JP2006053453A - Colored composition for red color filter and color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a color filter having excellent color reproducibility, color separability and high transmittance, and a colored composition for a red color filter. <P>SOLUTION: The colored composition contains C.I. Pigment Red 254 and C.I. Pigment Red 48:1 as red pigments and C.I. Pigment Yellow 139 as a yellow pigment, wherein a pigment blending ratio (wt.%) among C.I. Pigment Red 254, C.I. Pigment Red 48:1 and C.I. Pigment Yellow 139 is (5-70):(10-50):(3-50). The colored composition is used for red filter segments. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a color filter attached to a display such as a color liquid crystal display, an imaging tube element such as a digital camera, a video camera, a copying machine, and a scanner, and a coloring composition for the color filter.

  Color filters mounted on displays such as color liquid crystal displays, digital cameras, video cameras, copiers, scanners, and image pickup tubes are generally red (R) and green (G) on glass substrates and solid image pickup devices. , Blue (B), and colors such as cyan (C), magenta (M), and yellow (Y) complementary colors are provided as fine filter segments.

  Color filter manufacturing methods include dyeing methods using dyes as dyes, dye dispersion methods, pigment dispersion methods using pigments, printing methods, and electrodeposition methods. Among these, the dyeing method or the dyeing and dispersing method has a disadvantage that the heat resistance and the light resistance are slightly inferior because the dye is a dye. Therefore, a pigment having excellent heat resistance and light resistance is used as the coloring matter of the color filter, and the pigment dispersion method is often used as the manufacturing method because of the accuracy and stability of the forming method.

  In the pigment dispersion method, a color resist is formed by mixing and blending a photosensitive agent or an additive in a pigment in which pigment particles, which are pigments, are dispersed in a transparent resin, and this color resist is applied onto a substrate by a coating device such as a spin coater. It is formed into a coating film, selectively exposed through a mask with an aligner or stepper, etc., patterned by alkali development and thermosetting, and composed of fine filter segments by repeating this operation This is a method for producing a color filter.

In order to obtain the required color characteristics, it is common to perform toning using two or more pigments. For red, C.I. I. Pigment Red 177, 208, 224, 254 and the like are used (for example, see Patent Documents 1 to 4). However, C.I. I. When CI Pigment Red 254 is used, the rising characteristic of transition from the absorption band of 570 nm to 590 nm wavelength to the transmission band is good, but there is an unfavorable transmission peak in the wavelength range of 520 nm to 540 nm. In addition, C.I. I. Pigment Red 177 and 224 have the disadvantage that the wavelength of 50% transmittance is slightly shifted to the longer wavelength side, the rise characteristic is loose, and the peak transmittance at 600 to 630 nm is low. Therefore, when these red pigments are used alone, there is a problem in color purity.
JP 9-325209 A JP-A-10-130547 JP 2000-89025 A JP 2001-51112 A

This invention is made | formed in view of said situation, and makes it a subject to provide the coloring composition and color filter for red color filters which have the outstanding color reproducibility, color separation property, and high transmittance | permeability. Is.

  The present invention provides at least C.I. I. Pigment red 254 and C.I. I. Pigment Red 48: 1, C.I. I. Pigment Yellow 139, C.I. I. Pigment red 254 and C.I. I. Pigment red 48: 1 and C.I. I. The pigment blend ratio (wt%) of CI Pigment Yellow 139 is C.I. I. Pigment Red 254 is 5 to 70, C.I. I. Pigment Red 48: 1 is 10 to 50, C.I. I. Pigment Yellow 139 is a coloring composition for red color filter characterized by being 3-50.

  The present invention further comprises at least one red filter segment, at least one green filter segment, and at least one blue filter segment, wherein the at least one red filter segment is a coloring composition for a red color filter according to claim 1. The color filter is formed using an object.

  In the color filter according to the present invention, when the film thickness of the red filter segment is in the range of 0.5 to 2.5 μm, the spectral transmittance characteristic is in the wavelength region of 430 nm to 560 nm. The color filter is characterized in that the transmittance is 3% or less, the wavelength of the spectral transmittance 50% is in the wavelength region of 575 nm to 590 nm, and the spectral transmittance of the wavelength of 600 nm is 80% or more.

