JP5659919B2 - Photosensitive coloring composition and color filter using the same - Google Patents

Description

  The present invention relates to a photosensitive coloring composition, and in particular, a photosensitive coloring composition used for manufacturing a color filter used for a color liquid crystal display device, a color image pickup tube element, etc., particularly a thin film transistor (TFT) type color. A photosensitive coloring composition for use in a color filter of a color filter on array system (hereinafter sometimes abbreviated as COA system), comprising a filter segment having a colored layer formed on a driving substrate of a liquid crystal display device, and The present invention relates to a color filter formed using a photosensitive coloring composition.

  The color liquid crystal display device controls the amount of light passing through the second polarizing plate by controlling the degree of polarization of the light that has passed through the first polarizing plate by the liquid crystal layer sandwiched between the two polarizing plates. This is a display device that performs display. By providing a color filter between these two polarizing plates, color display is possible, and in recent years it has come to be used in televisions, personal computer monitors, etc., so there is a demand for higher brightness and higher contrast for color filters. Is growing.

  The color filter is formed by forming a colored layer directly or through a passivation film such as a silicon nitride film on a transparent substrate such as glass or a driving substrate on which a thin film transistor (TFT) is disposed. It consists of fine band (striped) filter segments of different colors or more arranged in parallel or intersecting, or fine filter segments arranged in a fixed arrangement. The filter segments are as fine as several microns to several hundreds of microns, and are regularly arranged in a predetermined arrangement for each hue.

  The liquid crystal used in such a liquid crystal display device is easily affected by the electrical characteristics of members such as a color filter inherent in the liquid crystal display device, and adversely affects liquid crystal orientation disorder and switching performance due to liquid crystal contamination. Display defects may become a problem. In order to solve such a problem, the color layer of the color filter is required to have insulation, and it is necessary to increase the insulation by increasing the film thickness or to form a color film having a low dielectric constant. In order to solve such a problem, a method of selecting a dielectric loss tangent of two layers obtained by laminating an overcoat layer in a color layer of a green (green) pixel within a specific range has been studied (see Patent Document 1). .

  In particular, a colored layer is formed directly or via a passivation film such as a silicon nitride film on a driving substrate on which a thin film transistor (TFT), which has recently been attracting attention, and a substrate on which the colored layer is formed. In the COA method (see Patent Document 2) in which a transparent electrode for driving a liquid crystal is bonded to a substrate formed by vapor deposition or sputtering (see Patent Document 2), coloring is directly performed on a driving substrate on which a thin film transistor (TFT) is arranged. In order to form a layer, the pixel aperture ratio (aperture ratio) can be greatly increased, so that it is possible to achieve high brightness and low power consumption. There is a problem that it is easily affected by characteristics.

  In order to solve such a problem, the color filter segment is usually formed with a thickness of about 1.6 to 2 μm, whereas in the COA method, it is formed with a thickness of about 3 μm or a film with a higher crosslinking density. In many cases, this is achieved by a method of reducing the influence of the electrical characteristics of the color filter. Furthermore, it is necessary to provide a contact hole for connecting the transparent electrode and the thin film transistor (TFT) in the color filter segment because the thick color filter segment is formed on the thin film transistor (TFT) instead of the insulating layer. For this reason, the photosensitive coloring composition forming the pixel needs to have a resolution superior to that of a normal photosensitive coloring composition. The resolution of the photosensitive coloring composition is generally adjusted by the type and amount of the photopolymerization initiator and monomer, and the photopolymerization initiator and monomer with low sensitivity are selected or the amount is selected. In some cases, it can be improved by adjusting, but on the other hand, the adhesiveness between the photosensitive coloring composition and the glass substrate is lowered due to a decrease in sensitivity, and pattern peeling tends to occur. In addition, a photopolymerization initiator with high sensitivity tends to have a thicker pattern than a mask, and it is difficult to open a minute contact hole. Further, in the COA system, required characteristics with respect to the profile angle (= an angle formed by the pattern cross section with the substrate) are strict, and it is difficult to control the profile angle with the conventional photosensitive coloring composition. That is, it is difficult to satisfy all of the pattern adhesion, contact hole opening, and profile angle.

