples of the brown pigment include C.I. I. Pigment brown 5, 23, 25, 26, 32, and the like. Examples of black pigments include C.I. I. Pigment black 7 and the like.
[0026]
Examples of the dye include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinone imine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.
[0027]
Examples of the azo dye include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Molded Red 7, C.I. I. Moldant Yellow 5, C.I. I. Examples thereof include Moldant Black 7.
[0028]
Examples of anthraquinone dyes include C.I. I. Bat Blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disperse thread 60, C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 60 etc. are mentioned.
[0029]
Other examples of the phthalocyanine dye include C.I. I. Pad Blue 5 and the like are quinone imine dyes such as C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 and the like are quinoline dyes such as C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like are nitro dyes such as C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 and the like.
[0030]
Specific examples of carbon black and dyes / pigments other than those described above include the following. Mitsubishi Carbon Black M1000, Mitsubishi Carbon Black MA-100, Mitsubishi Carbon Black # 40, Victoria Pure Blue (42595), Auramin O (41000), Catillon Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170), Sakuranin OK70: 100 (50240), Erioglaucine X (42080), NO. 120 / Lionol Yellow (21090), Lionol Yellow GRO (21090), Shimura First Yellow GRO (21090), Shimura First Yellow 8GF (21105), Benzidine Yellow 4J-564D (21095), Shimla First Red 4015 (12355), Lionol Red 7B4401 (15850), Fast Gen Blue JGR-L (74160), Lionol Blue SM (26150), Lionol Blue ES (Pigment Blue 15: 6, Pigment Blue 1536), Lionogen Red GD (Pigment Red 168) Pigment Red 108), Lionol Green 2YS (Pigment Green 36), and the like.
[0031]
The use ratio of the coloring material is usually 1 to 70% by weight, preferably 10 to 70% by weight, more preferably 20 to 60% by weight, based on the total solid content in the colored resin composition. In the present invention, the “solid content” means all components other than the solvent components described later.
[0032]
<Binder resin>
As the binder resin, for example, (meth) acrylic acid, (meth) acrylic ester, (meth) acrylamide, maleic acid, (meth) acrylonitrile, styrene, vinyl acetate, vinylidene chloride, maleimide, or other homopolymers, or Copolymers containing these monomers, polyethylene oxide, polyvinyl pyrrolidone, polyamide, polyurethane, polyester, polyether, polyethylene terephthalate, acetyl cellulose, novolac resin, resole resin, polyvinyl phenol, polyvinyl butyral and the like can be mentioned.
[0033]
In the present invention, “(meth) acrylic acid” means that both acrylic acid and methacrylic acid are included, and (meth) acrylate, (meth) acryloyl group, etc. have the same meaning, The term “) polymer” is meant to include both single polymers (homopolymers) and copolymers (copolymers). In the present invention, “acrylic resin” means a (co) polymer containing (meth) acrylic acid and a (co) polymer containing a (meth) acrylic ester having a carboxyl group.
[0034]
Among these, an acrylic resin containing a monomer having a carboxyl group or a phenolic hydroxyl group in the side chain or main chain is preferable. When an acrylic resin having these functional groups is used as the binder resin, the obtained color filter can be developed with an alkaline solution. Among them, an acrylic resin having a carboxyl group that can be developed with a highly alkaline solution, such as an acrylic acid (co) polymer, a styrene-maleic anhydride resin, an acid anhydride-modified resin of novolak epoxy acrylate, etc. It is. Among them, a (co) polymer containing (meth) acrylic acid or a (co) polymer containing a (meth) acrylic acid ester having a carboxyl group is particularly preferable. These acrylic resins are excellent in developability, transparency, etc., can be obtained in combination with various monomers to obtain copolymers having different performances, and have an advantage that the production method is easy to control.
[0035]
The acrylic resin as the binder resin is, for example, a (co) polymer mainly composed of the following monomers. Examples of the monomer include compounds obtained by adding an acid (anhydride) to hydroxyalkyl (meth) acrylate.
[0036]
And as said hydroxyalkyl (meth) acrylate, (meth) acrylic acid, succinic acid (2- (meth) acryloyloxyethyl) ester, adipic acid (2-acryloyloxyethyl) ester, phthalic acid (2 -(Meth) acryloyloxyethyl) ester, hexahydrophthalic acid (2- (meth) acryloyloxyethyl) ester, maleic acid (2- (meth) acryloyloxyethyl) ester, succinic acid (2- (meta ) Acryloyloxypropyl) ester, adipic acid (2- (meth) acryloyloxypropyl) ester, hexahydrophthalic acid (2- (meth) acryloyloxypropyl) ester, phthalic acid (2- (meth) acryloyl) Roxypropyl) ester, maleic acid (2- (meth) acryloyloxypropyl) Stealth, succinic acid (2- (meth) acryloyloxybutyl) ester, adipic acid (2- (meth) acryloyloxybutyl) ester, hexahydrophthalic acid (2- (meth) acryloyloxybutyl) ester, phthalate Examples include acid (2- (meth) acryloyloxybutyl) ester and maleic acid (2- (meth) acryloyloxybutyl) ester, and the acid (anhydride) includes (anhydrous) succinic acid and (anhydrous). Examples thereof include phthalic acid and (anhydrous) maleic acid.