  The present invention provides at least C.I. I. Pigment red 254 and C.I. I. Pigment Red 48: 1, C.I. I. Pigment Yellow 139, C.I. I. Pigment red 254 and C.I. I. Pigment red 48: 1 and C.I. I. The pigment blend ratio (wt%) of CI Pigment Yellow 139 is C.I. I. Pigment Red 254 is 5 to 70, C.I. I. Pigment Red 48: 1 is 10 to 50, C.I. I. Since Pigment Yellow 139 is a coloring composition for red color filters having a coloration of 3 to 50, it becomes a coloring composition for red color filters having excellent color reproducibility, color separation, and high transmittance.

  The present invention further comprises at least one red filter segment, at least one green filter segment, and at least one blue filter segment, wherein the at least one red filter segment is the coloring composition for a red color filter according to claim 1. When the film thickness of the red filter segment is in the range of 0.5 to 2.5 μm, the spectral transmittance characteristic is 3 in the wavelength region of 430 nm to 560 nm. %, The wavelength of 50% spectral transmittance is between 575 nm and 590 nm, and the spectral transmittance of 600 nm wavelength is 80% or more, so that excellent color reproducibility, color separation, and high A color filter having transmittance is obtained.

  Hereinafter, the coloring composition for red color filter of the present invention will be described in detail with reference to preferred embodiments, but the production method of the red color filter of the present invention is not particularly limited. Although a pigment dispersion method, a printing method, an electrodeposition method, and the like can be applied, a case where a pigment dispersion method that is generally used is used will be specifically described.

The coloring composition for red color filter of the present invention (hereinafter referred to as a coloring composition) is C.I. I. Pigment red 254 and C.I. I. Pigment Red 48: 1, C.I. I. Pigment Yellow 139 is used.
As described above, C.I. I. Pigment Red 254 has an undesirable transmission peak in the 520 nm to 540 nm wavelength region. I. Pigment Red 254 and C.I. I. Pigment Red 48: 1 and C.I. I. By toning with pigment yellow 139, C.I. I. It is possible to suppress an undesirable transmission peak in the wavelength region of 520 nm to 540 nm while maintaining the rising characteristic that shifts from the absorption band of 570 nm to 590 nm wavelength, which is the characteristic of Pigment Red 254. That is, the spectral transmittance in the wavelength region of 430 nm to 560 nm is 3% or less, the wavelength of 50% spectral transmittance is between the wavelength regions of 575 nm to 590 nm, and the spectral transmittance of 600 nm wavelength is 80% or more. A red color filter having both high color separation and high transmittance can be provided.

  Further, the ratio (% by weight) of these pigments is C.I. I. Pigment Red 254 is 1 to 90, C.I. I. Pigment Red 48: 1 is 1 to 50, C.I. I. Pigment Yellow 139 is preferably 1 to 50, more preferably C.I. I. Pigment Red 254 is 5 to 70, C.I. I. Pigment Red 48: 1 is 10 to 50, C.I. I. Pigment Yellow 139 is 3-50.

The pigment carrier in which the pigment contained in the coloring composition of the present invention is dispersed is composed of a transparent resin, a precursor thereof, or a mixture thereof. The transparent resin is a resin having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Transparent resins include thermoplastic resins, thermosetting resins, and active energy ray curable resins, and precursors thereof include monomers or oligomers that are cured by irradiation with active energy rays to form transparent resins. These can be used alone or in admixture of two or more.
When the composition is cured by ultraviolet irradiation, a photopolymerization initiator or the like is added to the colored composition.

Examples of the thermoplastic resin include butyral resin, styrene - maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. Acrylic resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resins, and the like. Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.

  As the active energy ray-curable resin, a (meth) acryl having a reactive substituent such as an isocyanate group, an aldehyde group or an epoxy group on a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group or an amino group. A resin in which a photocrosslinkable group such as a (meth) acryloyl group or a styryl group is introduced into the linear polymer by reacting a compound or cinnamic acid is used. Further, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is converted into a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. Half-esterified products are also used.

As monomers and oligomers, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate , Polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol Tri (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopen Cylglycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate, epoxy (meth) acrylate, urethane Various acrylates and methacrylates such as acrylates, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide , N-vinylformamide, acrylonitrile and the like, and these can be used alone or in admixture of two or more.

  Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane Acetophenone photopolymerization initiators such as -1-one, benzoin photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4 Benzophenone photopolymerization initiators such as phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2 Thioxanthone photopolymerization initiators such as 2,4-diisopropylthioxanthone, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p -Methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (Trichloromethyl) -s-triazine, 2,4-bis (tri (Loromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4 , 6-Bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4-trichloromethyl (4′-methoxystyryl) -6-triazine, etc. A polymerization initiator, a borate photopolymerization initiator, a carbazole photopolymerization initiator, an imidazole photopolymerization initiator, or the like is used.

  The above photopolymerization initiators are used alone or in combination of two or more. As sensitizers, α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone. , Camphorquinone, ethyl anthraquinone, 4,4′-diethylisophthalophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4,4′-diethylaminobenzophenone, etc. It can also be used together.

  The coloring composition of the present invention (coloring resist in the pigment dispersion method) can be prepared in the form of a solvent development type or alkali development type color resist. The colored resist is a dispersion of a pigment in a pigment carrier containing a thermoplastic resin, a thermosetting resin or a photosensitive resin and a monomer, and a pigment composition composed of a pigment or two or more pigments is used as necessary. In addition to the photoinitiator, it can be produced by finely dispersing in a pigment carrier using various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, a kneader, and an attritor. The colored composition of the present invention can also be produced by mixing several types of pigments separately dispersed on a pigment carrier.

When dispersing the pigment in the pigment carrier, a dispersion aid such as a resin-type pigment dispersant and a surfactant can be appropriately used. The dispersion aid is excellent in dispersing the pigment and has a great effect of preventing re-aggregation of the pigment after dispersion. Therefore, when a coloring composition obtained by dispersing the pigment in the pigment carrier using the dispersion aid is used. Provides a color filter excellent in transparency.

  The resin-type pigment dispersant has a pigment affinity part that has the property of adsorbing to the pigment and a part that is compatible with the pigment carrier, and acts to stabilize the dispersion of the pigment on the pigment carrier by adsorbing to the pigment. It is something to do. Specific examples of resin-type pigment dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamines. Salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly (lower alkylene imines) with polyesters having free carboxyl groups, and the like Water-based dispersants such as oily dispersants such as salts, (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone Resin, water-soluble polymer, polyester Modified polyacrylate, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, they can be used alone or in admixture of two or more.

  Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate. , Lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Anionic surfactant such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene Nonionic surfactants such as nylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; chaotic properties such as alkyl quaternary ammonium salts and their ethylene oxide adducts Surfactants: Examples include amphoteric surfactants such as alkylbetaines such as alkyldimethylaminoacetic acid betaine and alkylimidazolines, and these can be used alone or in admixture of two or more.

The coloring composition for a color filter of the present invention is selected from the following basic group of the formula (1), basic group of the formula (2), basic group of the formula (3) and basicity of the formula (4). It is preferable to contain at least one derivative selected from a pigment derivative, an anthraquinone derivative, a triazine derivative, or an acridone derivative, which has at least one basic group (hereinafter sometimes referred to as “specific basic group”).
The content of the derivative having the specific basic group is preferably 0.001 to 40% by weight, more preferably 1 to 25% by weight, based on the pigment.

上記式（１）〜（４）において、Ｘは、−ＳＯ₂ −、−ＣＯ−、−ＣＨ₂ ＮＨＣＯＣＨ₂ −、−ＣＨ₂ −または直接結合を表し、ｎは、１〜１０の整数を表し、Ｒ₁ およびＲ₂ は、それぞれ独立に、炭素数１〜３６の置換されていてもよいアルキル基、炭素数２〜３６の置換されていてもよいアルケニル基もしくは置換されていてもよいフェニル基を表すか、またはＲ₁ とＲ₂ とが結合して更なる窒素、酸素または硫黄原子を含む置換されていてもよい複素環を形成し、Ｒ₃ は、炭素数１〜３６の置換されていてもよいアルキル基、炭素数２〜３６の置換されていてもよいアルケニル基または置換されていてもよいフェニル基を表し、Ｒ₄ 、Ｒ₅ 、Ｒ₆ およびＲ₇ は、それぞれ独立に、水素原子、炭素数１〜３
６の置換されていてもよいアルキル基、炭素数２〜３６の置換されていてもよいアルケニル基または置換されていてもよいフェニル基を表し、Ｙは、−ＮＲ₈ −Ｚ−ＮＲ₉ −または直接結合を表し、Ｒ₈ およびＲ₉ は、それぞれ独立に、水素原子、炭素数１〜３６の置換されていてもよいアルキル基、炭素数２〜３６の置換されていてもよいアルケニル基または置換されていてもよいフェニル基を表し、Ｚは、炭素数１〜３６の置換されていてもよいアルキレン基、炭素数２〜３６の置換されていてもよいアルケニレン基、または置換されていてもよいフェニレン基を表し、Ｒは、下記式（５）で示される置換基、または下記式（６）で示される置換基を表し、Ｑは、水酸基、アルコキシル基、下記式（５）で示される置換基または下記式（６）で示される置換基を表す。