  In recent years, color filters have been required to have higher transparency and higher density. In order to produce a high-concentration color filter, it is necessary to increase the colorant concentration in the color composition to be used. By increasing the colorant concentration of the color composition, exposure sensitivity and solubility during development, etc. Characteristics that contribute to image formation are relatively lowered. As a result, the solubility of the non-exposed area in the development process deteriorates, and the colored composition in the non-exposed area remains undissolved during development, or the resist remains undissolved on the substrate as a peeled piece. May cause color misregistration. As a result, the quality of the color filter and the yield during production are reduced. Furthermore, liquid crystal is a material with extremely high insulating properties, and when the polar compound remaining in the color filter composition is eluted into the liquid crystal cell, the voltage between the electrodes decreases, leading to a decrease in voltage holding ratio, resulting in display unevenness. Generation | occurrence | production, orientation failure, etc. arise and it becomes the cause of reducing the performance as a liquid crystal display element. Therefore, the coloring composition is required to have insolubility in liquid crystals (this resistance is referred to as voltage holding characteristic, which is an index of electric characteristics representing the display performance of a liquid crystal display element (LCD)).

JP 2004-117537 A JP 2004-94263 A

  The present invention has a high resolution while being a thick film, good adhesion to a glass substrate, excellent solubility in an alkaline developer and voltage holding characteristics, and developability, particularly with a good profile angle. It aims at providing the photosensitive coloring composition which can form a pattern, and a color filter using the same.

  In the present invention, the monomer (C) contains a large amount of at least a polyfunctional monomer (C1) having an acidic group. Further, as a photopolymerization initiator (D), an acetophenone compound and an acyl phosphine oxide compound are used as an acetophenone compound. Compound / acylphosphine oxide-based compound = 60/40 to 90/10 In a photosensitive coloring composition characterized by comprising.

  By using the polyfunctional monomer (C1) having an acidic group, the photosensitive coloring composition configured as described above has excellent adhesion to a glass substrate, excellent solubility in an alkali developer, and high voltage retention characteristics. By using a polyfunctional monomer (C1) having an acidic group and a photopolymerization initiator having a specific ratio, an excellent profile angle pattern can be formed.

  The photosensitive coloring composition of the present invention has a high resolution while being a thick film, good adhesion to a glass substrate, excellent solubility in an alkaline developer and high voltage retention characteristics, and developability. In particular, a photosensitive coloring composition capable of forming a pattern with a particularly good profile angle and a color filter using the same were obtained.

  First, the photosensitive coloring composition of this invention is demonstrated.

  The photosensitive coloring composition of the present invention contains a colorant (A), a resin (B), a monomer (C), and a photopolymerization initiator (D).

<Colorant (A)>
Examples of the red colorant include C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 146, 166, 168, 169, 176, 177, 178, 179, 184, 185, 187, 200, 202, 208, 210, 221, 242, 246, 254, 255, 264, 270, 272, 273, 274, 276, Red pigments such as 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, or 287 are used. Further, basic dyes exhibiting red color, acidic dyes, and salt-forming compounds of these dyes can also be used.

  Red colorants include C.I. I. Pigment Orange 36, 38, 43, 71, or 73, and / or 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, 181 182,185,187,188,193,194,198,199,213,214,218,219,220, or may be used in combination of a yellow pigment 221, and the like. Further, basic dyes exhibiting orange and / or yellow, acid dyes, and salt-forming compounds of these dyes can also be used.

  Examples of the green colorant include C.I. I. Pigment green 7, 10, 36, 37, 58 and the like. Among them, C.I. I. It is preferable to use Pigment Green 58 in that high brightness can be achieved. C. I. Pigment Green 58 is difficult to ensure dispersion stability compared to other pigment types due to its high acidity, but by using the photosensitive coloring composition of the present invention, the crystalline foreign matter of the coating film is also reduced. It is possible to suppress.