[0037]
Monomers that can be copolymerized with the above monomers include styrene monomers such as styrene, α-methylstyrene, vinyltoluene, cinnamic acid, maleic acid, fumaric acid, maleic anhydride, itacone. Unsaturated group-containing carboxylic acids such as acids, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, allyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxyethyl Esters of (meth) acrylic acid such as (meth) acrylate, hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, hydroxyphenyl (meth) acrylate, methoxyphenyl (meth) acrylate, and (meth) acrylic acid Caprolactone, β-propiolac , Γ-butyrolactone, δ-valerolactone and other lactones, acrylonitrile, methacrylonitrile and other acrylonitriles, (meth) acrylamide, N-methylolacrylamide, N, N-dimethylacrylamide, N-methacryloyl Acrylamides such as morpholine, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminoethylacrylamide, vinyl acids such as vinyl acetate, vinyl versatate, vinyl propionate, vinyl cinnamate and vinyl pivalate Etc.
[0038]
In particular, as a preferred binder resin for improving the strength of the coating film on the substrate, at least one of the following monomers (a) is copolymerized with at least one of the following monomers (b): An acrylic resin that has been removed.
[0039]
Examples of the monomer (a) include styrene, α-methylstyrene, benzyl (meth) acrylate, hydroxyphenyl (meth) acrylate, methoxyphenyl (meth) acrylate, hydroxyphenyl (meth) acrylamide, and hydroxyphenyl (meth). Examples thereof include monomers having a phenyl group such as acrylic sulfoamide.
[0040]
As said monomer (b), (meth) acrylic acid or succinic acid (2- (meth) acryloyloxyethyl) ester, adipic acid (2-acryloyloxyethyl) ester, phthalic acid (2 -Having a carboxyl group such as (meth) acryloyloxyethyl) ester, hexahydrophthalic acid (2- (meth) acryloyloxyethyl) ester, maleic acid (2- (meth) acryloyloxyethyl) ester (meta ) Acrylic acid ester and the like.
[0041]
The monomer (a) is usually 10 to 98 mol%, preferably 20 to 80 mol%, more preferably 30 to 70 mol%, and the monomer (b) is usually 2 to 90 mol%, preferably 20 It is used in a proportion of ˜80 mol%, more preferably 30 to 70 mol%.
[0042]
The binder resin is preferably an acrylic resin having an ethylenic double bond in the side chain. By using such an acrylic resin, the photocurability of the colored resin composition for a color filter according to the present invention is improved, so that the resolution of the color filter according to the second invention and the adhesion to the substrate are further improved. I can do it.
[0043]
As a method for introducing an ethylenic double bond into the side chain of the acrylic resin, for example, the method described in Japanese Patent Publication No. 50-34443, Japanese Patent Publication No. 50-34444, etc., (1) Acrylic resin And a method in which a compound having both a glycidyl group or an epoxycyclohexyl group and a (meth) acryloyl group is reacted with the carboxyl group possessed by (2) a method in which acrylic acid chloride is reacted with the hydroxyl group of the acrylic resin.
[0044]
Specifically, an acrylic resin having a carboxyl group or a hydroxyl group is added to glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl α-ethyl acrylate, crotonyl glycidyl ether, (iso) crotonic acid glycidyl ether, (3, By reacting compounds such as 4-epoxycyclohexyl) methyl (meth) acrylate, (meth) acrylic acid chloride, and (meth) allyl chloride, an acrylic resin having an ethylenic double bond group in the side chain can be obtained. I can do it. Especially, what made the alicyclic epoxy compound like (3,4-epoxycyclohexyl) methyl (meth) acrylate react with acrylic resin which has a carboxyl group and a hydroxyl group is preferable.
[0045]
As described above, the method for introducing an ethylenic double bond into an acrylic resin having a carboxylic acid group or a hydroxyl group in advance is usually 2 to 50 mol%, preferably 5 to 40 mol% of a carboxyl group or hydroxyl group. A method of bonding a compound having an ethylenic double bond is preferred. The carboxyl group content is preferably in the range of 5 to 200 as the acid value. When the acid value is 5 or less, it becomes insoluble in an alkaline developer, and when it exceeds 200, the development sensitivity may be lowered.
[0046]
The weight average molecular weight (Mw) measured by GPC of the acrylic resin is preferably in the range of 1,000 to 100,000. When the weight average molecular weight is 1,000 or less, it is difficult to obtain a uniform coating film, and when it exceeds 100,000, the developability tends to decrease.
[0047]
The ratio of binder resin is 10-80 weight% normally with respect to the total solid in the curable resin composition based on this invention, Preferably it is 20-70 weight%. A silane coupling agent can be blended for the purpose of improving the affinity of the interface between the colorant and the binder resin. The ratio of the silane coupling agent is preferably in the range of 1 to 10% by weight as the ratio in the solid content.