In the above formulas (1) to (4), X represents —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ — or a direct bond, and n represents an integer of 1 to 10. , R ₁ and R ₂ are each independently an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or an optionally substituted phenyl group. Or R ₁ and R ₂ are combined to form an optionally substituted heterocyclic ring containing an additional nitrogen, oxygen or sulfur atom, and R ₃ is substituted with 1 to 36 carbon atoms Represents an optionally substituted alkyl group, an optionally substituted alkenyl group having 2 to 36 carbon atoms or an optionally substituted phenyl group, wherein R ₄ , R ₅ , R ₆ and R ₇ are each independently hydrogen Atoms, 1 to 3 carbon atoms
6 represents an optionally substituted alkyl group, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or an optionally substituted phenyl group, and Y represents —NR ₈ —Z—NR ₉ — or R ₈ and R ₉ each independently represent a hydrogen atom, an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or a substituted group. Represents an optionally substituted phenyl group, and Z represents an optionally substituted alkylene group having 1 to 36 carbon atoms, an optionally substituted alkenylene group having 2 to 36 carbon atoms, or optionally substituted. Represents a phenylene group, R represents a substituent represented by the following formula (5) or a substituent represented by the following formula (6), and Q represents a hydroxyl group, an alkoxyl group, a substituent represented by the following formula (5). Group or the following formula (6 Represents a substituent represented by

特定の塩基性基を有する顔料誘導体を構成する有機顔料としては、例えば、ジケトピロロピロール系顔料、アゾ、ジスアゾ、ポリアゾ等のアゾ系顔料、フタロシアニン系顔料、ジアミノジアントラキノン、アントラピリミジン、フラバントロン、アントアントロン、インダントロン、ピラントロン、ビオラントロン等のアントラキノン系顔料、キナクリドン系顔料、ジオキサジン系顔料、ペリノン系玩弄、ペリレン系顔料、チオインジゴ系顔料、イソインドリン系顔料、イソインドリノン系顔料、キノフタロン系顔料、スレン系顔料、金属錯体系顔料が挙げられる。また、後述する、着色組成物に用いられる顔料でもよい。
また、特定の塩基性基を有するアントラキノン誘導体および特定の塩基性基を有するアクリドン誘導体を構成するアントラキノンおよびアクリドンは、メチル基、エチル基等のアルキル基、アミノ基、ニトロ基、水酸基、またはメトキシ基、エトキシ基等のアルコキシ基、または塩素等のハロゲン等の置換基を有していてもよいアントラキノンおよびアクリドンである。

Examples of the organic pigment constituting the pigment derivative having a specific basic group include diketopyrrolopyrrole pigments, azo pigments such as azo, disazo, and polyazo, phthalocyanine pigments, diaminodianthraquinone, anthrapyrimidine, and flavantrons. , Antanthrone, Indanthrone, Pyrantron, Violanthrone and other anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thioindigo pigments, isoindoline pigments, isoindolinone pigments, quinophthalone pigments Selenium pigments and metal complex pigments. Moreover, the pigment used for the coloring composition mentioned later may be sufficient.
Anthraquinone and acridone constituting an anthraquinone derivative having a specific basic group and an acridone derivative having a specific basic group are an alkyl group such as a methyl group, an ethyl group, an amino group, a nitro group, a hydroxyl group, or a methoxy group. Anthraquinone and acridone which may have a substituent such as an alkoxy group such as ethoxy group or a halogen such as chlorine.