  A yellow pigment can be used in combination with the green colorant. Examples of yellow pigments that can be used in combination include 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, Mention may be made of yellow pigments such as 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220 or 221. Further, basic dyes exhibiting yellow, acidic dyes and salt-forming compounds of these dyes can be used in combination.

  Examples of the blue colorant include C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64 or the like can be used. Blue coloring compositions include C.I. I. Purple violet pigments such as CI Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, or 50 can be used in combination. Further, basic dyes exhibiting purple, acidic dyes and salt-forming compounds of these dyes can be used in combination.

(Miniaturization of pigment)
In the present invention, the pigment can be refined by salt milling. The primary particle diameter of the pigment is preferably 20 nm or more because of good dispersion in the colorant carrier. Moreover, since it can form a filter segment with high contrast ratio, it is preferable that it is 100 nm or less. A particularly preferable range is a range of 25 to 85 nm. The primary particle diameter of the pigment was measured by directly measuring the size of the primary particle from an electron micrograph of the pigment using a TEM (transmission electron microscope). Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle diameter of the pigment particles. Next, for 100 or more pigment particles, the volume of each particle is obtained by approximating it to a cube of the obtained particle size, and the volume average particle size is defined as the average primary particle size.

  Salt milling is a process in which a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent is heated using a kneader such as a kneader, two-roll mill, three-roll mill, trimix, ball mill, attritor, or sand mill. Then, after mechanically kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt serves as a crushing aid, and the pigment is crushed using the high hardness of the inorganic salt during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a sharp particle size distribution with a very fine primary particle diameter and a wide distribution range.

  As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by weight, and most preferably 300 to 1000 parts by weight with respect to 100 parts by weight of the pigment, from the viewpoint of both processing efficiency and production efficiency.

  The water-soluble organic solvent functions to wet the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt to be used. However, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety because the temperature rises during salt milling and the solvent is easily evaporated. For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by weight, and most preferably 50 to 500 parts by weight, based on 100 parts by weight of the pigment.

  When the salt is milled, a resin may be added as necessary. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin used is solid at room temperature, preferably insoluble in water, and more preferably partially soluble in the organic solvent. The amount of the resin used is preferably in the range of 5 to 200 parts by weight with respect to 100 parts by weight of the pigment.

<Resin (B)>
The resin is for dispersing a colorant, and is preferably a thermoplastic resin, a thermosetting resin, or the like.
The resin (B) is preferably a resin having a spectral 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. Moreover, when using with the form of an alkali image development type colored resist material, it is preferable to use the alkali-soluble vinyl resin which copolymerized the acidic group containing ethylenically unsaturated monomer. In order to further improve the photosensitivity, an energy ray curable resin having an ethylenically unsaturated active double bond can also be used.

  The weight average molecular weight (hereinafter also referred to as Mw) of the resin (B) is preferably in the range of 10,000 to 100,000, more preferably 10,000 to 80 in order to disperse the colorant (A) preferably. , 000. The number average molecular weight (hereinafter also referred to as Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.

  Further, from the viewpoint of pigment dispersibility, developability, and heat resistance, a carboxyl group that functions as a pigment adsorbing group and an alkali-soluble group during development, an aliphatic group and an aromatic group that function as an affinity group for a pigment carrier and a solvent. The balance is important for pigment dispersibility, developability, and durability, and it is preferable to use a resin having an acid value of 20 to 300 mgKOH / g. When the acid value is less than 20 mgKOH / g, the solubility in the developer is deteriorated, and it may be difficult to form a fine pattern. On the other hand, if it exceeds 300 mgKOH / g, the fine pattern may not remain.

  The resin (B) is preferably used in an amount of 30 parts by weight or more with respect to 100 parts by weight of the colorant (A) from the viewpoint of film formability and various resistances, and has a high colorant concentration and good color characteristics. Since it can be expressed, it is preferably used in an amount of 500 parts by weight or less, more preferably 40 parts by weight or more and 300 parts by weight or less.

(Thermoplastic resin)
Examples of the thermoplastic resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, and polyurethane resin. Polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins.