[0048]
<Binder resin monomer>
The monomer of the binder resin is not particularly limited as long as it is a polymerizable low-molecular compound, but it is an addition-polymerizable compound having at least one ethylenic double bond (hereinafter abbreviated as “ethylenic compound”). ) Is preferred. When the curable resin composition according to the present invention is irradiated with actinic rays, such an ethylenic compound is cured by addition polymerization by the action of a photopolymerization initiator system described later. In the present invention, the “monomer” has a meaning corresponding to a so-called polymer substance, and includes a dimer, a trimer, an oligomer and the like in addition to a monomer in a narrow sense.
[0049]
Examples of the ethylenic compound include unsaturated carboxylic acids, esters thereof with monohydroxy compounds, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids, aromatic polyhydroxy compounds and unsaturated carboxylic acids, and the like. Esters, polyisocyanate compounds obtained by esterification reaction with unsaturated carboxylic acid and polyvalent carboxylic acid, and polyhydric hydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds described above ( Examples thereof include an ethylenic compound having a urethane skeleton obtained by reacting with a (meth) acryloyl-containing hydroxy compound.
[0050]
Esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylol ethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, Examples thereof include acrylic acid esters such as pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate. Furthermore, the acrylic acid part of these acrylates is a methacrylic acid ester replaced with a methacrylic acid part, an itaconic acid ester replaced with an itaconic acid part, a crotonic acid ester replaced with a crotonic acid part, or a maleic acid replaced with a maleic acid part Examples include esters.
[0051]
Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, pyrogallol triacrylate, and the like.
[0052]
The esters obtained by the esterification reaction of an unsaturated carboxylic acid with a polyvalent carboxylic acid and a polyvalent hydroxy compound are not necessarily a single substance, and may be a mixture. Typical examples include condensates of acrylic acid, phthalic acid and ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, acrylic acid, adipic acid, butanediol and glycerin. And the like.
[0053]
Examples of the ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound and a (meth) acryloyl group-containing hydroxy compound include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate, and fats such as cyclohexane diisocyanate and isophorone diisocyanate. Aromatic diisocyanates such as cyclic diisocyanates, tolylene diisocyanate, diphenylmethane diisocyanate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy (1,1,1-triacryloyloxymethyl) propane, 3- With (meth) acryloyl group-containing hydroxy compounds such as hydroxy (1,1,1-trimethacryloyloxymethyl) propane Applied Physics and the like.
[0054]
Examples of ethylenic compounds other than those described above include acrylamides such as ethylene bisacrylamide, allyl esters such as diallyl phthalate, and vinyl group-containing compounds such as divinyl phthalate.
[0055]
The ratio of the binder resin monomer is generally 10 to 80% by weight, preferably 20 to 70% by weight, based on the total solid content in the curable resin composition according to the present invention.
[0056]
When the colored resin composition of the present invention contains the above-described ethylenic compound, it has a function of directly absorbing light or photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction to generate a polymerization active radical. It is necessary to blend a photopolymerization initiator system into the colored resin composition. In the present invention, the “photopolymerization initiator system” means a mixture in which an additive such as an accelerator and a sensitizing dye is used in combination with the photopolymerization initiator.
[0057]
When a black photopolymerizable layer is formed from a colored resin composition, the photopolymerization initiator system is exposed to light from the photopolymerizable layer through a pattern mask. It means a compound that exhibits, and it is preferable to use an exposure light source corresponding to the image exposure. Also, in each of the red, green, and blue photopolymerizable layers, red, green, and blue pixel image patterns are formed between the black matrix patterns by exposure through a pattern mask of each color and other methods. As in the case of the black matrix pattern, the photopolymerization initiator system is preferably a compound that exhibits sensitivity to ultraviolet light to visible light, particularly a compound that exhibits spectral sensitivity at a wavelength of 450 nm or less, particularly 400 nm or less.
[0058]
Examples of the photopolymerization initiator include metallocene compounds including titanocene compounds described in JP-A Nos. 59-152396 and 61-151197, and JP-A-10-39503. N-aryl-α-amino acids such as hexaarylbiimidazole derivatives, halomethyl-s-triazine derivatives, N-phenylglycine, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters described And radical activators such as
[0059]
Examples of the accelerator include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, and 2-mercaptobenzimidazole. And a mercapto compound having a heterocyclic ring and an aliphatic polyfunctional mercapto compound. Two or more kinds of mixtures may be sufficient as a photoinitiator and an accelerator, respectively.
[0060]
Specific examples of the photopolymerization initiator system include dialkyl acetophenone series described in pages 16 to 26 of “Fine Chemical” (March 1, 1991, vol. 20, No. 4), In addition to benzoin, thioxanthone derivatives, etc., as described in JP-A-58-403023 and JP-B-45-37377, hexaarylbiimidazole series, S-trihalomethyltriazine series, JP-A-4-221958 Examples thereof include a combination of titanocene and a xanthene dye, an addition-polymerizable ethylenic saturated double bond-containing compound having an amino group or a urethane group, which are described in JP-A-4-219756.