  Triazines constituting triazine derivatives having specific basic groups are alkyl groups such as methyl and ethyl groups, amino groups or dimethylamino groups, alkylamino groups such as diethylamino groups and dibutylamino groups, nitro groups, and hydroxyl groups. Or a phenyl group or a methyl group which may be substituted with an alkoxy group such as a methoxy group, an ethoxy group or a butoxy group, a halogen such as chlorine, or a methyl group, a methoxy group, an amino group, a dimethylamino group or a hydroxyl group; Group, methoxy group, ethoxy group, amino group, dimethylamino group, diethylamino group, nitro group, optionally substituted with phenylamino group etc. Triazine.

  Pigment derivatives, anthraquinone derivatives and acridone derivatives having a specific basic group can be synthesized by various synthetic routes. For example, after introducing a substituent represented by the following formulas (7) to (10) into an organic pigment, anthraquinone or acridone, it reacts with the substituent and is represented by the general formulas (1) to (4). Amine components that form substituents such as N, N-dimethylaminopropylamine, N-methylpiperazine, diethylamine or 4- [4-hydroxy-6- [3- (dibutylamino) propylamino] -1,3 It can be obtained by reacting 5-triazin-2-ylamino] aniline or the like.

有機顔料がアゾ系顔料である場合は、一般式（１）〜（４）で表される置換基をあらかじめジアゾ成分またはカップリング成分に導入し、その後カップリング反応を行うことによって塩基性基を有するアゾ系顔料誘導体を製造することもできる。

When the organic pigment is an azo pigment, a basic group is introduced by introducing a substituent represented by the general formulas (1) to (4) into a diazo component or a coupling component in advance and then performing a coupling reaction. An azo pigment derivative having the same can also be produced.

Triazine derivatives having a specific basic group can also be synthesized by various synthetic routes. For example, starting from cyanuric chloride, an amine component that forms a substituent represented by the general formulas (1) to (4) on at least one chlorine of cyanuric chloride, such as N, N-dimethylaminopropylamine or N It is obtained by reacting methylpiperazine or the like and then reacting the remaining chlorine of cyanuric chloride with various amines or alcohols.

  Examples of the amine component used for forming a specific basic group include dimethylamine, diethylamine, N, N-ethylisopropylamine, N, N-ethylpropylamine, N, N-methylbutylamine, N, N-methylisobutylamine, N, N-butylethylamine, N, N-tert-butylethylamine, diisopropylamine, dipropylamine, N, N-sec-butylpropylamine, dibutylamine, disec-butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine, diisoamylamine, dihexylamine, di (2-ethylhexyl) amine, dioctylamine, N, N-methyloctadecylamine, didecylamine, diallylamine, N, N-ethyl- 1,2- Methylpropylamine, N, N-methylhexylamine, dioleylamine, distearylamine, N, N-dimethylaminomethylamine, N, N-dimethylaminoethylamine, N, N-dimethylaminoamylamine, N, N-dimethyl Aminobutylamine, N, N-diethylaminoethylamine, N, N-diethylaminopropylamine, N, N-diethylaminohexylamine, N, N-diethylaminobutylamine, N, N-diethylaminopentylamine, N, N-dipropylaminobutylamine, N, N-dibutylaminopropylamine, N, N-dibutylaminoethylamine, N, N-dibutylaminobutylamine, N, N-diisobutylaminopentylamine, N, N-methyl-laurylaminopropylamine, N, N- Tyruhexylaminoethylamine, N, N-distearylaminoethylamine, N, N-dioleylaminoethylamine, N, N-distearylaminobutylamine, piperidine, 2-pipecoline, 3-pipecholine, 4-pipecholine, 2,4- Lupetidine, 2,6-Lupetidine, 3,5-Lupetidine, 3-piperidinemethanol, Pipecolic acid, Isonipecotic acid, Methyl isonicopetinate, Ethyl isicopetinate, 2-piperidineethanol, Pyrrolidine, 3-hydroxypyrrolidine, N-aminoethylpiperidine N-aminoethyl-4-pipecoline, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl-2-pipecoline, N-aminopropyl-4-pipecoline, N-aminopropylmorpholine, N -Methylpiperazine, N-butylpiperazine, N-methylhomopiperazine, 1-cyclopentylpiperazine, 1-amino-4-methylpiperazine, 1-cyclopentylpiperazine and the like.