  Examples of the alkali-soluble resin obtained by copolymerizing an acidic group-containing ethylenically unsaturated monomer include resins having an acidic group such as a carboxyl group and a sulfone group. Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or Examples include isobutylene / (anhydrous) maleic acid copolymer. Among these, at least one resin selected from an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic group, is preferably used because of its high heat resistance and transparency.

  Examples of the energy ray-curable resin having an ethylenically unsaturated active double bond include a resin into which an unsaturated ethylenic double bond is introduced by the following methods (a) and (b).

<Method (a)>
As the method (a), for example, a side chain epoxy group of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having an epoxy group and one or more other monomers is used. Then, the carboxyl group of an unsaturated monobasic acid having an unsaturated elenic double bond is added, and the resulting hydroxyl group is reacted with a polybasic acid anhydride to give an unsaturated ethylenic double bond and a carboxyl group. There is a way to introduce.

  Examples of the unsaturated ethylenic monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, and 3,4-epoxybutyl (meth) acrylate. And 3,4-epoxycyclohexyl (meth) acrylate, which may be used alone or in combination of two or more. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth) acrylate is preferred.

  Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano substituted products, etc. Monocarboxylic acid etc. are mentioned, These may be used independently or may use 2 or more types together.

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., and these may be used alone or in combination of two or more. It doesn't matter. If necessary, use a tricarboxylic anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride to increase the number of carboxyl groups. The group can also be hydrolyzed. Moreover, when an etrahydrophthalic anhydride or maleic anhydride having an unsaturated ethylenic double bond is used as the polybasic acid anhydride, the number of unsaturated ethylenic double bonds can be increased.

As a method similar to the method (a), for example, a side chain of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having a carboxyl group and one or more other monomers. There is a method in which an unsaturated ethylenic monomer having an epoxy group is added to a part of a carboxyl group to introduce an unsaturated ethylenic double bond and a carboxyl group.
<Method (b)>
As the method (b), an unsaturated ethylenic monomer having a hydroxyl group is used, and an unsaturated monobasic acid monomer having another carboxyl group or another monomer is copolymerized. There is a method of reacting an isocyanate group of an unsaturated ethylenic monomer having an isocyanate group with a side chain hydroxyl group of the obtained copolymer.

  Examples of unsaturated ethylenic monomers having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, and glycerol. Examples thereof include hydroxyalkyl (meth) acrylates such as (meth) acrylate or cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. Further, polyether mono (meth) acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the above hydroxyalkyl (meth) acrylate, (poly) γ-valerolactone, (poly) ε-caprolactone And / or (poly) 12-hydroxystearic acid added (poly) ester mono (meth) acrylate can also be used. From the viewpoint of suppressing foreign matter on the coating film, 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferable.

  Examples of the unsaturated ethylenic monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis [(meth) acryloyloxy] ethyl isocyanate, and the like. In addition, two or more types can be used in combination.

(Thermosetting resin)
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.

<Monomer (C)>
It is important that the monomer (C) of the present invention contains at least a polyfunctional monomer (C1) having an acidic group. Use of the polyfunctional monomer (C1) having an acidic group is important because it can achieve both adhesion to a glass substrate, excellent solubility in an alkali developer, and high voltage retention characteristics. In the present invention, the monomer (C) further contains an oligomer in addition to a monomer capable of reacting with ultraviolet rays or heat, and is preferably a polyfunctional monomer / oligomer. It is also preferable to use a monomer / oligomer having no acidic group in combination.

  The blending amount of the monomer (C) is preferably 20 to 50% by weight in 100% by weight of the nonvolatile content of the coloring composition, and is 30 to 45% by weight from the viewpoints of photocurability, resolution and fringe shape. It is more preferable.