[0061]
The proportion of the photopolymerization initiator system is usually 0.1 to 30% by weight, preferably 0.5 to 20% by weight, more preferably 0.7 to 0%, based on the total solid content in the colored resin composition of the present invention. 10% by weight. If the ratio of the photopolymerization initiator system is extremely low, the sensitivity to exposure light may be reduced. On the other hand, if it is extremely high, the solubility of the unexposed part in the developer may be reduced, causing development failure. This is not preferable.
[0062]
If necessary, a sensitizing dye corresponding to the wavelength of the image exposure light source can be blended with the photopolymerization initiator system for the purpose of improving the sensitivity. Examples of the sensitizing dye include xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, JP-A-3-239703, JP-A-5-289335, and the like. Coumarin dyes having a heterocyclic ring, 3-ketocoumarin compounds described in JP-A-3-239703, JP-A-5-289335, etc., pyromethene dyes described in JP-A-6-19240, and others JP-A-47-2528, JP-A-54-155292, JP-B-45-37377, JP-A-48-84183, JP-A-52-112681, JP-A-58- No. 15503, JP-A-60-88005, JP-A-59-56403, JP-A-2-69, JP-A-57-16 088, JP-A No. 5-107761, JP-A No. 5-210240, JP-like dyes having a dialkyl aminobenzene skeleton are described in, JP-A-4-288818 discloses the like.
[0063]
The sensitizing dye is preferably an amino group-containing sensitizing dye, and more preferably a compound having both an amino group and a biphenyl group in the same molecule. Specifically, for example, 4,4′-bis (dimethylamino) benzophenone (Michler's ketone), 4,4′-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4′-diaminobenzophenone, 3, Benzophenone compounds such as 3′-diaminobenzophenone and 3,4-diaminobenzophenone, 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) ) Benzo [4,5] benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-oxazole, 2- ( p-dimethylaminophenyl) benzothiazo 2- (p-diethylaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) 1, 3,4-thiadiazole, (p-dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, p-dialkylaminophenyl group-containing compounds such as p-diethylaminophenyl) pyrimidine. Of these, 4,4′-dialkylaminobenzophenone is most preferred.
[0064]
The proportion of the sensitizing dye is usually 0 to 20% by weight, preferably 0.2 to 15% by weight, more preferably 0.5 to 10% by weight, based on the total solid content in the colored resin composition of the present invention. %.
[0065]
<Thermal polymerization inhibitor>
Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-t-butyl-p-cresol, β-naphthol and the like. The blending amount of the thermal polymerization inhibitor is usually 3% by weight or less with respect to the total solid content in the colored resin composition.
[0066]
<Plasticizer>
Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin and the like. The compounding quantity of a plasticizer is 10 weight% or less normally with respect to the total solid in a colored coloring resin composition. .
[0067]
<Other additives>
In the present invention, in addition to the above, if necessary, a dispersant, a dispersion aid, a storage stabilizer, a surface protective agent, a smoothing agent, a coating aid, an adhesion improver, a coatability improver, a development improver, a silane cup A ring agent or the like can be added.
[0068]
The feature of the colored resin composition of the present invention is that a specific solvent is used to achieve the object of the present invention. That is, the colored resin composition according to the first aspect of the present invention uses a solvent having a volume average particle diameter (mv1) defined in the following (a) of 200 nm or less, and the second aspect of the present invention. The colored resin composition uses a solvent in which the volume average particle size (mv1) specified in the following (a) is 1.5 times or less the volume average particle size (mv2) specified in the following (b). use. In addition, the measuring method of a volume average particle diameter is demonstrated in an Example.
[0069]
(A) Volume average particle diameter (mv1) in the redispersed liquid when the dried film formed by the colored resin composition is immersed in a solvent 1000 times by weight and redispersed.
[0070]
(B) Volume average particle diameter (mv2) in the colored resin composition dilution when the colored resin composition is diluted with a solvent of 1000 times by weight or more
[0071]
<Solvent>
In general, the solvent has a function of adjusting the viscosity by dissolving or dispersing each of the above-mentioned components. In the present invention, the solvent satisfying the above-described conditions includes a solvent containing alcohols and / or alkyl alcohol ethers. Are preferably used. In a preferred embodiment, an alkyl alcohol ether acetate is further contained, and another solvent having a boiling point (boiling point under a pressure of 1013.25 [hPa] condition, hereinafter the same) is 150 ° C. or higher. Moreover, other solvents other than these are contained as required.
[0072]
As the alcohols and alkyl alcohol ethers, those having a monovalent to divalent alcoholic hydroxyl group are preferable. Specifically, aliphatic alcohols such as propanol, butanol, propylene glycol and butanediol, aromatic alcohols such as benzyl alcohol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol mono n-butyl ether, propylene glycol methyl Examples include ethers and glycol ethers such as diethylene glycol monoethyl ether. Among these, alkyl alcohol ethers are preferable, and glycol monoethers are particularly preferable.