  In the coloring composition of the present invention, a pigment is sufficiently dispersed in a pigment carrier, and applied to a transparent substrate such as a glass substrate so that the dry film thickness is 0.2 to 2.5 μm to form a filter segment. A solvent can be included to facilitate the process. Examples of the solvent include cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, xylene, ethyl cellosolve, methyl-n amyl ketone, propylene glycol monomethyl ether toluene, Examples include methyl ethyl ketone, ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, petroleum solvent, and the like. These may be used alone or in combination.

In addition, the colored composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity with time of the composition. Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Organic phosphines, phosphites and the like can be mentioned.
The pigment is preferably contained in the coloring composition at a ratio of 1.5 to 7% by weight. Further, the pigment is preferably contained in the final filter segment in a proportion of 10 to 40% by weight, more preferably 20 to 40% by weight, and the remainder substantially consists of a resinous binder provided by the pigment carrier. .

  The coloring composition of the present invention is mixed with coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more and coarse particles by means of centrifugation, sintered filter, membrane filter or the like. It is preferable to remove dust.

The color filter of the present invention comprises at least one red filter segment, at least one green filter segment, and at least one blue filter segment, wherein the at least one red filter segment is for the red color filter of the present invention. It is formed using a coloring composition.
The red filter segment can be formed with a film thickness in the range of 0.2 to 2.5 μm, but in order to obtain an appropriate spectral characteristic while maintaining a preferable pigment concentration, the thickness is 0.5 to 2.5 μm. The most preferable range is 0.7 to 2.3 μm.

  The blue filter segment can be formed using a normal blue coloring composition. Examples of the blue coloring composition include C.I. I. Blue pigments such as Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, and 64 can be used. Blue coloring compositions include C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50, and other purple pigments can be used in combination.

  Moreover, a green filter segment can be formed using a normal green coloring composition. Examples of the green coloring composition include C.I. I. This is a composition obtained using a green pigment such as Pigment Green 7, 10, 36, 37. The green coloring composition includes C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180 , 181, 182, 185, 187, 188, 193, 194, 198, 199, 213, 214 and the like can be used in combination.

The color filter of the present invention can be produced by, for example, forming a red filter segment on a transparent substrate using the colored composition of the present invention by a printing method or a photolithography method.
As the transparent substrate, a glass plate or a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate is used.

  The formation of each color filter segment by the printing method can be patterned simply by repeating the printing and drying of the colored composition prepared as the above various printing inks. Therefore, the color filter manufacturing method is low-cost and excellent in mass productivity. ing. Further, fine patterns having high dimensional accuracy and smoothness can be printed by the development of printing technology. In order to perform printing, it is preferable that the ink does not dry and solidify on the printing plate or on the blanket. Control of ink fluidity on a printing press is also important, and ink viscosity can be adjusted with a dispersant or extender pigment.

When each color filter segment is formed by photolithography, the colored composition prepared as the solvent development type or alkali development type color resist is applied on a transparent substrate, such as spray coating, spin coating, slit coating, roll coating, etc. By a method, it applies so that a dry film thickness may be set to 0.2-5 micrometers. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Then, after immersing in a solvent or alkali developer or spraying the developer by spraying or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate the polymerization of the colored resist, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the above printing method can be manufactured.

In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.
In order to increase the UV exposure sensitivity, after coating and drying the above colored resist, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Then, ultraviolet exposure can be performed.

  The color filter of the present invention can be produced by an electrodeposition method, a transfer method, or the like in addition to the above method, but the colored composition of the present invention can be used in any method. The electrodeposition method is a method for producing a color filter by using a transparent conductive film formed on a transparent substrate and forming each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. is there. The transfer method is a method in which a color filter layer is formed in advance on the surface of a peelable transfer base sheet, and this color filter layer is transferred to a desired transparent substrate.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples, “parts” means “parts by weight”.
First, a production example of an acrylic resin solution used in the examples, a salt milling treatment example of a pigment, and a production example of a pigment dispersion will be described.

(Preparation of acrylic resin solution)
A reaction vessel was charged with 800 parts of cyclohexanone, heated to 100 ° C. while injecting nitrogen gas into the vessel, and a mixture of the following monomer and thermal polymerization initiator was added dropwise at the same temperature over 1 hour to carry out a polymerization reaction.
Styrene 60.0 parts Methacrylic acid 60.0 parts Methyl methacrylate 65.0 parts Butyl methacrylate 65.0 parts Azobisisobutyronitrile 10.0 parts After dropping and further reacting at 100 ° C. for 3 hours, azobisisobuty A solution obtained by dissolving 2.0 parts of nitrile in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour to obtain an acrylic resin solution having a weight average molecular weight of about 40,000. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. To prepare an acrylic resin solution.