(Polyfunctional monomer having an acid group (C1))
As the polyfunctional monomer (C1) having an acid group, for example, an esterified product of a poly (meth) acrylate containing a free hydroxyl group of a polyhydric alcohol and (meth) acrylic acid and a dicarboxylic acid; a polycarboxylic acid; Esterified products with monohydroxyalkyl (meth) acrylates are preferred. Specific examples include monohydroxy oligoacrylates or monohydroxy oligomethacrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, etc. Monoesterified products of carboxylic acids with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, terephthalic acid; propane-1,2,3-tricarboxylic acid (tricarballylic acid), butane-1,2, Tricalic acid such as 4-tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid Free carboxyl group-containing oligoesterified products of boric acids and monohydroxy monoacrylates or monohydroxy monomethacrylates such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, etc. Can be mentioned.
Moreover, as the polyfunctional monomer (C1) having an acid group, a compound represented by the following general formula (1) is also preferable. By using the compound of the general formula (1), the solubility of the photosensitive coloring composition of the present invention in an alkaline developer is improved, and the generation of insoluble matter with the developer is prevented in the development process on the production line. This can prevent clogging of the filter.

General formula (1):
_{(H 2 C = C (R} 1) COO) m -X- (OCOCH (R 1) CH 2 S (R 2) COOH) n
(In the formula, R ¹ is a hydrogen atom or a methyl group, R ² is a hydrocarbon group having 1 to 12 carbon atoms, and X is an (m + n) -valent carbon atom having 3 to 60 carbon atoms. Organic group, m represents an integer of 2 to 18, and n represents an integer of 1 to 3. )

Here, the compound represented by the general formula (1) can be easily obtained, for example, by the following method.
(1) A method of adding a mercapto compound to an obtained compound after esterifying the compound giving an organic group represented by X with acrylic acid to acrylate.
(2) After modifying the compound giving an organic group represented by X with a polyisocyanate compound, the resulting compound is acrylated with an acrylate compound having a hydroxyl group, and then a mercapto compound is added to the obtained compound. Method.
(3) A method in which a compound giving an organic group represented by X is esterified with acrylic acid to be acrylated, then modified with a polyisocyanate compound, and a mercapto compound is added to the obtained compound.

  Examples of the compound giving an organic group represented by X include pentaerythritol, pentaerythritol modified caprolactone, pentaerythritol modified polyisocyanate, dipentaerythritol, dipentaerythritol caprolactone modified, dipentaerythritol polyisocyanate Denatured products can be mentioned.

Examples of the mercapto compound include mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, o-mercaptobenzoic acid, 2-mercaptonicotinic acid, mercaptosuccinic acid, and the like.
The said polyfunctional monomer (C1) which has an acid group can be used individually or in mixture of 2 or more types. The usage-amount of the polyfunctional monomer (C1) which has an acid group in this invention is 20 to 50 weight% in the non volatile matter of 100 weight% of a photosensitive coloring composition, Preferably it is 30 to 45%. In this case, if the amount of the polyfunctional monomer having an acid group is less than 5 parts by weight, the pixel strength or the smoothness of the pixel surface tends to decrease. There is a tendency for the background to be lowered or to become soiled or film remaining in areas other than the area where the pixels are formed.

  The monomer (C) in the present invention includes the polyfunctional monomer (C1) having the acidic group, and may further include a polyfunctional monomer or a monofunctional monomer having no acidic group.

(Polyfunctional monomer)
Examples of the polyfunctional monomer include polyethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, epoxy (meth) acrylate, EO-modified bisphenol A di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyester (meth) acrylate, trimethylolpropane tri (meth) ) Acrylate, tris (acryloxyethyl) isocyanurate, tris (methacryloxyethyl) isocyanurate, dipentaerythritol penta (meth) acrylate, capro Lactone-modified dipentaerythritol hexaacrylate, ditrimethylolpropane tetra (meth) acrylate, epoxy acrylate, and pentaerythritol tetra (meth) acrylate.

(Monofunctional monomer)
Examples of the monofunctional monomer include ω-carboxy-polycaprolactone monoacrylate, ω-carboxy-polycaprolactone monomethacrylate, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxypropyl succinic acid, 2 -Methacryloyloxypropyl succinic acid, methoxyethylene glycol acrylate, methoxyethylene glycol methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxydipropylene Glico Acrylate, methoxydipropylene glycol methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, and commercially available products such as 2-acryloyloxyethyl succinic acid (trade name M-5300) Can be mentioned.