[0073]
Among the above alcohols and alkyl alcohol ethers, those having a boiling point of 50 to 300 ° C. are preferable. When the boiling point is less than 50 ° C., drying is promoted in the coating process or the like, and thus the effect of adding alcohols and / or alkyl alcohol ethers may be offset. When the boiling point exceeds 300 ° C., the effect of suppressing the drying property of the colored resin composition is high, but a large amount of residual solvent is present in the coating film even after heat baking, which may cause quality defects. A preferred range of boiling points of alcohols and alkyl alcohol ethers is 100 to 250 ° C.
[0074]
The content of alcohols and alkyl alcohol ethers in the solvent is usually 1 to 70% by weight, preferably 10 to 40% by weight, and more preferably 20 to 40% by weight.
[0075]
Alkyl alcohol ether acetate improves the solubility of the solvent and stabilizes the dispersibility of the dispersed components. Examples of the alkyl alcohol ether acetate include propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate and the like. Of these, propylene glycol monomethyl ether acetate is preferred.
[0076]
The alkyl alcohol ether acetate preferably has a higher boiling point than alcohols and alkyl alcohol ethers. When the boiling point of the alkyl alcohol ether acetate is extremely low, the alkyl alcohol ether acetate volatilizes prior to the alcohol or alkyl alcohol ether when the drying proceeds, and aggregation of the coloring material in the concentrate may occur. is there.
[0077]
The content of the alkyl alcohol ether acetate in the solvent is usually 30 to 90% by weight, preferably 50 to 80% by weight.
[0078]
Other solvents having a boiling point of 150 ° C. or higher suppress solvent drying. Examples of such solvents include ethyl 3-ethoxypropionate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and ethylene glycol diacetate. It is done. Of these, ethyl 3-ethoxypropionate and diethylene glycol monoethyl ether acetate are preferred. The content of other solvents having a boiling point of 150 ° C. or higher in the solvent is usually 1 to 60% by weight, preferably 10 to 30% by weight.
[0079]
Examples of other solvents other than the above include, for example, diisopropyl ether, mineral spirit, n-pentane, amyl ether, ethyl caprylate, n-hexane, diethyl ether, isoprene, ethyl isobutyl ether, butyl stearate, n-octane, di- Isobutylene, amyl acetate, butyl acetate, apcocinner, butyl ether, diisobutyl ketone, methylcyclohexene, methyl nonyl ketone, propyl ether, dodecane, soak solvent No. 1 and no. 2, amyl formate, dihexyl ether, diisopropyl ketone, Solvesso # 150, (n, sec, t-) butyl acetate, hexene, shell TS28 solvent, butyl chloride, ethyl amyl ketone, ethyl benzoate, amyl chloride, ethylene glycol diethyl ether , Ethyl orthoformate, methoxymethylpentanone, methyl butyl ketone, methyl hexyl ketone, methyl isobutyrate, benzonitrile, ethyl propionate, methyl isoamyl ketone, methyl isobutyl ketone, propyl acetate, amyl acetate, amyl formate, Bicyclohexyl, dipentene, methoxymethylpentanol, methyl amyl ketone, methyl isopropyl ketone, propyl propionate, propylene glycol-t Butyl ether, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, carbitol, cyclohexanone, ethyl acetate, propylene glycol, diglyme, ethylene glycol acetate, ethyl carbitol, butyl carbitol, ethylene glycol monobutyl ether, propylene glycol t-butyl ether , 3-methyl-3-methoxybutanol, tripropylene glycol methyl ether, 3-methyl-3-methoxybutyl acetate and the like. Such a solvent functions to uniformly dissolve or disperse the photopolymerization initiator system and other additives in addition to adjusting the viscosity of the colored resin composition of the present invention.
[0080]
The content of the solvent is usually 99% by weight or less, preferably 50 to 90% by weight, and more preferably 60 to 85% by weight as a ratio with respect to the entire colored resin composition. If the solvent content exceeds 99% by weight, the coloring material, binder resin, etc. will be too small to form a coating film, and if the solvent content is too low, the viscosity will increase. Therefore, it becomes unsuitable for application.
[0081]
The coloring resin composition of the present invention is prepared as follows. First, a predetermined amount of a coloring material and a solvent are weighed, and both are dispersed in a dispersion treatment step to obtain a liquid colored resin composition (ink-like material). In this dispersion treatment step, a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like can be used. Since the coloring material is made fine particles by this dispersion treatment, the coating characteristics of the colored resin composition are improved, and the transmittance of transmitted light is improved.
[0082]
In the above dispersion treatment, it is preferable to use a dispersant such as a surfactant, a dispersion aid and the like as appropriate. In particular, the use of a polymer dispersant is preferable because a colored resin composition having excellent dispersion stability over time can be obtained. For example, when the dispersion treatment is performed with a sand grinder, glass (or zirconia) beads having a diameter of 0.1 to several millimeters are preferably used. The temperature during the dispersion treatment is usually from 0 ° C to 100 ° C, preferably from room temperature to 80 ° C. The dispersion time varies depending on the composition of the ink-like material (coloring material, solvent, dispersant), the size of the sand grinder apparatus, and the like, and therefore needs to be adjusted appropriately.