(Manufacture of yellow salt milled pigment)
250 g of yellow pigment (CI pigment yellow 139, manufactured by BASF "Pariol Yellow D1819"), 700 g of sodium chloride, maleic resin ("Marquide No. 3002" manufactured by Arakawa Chemical Co., acid value: 100) 107 g and polyethylene 160 g of glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) 160 g was charged into a stainless gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 3 hours. Next, this mixture was poured into about 3 liters of warm water, heated to about 80 ° C. and stirred for about 1 hour with a high speed mixer to form a slurry, filtered, washed with water to remove sodium chloride and solvent, It was dried in a hot air oven at 0 ° C. for about 24 hours to obtain “PYY139 salt milled pigment”.

(Production of red pigment dispersion)
After the mixture having the following composition was uniformly stirred and mixed, the mixture was dispersed with an Eiger mill for 10 hours using zirconia beads having a diameter of 0.5 mm, and then filtered with a 1.0 μm filter to obtain a red pigment dispersion (“PR” .254 dispersion ").
C. I. pigment red 254 (“Chromophthal Red B-CF” manufactured by Ciba Specialty Chemicals Co., Ltd.) 8.0 parts Dispersant (“Solspers 20000” manufactured by Zeneca) 1.0 part acrylic resin solution 40.0 parts 48.0 parts of cyclohexanone (production of yellow pigment dispersion)
A mixture having the following composition was stirred and mixed uniformly, and then dispersed with an Eiger mill for 10 hours using zirconia beads having a diameter of 0.5 mm, and then filtered with a 1.0 μm filter to obtain a yellow pigment dispersion (“PY .139 Sol Trimmed Product Dispersion ").
P. Y. 139 salt milled pigment 8.0 parts dispersant (“Solsper's 20000” manufactured by Zeneca) 1.0 part acrylic resin solution 40.0 parts cyclohexanone 48.0 parts (production of red salt milled pigment)
C. instead of Pariotello D1819 for the production of salt milled pigments I. Pigment red 48: 1 (“Rionol Red 2BFG3300” manufactured by Toyo Ink Manufacturing Co., Ltd.) was used to produce “PR 48: 1 salt milled pigment” in the same manner as in the production example of the salt milled pigment. Produced.

(Production of red pigment dispersion)
After using the obtained “PR 48: 1 salt milled pigment”, the mixture was uniformly stirred and mixed with the following composition, and then dispersed with an Eiger mill for 10 hours using zirconia beads having a diameter of 0.5 mm. And filtered through a 1.0 μm filter to prepare a red pigment dispersion (“PR 48: 1 salt milled product dispersion”).
P. R. 48: 1 salt milled pigment 8.0 parts dispersant (“Solsper's 20000” manufactured by Zeneca) 1.0 part acrylic resin solution 40.0 parts cyclohexanone 48.0 parts

<Example>
Using the obtained “PR.254 dispersion”, “P.Y.139 sol-trimmed product dispersion”, and “PR.48: 1 salt milled product dispersion”, the following: The composition mixture was stirred and mixed so as to be uniform, and then filtered through a 0.6 μm filter to obtain a red resist.
P. R. 254 dispersion 30.0 parts P.I. Y. 139 Salt milled product dispersion 12.0 parts P.I. R. 48: 1 salt milled product dispersion 18.0 parts acrylic resin solution 10.0 parts trimethylolpropane triacrylate 3.0 parts ("NK ester ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.)
Photopolymerization initiator ("Irgacure 907" manufactured by Ciba Geigy) 1.8 parts sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.2 parts cyclohexanone 25.0 parts <Comparative Example 1>
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 0.6 μm filter to obtain a red resist.
P. R. 254 dispersion 36.0 parts P.I. Y. 139 Salt milled product dispersion 21.0 parts P.I. R. 48: 1 salt mill treated product dispersion 3.0 parts acrylic resin solution 10.0 parts trimethylolpropane triacrylate 3.0 parts ("NK ester ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.)
Photopolymerization initiator ("Irgacure 907" manufactured by Ciba Geigy Co., Ltd.) 1.8 parts sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.2 parts cyclohexanone 25.0 parts <Comparative Example 2>
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 0.6 μm filter to obtain a red resist.
P. R. 254 dispersion 36.0 parts P.I. Y. 139 Salt milled product dispersion 24.0 parts Acrylic resin solution 10.0 parts Trimethylolpropane triacrylate 3.0 parts ("NK ester ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.)
Photopolymerization initiator ("Irgacure 907" manufactured by Ciba Geigy Co., Ltd.) 1.8 parts sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.2 part cyclohexanone 25.0 parts It was applied to a glass substrate with a spin coater, dried, exposed, developed, and dried again to obtain a color filter of the present invention having a thickness of 1.0 μm. When the transmittance of the obtained color filter was measured with a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.), the transmittance was 3% or less in the wavelength range of 430 nm to 560 nm. The 50% transmission wavelength is 583 nm, and the transmittance at 600 nm is 93%. I. It was possible to obtain a red color filter having a high color purity without an undesirable peak in the wavelength range of 520 nm to 540 nm peculiar to pigment red 254. The results are shown in Table 1 and FIG.