[0083]
To the ink-like material obtained by the above dispersion treatment step, a binder resin and / or its monomer, and if necessary, a predetermined amount of a photopolymerization initiator system, a thermal polymerization inhibitor, a plasticizer, other Additives etc. are mixed to make a uniform dispersion solution. In addition, in each process of a dispersion | distribution process and a mixing process, since fine refuse may mix, it is preferable to filter the obtained ink-like thing with a filter etc.
[0084]
Since the colored resin composition of the present invention contains the specific solvent described above, it has a feature that it can suppress the generation of dry agglomerates at the tip of the die lip in the coating process. Therefore, the colored resin composition of the present invention is suitably used for a die coating method, and particularly used for forming a color filter described later.
[0085]
Next, the color filter of the present invention will be described. The color filter of the present invention is formed by using a colored resin composition by a die coating method. When the colored resin composition to be used uses only a binder resin and does not use the monomer, the type of binder resin suitable for the desired pixel image formability and performance, the production method to be adopted, etc. Is appropriately selected. When the binder resin and its monomer are used in combination, the properties of the colorable resin composition, the physical properties after curing (particularly after photocuring), for example, the compatibility with the solvent, and the coating of the colored resin composition on the substrate Formability, adhesion to the substrate, developability of the coating film, etc. are improved.
[0086]
The material of the transparent substrate for the color filter is not particularly limited as long as it is transparent and has an appropriate strength. For example, thermosetting of polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, thermoplastic resins of polycarbonate, polymethyl methacrylate, polysulfone, epoxy resins, unsaturated polyester resins, poly (meth) acrylic resins, etc. Resin, various kinds of glass and the like. Among these, from the viewpoint of heat resistance, glass or a resin excellent in heat resistance is preferable.
[0087]
To improve surface properties such as adhesiveness, transparent substrates and black matrix forming substrates are subjected to corona discharge treatment, ozone treatment, thin film formation treatment of various resins such as silane coupling agents and urethane resins as necessary. You may go. The thickness of the transparent substrate is usually 0.05 to 10 mm, preferably 0.1 to 7 mm. Moreover, when performing the thin film formation process of various resin, the film thickness is 0.01-10 micrometers normally, Preferably it is the range of 0.05-5 micrometers.
[0088]
A color filter is manufactured by providing a black matrix on a transparent substrate and forming red, green, and blue pixel images. The colored resin composition of the present invention described above is used as at least one resist forming coating solution of black, red, green, and blue.
[0089]
The black resist is formed on the transparent substrate (on the raw glass surface) by applying, heating and drying, image exposure, development and thermosetting. For red, green, and blue, coating, heating and drying on a resin black matrix forming surface formed on a transparent substrate or a metal black matrix forming surface formed using a chromium compound or other light shielding metal material Then, image exposure, development, and thermosetting are performed to form pixel images of each color.
[0090]
As the light shielding metal material used for forming the metal black matrix, chromium compounds such as metal chromium, chromium oxide and chromium nitride, nickel and tungsten alloys, etc. are used, and these may be laminated in a plurality of layers. Good. The light shielding metal thin film is generally formed by a sputtering method. Then, after forming a desired pattern in a film shape with a positive photoresist, an etchant mixed with ceric ammonium nitrate and perchloric acid is used for chromium, and for other materials The black matrix can be formed by etching using an etching solution according to the material and finally stripping the positive photoresist with a dedicated stripper.
[0091]
The application of the colored resin composition by the die coating method can be performed using a known die coater, and the application conditions at that time may be appropriately selected depending on the composition of the colored resin composition, the type of the color filter to be manufactured, and the like. Good. For example, the lip width at the nozzle tip is preferably 50 to 500 μm, and the distance between the nozzle tip and the substrate surface is preferably 30 to 300 μm. In order to adjust the thickness of the coating film, the running speed of the lip and the discharge amount from the lip may be adjusted.
[0092]
The coating film after the colored resin composition is applied to the substrate is preferably dried by a drying method using a hot plate, an IR oven, or a convection oven. Usually, after preliminary drying, it is dried by heating again. The conditions for the preliminary drying can be appropriately selected according to the type of the solvent in the colored resin composition, the performance of the dryer to be used, and the like. Usually, it is selected at a temperature of 40 to 80 ° C. for 15 seconds to 5 minutes, preferably at a temperature of 50 to 70 ° C. for 30 seconds to 3 minutes.
[0093]
The temperature condition for the reheating drying is usually 50 to 200 ° C., preferably 70 to 160 ° C., more preferably 70 to 130 ° C. higher than the preliminary drying temperature. Further, although depending on the heating temperature, the time is usually 10 seconds to 10 minutes, preferably 15 seconds to 5 minutes. The higher the temperature is, the better the adhesion to the transparent substrate is. However, when the temperature is too high, the compound constituting the photopolymerization initiator system may be decomposed to induce thermal polymerization and cause poor development. The thickness of the colored resin composition coating film after reheating and drying is usually 0.5 to 3 μm, preferably 1 to 2 μm. Note that this step may be a vacuum drying method that is performed in a vacuum chamber without increasing the temperature.
[0094]
Image exposure is performed by superimposing a negative matrix pattern on the coating film of the colored resin composition and irradiating a UV or visible light source through this matrix pattern. Under the present circumstances, in order to prevent the fall of the sensitivity by the oxygen of a photoinitiator type | system | group at this time, you may expose, after forming oxygen barrier layers, such as a polyvinyl alcohol layer, on the coating film of a colored resin composition.
[0095]
Examples of the light source used for the above image exposure include a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a lamp light source such as a carbon arc, a fluorescent lamp, Examples thereof include laser light sources such as argon ion laser, YAG laser, excimer laser, nitrogen laser, helium cadmium laser, and semiconductor laser. When irradiating and using light of a specific wavelength, an optical filter can be used.
[0096]
Development can be performed using an organic solvent or an aqueous solution containing a surfactant and an alkaline compound. This developer may contain an organic solvent, a buffering agent, a complexing agent, a dye or a pigment.
[0097]
Examples of the alkaline compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, phosphorus Inorganic alkaline compounds such as potassium acid, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-di- or triethanolamine, mono-di- or Trimethylamine, mono-di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline, etc. Yes And alkali compounds. These alkaline compounds may be used as a mixture of two or more.
[0098]
Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and alkylbenzenes. Examples include anionic surfactants such as sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinate esters, and amphoteric surfactants such as alkylbetaines and amino acids.
[0099]
Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like. The organic solvent can be used by mixing with water.
[0100]
The temperature of development processing is 10-50 degreeC normally, Preferably it is 15-45 degreeC, More preferably, it is 20-40 degreeC. Further, the developing method may be any of immersion developing method, spray developing method, brush developing method, ultrasonic developing method and the like. After the development process, a thermosetting process is performed. The temperature at this time is usually 100 to 280 ° C., preferably 150 to 250 ° C., and the time is usually in the range of 5 to 60 minutes.
[0101]
The patterning image formation for one color is completed through the above series of steps. This process is sequentially repeated to pattern black, red, green, and blue to form a color filter. Note that the order of patterning the four colors is not limited to the order described above.
[0102]
In the present invention, a color filter can also be produced using a colored resin composition that does not contain a photopolymerization initiation system. In this case, the colored resin composition is applied to the substrate, and a pixel image is formed by an etching method.
[0103]
The color filter of the present invention forms a transparent electrode such as ITO on the image as it is, and is used as a part of components such as a color display and a liquid crystal display device, in order to improve surface smoothness and durability. If necessary, a top coat layer such as polyamide or polyimide can be provided on the image. Further, in some applications such as a planar alignment type drive system (IPS mode), the transparent electrode may not be formed.
[0104]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to a following example, unless the summary is exceeded. In the following examples and comparative examples, the details of the used coloring materials are as shown in Table 1, and the details of the solvent components used are as shown in Table 2.
[0105]
[Table 1]

[0106]
[Table 2]

[0107]
Example 1 3 And Comparative Examples 1-2
<Preparation of colored resin composition>
Each component of each blending amount shown in Table 3 and 3.6 times by weight of zirconia beads (diameter 0.5 mm) with respect to the total amount are housed in a paint shaker and subjected to a dispersion treatment for 7 hours to give an ink-like color. A resin composition was prepared.
[0108]
[Table 3]

[0109]
[Chemical 1]

[0110]
[Chemical formula 2]

[0111]
<Manufacture of color filters>
An ink-like black colored resin composition was applied to a glass substrate (“AN635” manufactured by Asahi Glass Co., Ltd.) having a length of 370 mm, a width of 470 mm, and a thickness of 0.7 mm using a die coater. The die coater used was a 360 mm wide die coater, the lip interval was 200 μm, and the gap with the glass substrate surface was 100 μm. At the time of coating, the discharge amount of the coating liquid was adjusted so that the dry film thickness was 0.7 μm. Then, after drying at 60 degreeC for 1 minute, it heat-dried at 110 degreeC for 2 minutes. Thereafter, an aqueous polyvinyl alcohol solution was applied on the coating film of the colored resin composition so that the film thickness after drying was 1.5 μm and then dried to form an oxygen blocking layer.
[0112]
Next, using a black matrix negative photomask repeated at a pitch of 30 μm in width, 330 μm in length and 110 μm in width, using a 2 kW high pressure mercury lamp, 300 mJ / cm ² The exposure process was performed with the exposure amount of. Thereafter, development processing was performed using a 0.1 wt% aqueous sodium carbonate solution at a liquid temperature of 23 ° C. Then 3Kg / cm ² The black water was formed by spraying with water for 30 seconds. Then, the thermosetting process for 7 minutes was performed at the temperature of 200 degreeC.