比較例１、比較例２により得られたカラーレジストを用いて、実施例と同様にしてカラーフィルタを得た。得られたカラーフィルタの透過率を顕微分光光度計（オリンパス光学社製「ＯＳＰ−ＳＰ１００」）を用いて、分光透過率の測定をした。

Using the color resist obtained in Comparative Example 1 and Comparative Example 2, a color filter was obtained in the same manner as in the example. The transmittance of the obtained color filter was measured for the spectral transmittance using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.).

The color filter using the color resist obtained in Comparative Example 1 has a transmittance at 450 nm of 1.5%, a transmittance at 530 nm of 3.9%, a transmittance at 560 nm of 1.0%, and 50%. The transmission wavelength was 582 nm, and the transmittance at 600 nm was 86.0%. Further, the color filter using the color resist obtained in Comparative Example 2 has a transmittance at 450 nm of 0.7%, a transmittance at 530 nm of 4.5%, and 560 n.
The transmittance at m was 1.1%, the 50% transmission wavelength was 582 nm, and the transmittance at 600 nm was 86.0%. The resulting spectral curve is C.I. I. Pigment red 254 had a spectrum with an undesirable peak in the 520 nm to 540 nm wavelength region. The results are shown in Table 1 and FIG.

  As is clear from the above, the spectral transmittance in the wavelength region of 520 nm to 540 nm of the red filter segment of the color filter of the present invention is greatly reduced as compared with the color filters of Comparative Example 1 and Comparative Example 2. It can be seen that a color filter having a spectral transmittance with good color separation was obtained by the present invention.

  The coloring composition for a red color filter of the present invention includes C.I. I. Pigment red 254 and C.I. I. Pigment Red 48: 1 and C.I. I. By using a coloring composition containing Pigment Yellow 139, it can be applied to a color filter having excellent color reproducibility and excellent color separation used for a color liquid crystal display, a color image pickup tube element and the like.

It is explanatory drawing of the spectral transmittance of an Example and Comparative Examples 1 and 2. FIG.

Claims (3)

  As a red pigment, at least C.I. I. Pigment red 254 and C.I. I. Pigment Red 48: 1, C.I. I. Pigment Yellow 139, C.I. I. Pigment red 254 and C.I. I. Pigment red 48: 1 and C.I. I. The pigment blend ratio (wt%) of CI Pigment Yellow 139 is C.I. I. Pigment Red 254 is 5 to 70, C.I. I. Pigment Red 48: 1 is 10 to 50, C.I. I. Pigment Yellow 139 is 3 to 50, and a coloring composition for a red color filter.   The color filter composition according to claim 1, comprising at least one red filter segment, at least one green filter segment, and at least one blue filter segment, wherein the at least one red filter segment is formed using the coloring composition for red color filter according to claim 1. A color filter characterized by that.   When the film thickness of the red filter segment is in the range of 0.5 to 2.5 μm, the spectral transmittance characteristic is 3% or less in the wavelength region of 430 nm to 560 nm, and the spectral transmittance is 50%. The color filter according to claim 2, wherein the wavelength is between 575 nm and 590 nm, and the spectral transmittance at a wavelength of 600 nm is 80% or more.

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