[0113]
Next, using a liquid colored resin composition containing each color material of red, green, and blue, each process of coating, preliminary drying, heat drying, exposure, development, washing with water, and thermosetting is performed in the same procedure as described above. Each color pattern was sequentially formed to obtain a color filter. At this time, the liquid discharge amount of the coating liquid was adjusted so that the dry film thickness was 1.3 μm. The exposure amount is 500 mJ / cm for each color. ² The development processing was performed at a liquid temperature of 25 ° C. using a 0.1 wt% aqueous sodium carbonate solution. 10kg / cm after development ² The spray water washing process was performed at a water pressure of 30 seconds. At the end of each color, a thermosetting treatment at 200 ° C. for 15 minutes was performed. The developing machine used was the same as that used for forming the black matrix. In this way, Examples 1 to 3 Using the colored resin compositions having the compositions of Comparative Examples 1 to 3, 100 color filters with a resin black matrix were prepared.
[0114]
<Measurement of volume average particle diameter mv>
Example 1 3 The colored resin compositions having the compositions of Comparative Examples 1 and 2 were each applied to a 50 mm square glass substrate by a spin coating method with a dry film thickness of 2.5 μm, and air-dried for 60 minutes. Thereafter, it was immersed in 6.25 g of the solvent for forming the colored resin composition at 23 ° C. for 3 minutes, redispersed, and after 10 minutes from the start of immersion, the particle size distribution was measured with “Microtrac UPA” manufactured by Nikkiso Co. The volume average particle diameter (mv1) was calculated. The results are shown in Table 4.
[0115]
At the same time, 0.1 g of the colored resin composition was gradually added dropwise to 100 g of the solvent while stirring at 23 ° C. to prepare a diluted solution. Ten minutes after preparation of the diluted solution, the particle size distribution was measured in the same manner as described above, and the volume average particle size (mv2) was calculated. The results are shown in Table 4.
[0116]
[Table 4]

[0117]
<Color filter evaluation test>
The obtained color filter was measured for the presence or absence of foreign matter defects, and the foreign matter defect occurrence rate is shown in Table 5. In Table 5, black, red, green, and blue mean a colored resin composition (resist) that exhibits an ink form of each color. In addition, foreign matter defects are [(major axis) ² + (Minor axis) ² ] Having a square root of 60 μm or more is defined as foreign matter, and a value obtained by dividing the number of color filters in which foreign matter defects due to aggregation of each color resist are recognized by the total number of manufactured products (100 pieces) is defined as the foreign matter defect occurrence rate. Defined.
[0118]
[Table 5]

[0119]
From Tables 1 to 5, the following is clear.
(1) Since the colored resin composition of the present invention has the solvent component satisfying claims 1 and 2, the color filter produced by applying these compositions has a low incidence of foreign matter defects (Examples 1 to 2). 3 reference).
(2) On the other hand, the color filter manufactured by applying a colored resin composition whose solvent component does not satisfy the requirements of claims 1 and 2 has a high foreign matter defect occurrence rate (see Comparative Examples 1 and 2).
[0120]
【The invention's effect】
The present invention is as described in detail above, and has the following particularly advantageous effects, and its industrial utility value is extremely large.
(1) The colored resin composition of the present invention is difficult to dry and agglomerate in the step of applying to the substrate surface even when the colorant is high in concentration, and the generation of foreign matters is small.
(2) When the colored resin composition of the present invention is applied to the substrate surface by the die coating method, agglomerates are hardly formed on the die lip, and a high-quality product can be obtained with a high yield.
(3) Since the color filter according to the present invention is of high quality, a color display, a liquid crystal display device and the like using the color filter are also of high quality.

Claims (5)

A colored resin composition for a color filter containing a coloring material, a binder resin, its monomer, a solvent, and a polymer dispersant and used in a die coating method, wherein the binder resin has a carboxyl group in the side chain or main chain An acrylic resin containing a monomer having a group or a phenolic hydroxyl group, the solid component concentration in the entire colored resin composition is 15 to 40% by weight, and alcohols and / or alkyl alcohol ethers as a solvent And a solvent having a volume average particle diameter (mv1) defined in the following (a) of 200 nm or less, and a colored resin comprising: Composition.
(A) Volume average particle diameter (mv1) in the redispersed liquid when the dried film formed by the colored resin composition is immersed in a solvent 1000 times by weight and redispersed. A colored resin composition for a color filter containing a coloring material, a binder resin, its monomer, a solvent, and a polymer dispersant and used in a die coating method, wherein the binder resin has a carboxyl group in the side chain or main chain An acrylic resin containing a monomer having a group or a phenolic hydroxyl group, the solid component concentration in the entire colored resin composition is 15 to 40% by weight, and alcohols and / or alkyl alcohol ethers as a solvent And an alkyl alcohol ether acetate having a boiling point higher than these, and the volume average particle diameter (mv1) defined in (a) of claim 1 is the volume average particle diameter (mv2) defined in (b) below: A colored resin composition characterized by using a solvent that is 1.5 times or less of the above.
(B) Volume average particle diameter (mv2) in the colored resin composition dilution when the colored resin composition is diluted with a solvent of 1000 times by weight or more The colored resin composition according to claim 1 or 2, comprising a photopolymerization initiator system component .   A color filter formed by a die coating method using the colored resin composition according to claim 1. A liquid crystal display device formed by using the color filter according to claim 4 .