  When the polyfunctional monomer (C1) having an acid group is used in combination with another monomer, these other monomers can be used alone or in combination of two or more. . In that case, the usage-amount of another monomer is 0-90 weight part normally with respect to a total of 100 weight part with the polyfunctional monomer (C1) which has an acid group which is the total monomer amount, Preferably it is 0-50. Parts by weight.

  In the present invention, it is preferable to use a monomer that does not use laprolactone as a raw material from the viewpoint of voltage holding ratio.

<Photopolymerization initiator (D)>
In the present invention, the photopolymerization initiator (D) is used in combination with an acetophenone compound and an acyl phosphine oxide compound, and further in a ratio of acetophenone compound / acyl phosphine oxide compound = 60/40 to 90/10. This is very important. The combination of the photopolymerization initiator and the polyfunctional monomer (C1) having an acid group enables good pattern formation.

  Examples of the acetophenone compound include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, p-dimethylaminoacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1 -One, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpho And linophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, and the like.

  Examples of the acyl phosphine oxide compound include bis (2,4,6-trimethylbenzoyl) phenyl phosphine oxide and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.

  As the photopolymerization initiator (D), a photopolymerization initiator other than the acetophenone compound and the acylphosphine oxide compound can be further used. Specifically, for example, 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime)], O- (acetyl) -N- (1-phenyl-2-oxo -2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine and other oxime compounds, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyldimethyl ketal and other benzoin compounds, benzophenone, benzoylbenzoic acid, Such as methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, etc. Be Zophenone compounds, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, thioxanthone compounds such as 2,4-diethylthioxanthone, 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 (trichloromethyl) -6-styryl-s-triazine, 2, -(Naphtho-1-yl) -4,6-bis (trichloromethyl) -s-tri Gin, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4-trichloro Triazine compounds such as methyl (4′-methoxystyryl) -6-triazine, 2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole 2,2′-bis (o-methoxyphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5 ′ -Imidazole compounds such as tetra (p-methylphenyl) biimidazole, quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone, borate compounds , Carbazole-based compounds, titanocene compounds, and the like. These photopolymerization initiators can be used alone or in combination of two or more at any ratio as required.

  In the present invention, the adhesion can be improved by using a large amount of the photopolymerization initiator (D). Specifically, 3 to 20% by weight is preferable in the nonvolatile content of 100% by weight of the photosensitive coloring composition, and 8 to 13% by weight is more preferable. As characteristics when the photosensitive coloring composition is used for COA, the profile angle is preferably 35 to 65 °, more preferably 40 to 60 °, and the taper length is preferably 7 μm or less. Therefore, when the monomer amount and the initiator amount are within the above ranges, the profile angle and the taper length can be controlled to the required values, and a color filter suitable for the COA method can be manufactured.

<Solvent>
The photosensitive coloring composition of the present invention can contain a solvent. Thus, the colorant is sufficiently dispersed and permeated in the photosensitive coloring composition, and is applied on a substrate such as a glass substrate so as to have a dry film thickness of 0.5 to 5.0 μm to form a filter segment. Can be made easier.

  Examples of the solvent include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2 -Heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl- 1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m- Diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propylacetate , O-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene Glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl Ether, ethylene glycol monohexyl ether, ethylene glycol Methyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, Cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether Dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene Glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, Acetate Amyl, isobutyl acetate, propyl acetate, and a dibasic acid ester and the like.

Among them, from the viewpoint of storage stability of the colored composition of the present invention, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, glycol acetates such as ethylene glycol monoethyl ether acetate, benzyl alcohol, etc. It is preferable to use ketones such as aromatic alcohols and cyclohexanone.
A solvent can be used individually by 1 type or in mixture of 2 or more types. Moreover, since a solvent can adjust a coloring composition to appropriate viscosity and can form the filter segment of the target uniform film thickness, it is used in the quantity of 800-4000 weight part with respect to 100 weight part of coloring agents (A). It is preferable.

<Production of photosensitive coloring composition>
The photosensitive coloring composition of the present invention can be prepared as a solvent developing type or alkali developing type photosensitive coloring composition. The solvent development type or alkali development type photosensitive coloring composition is generally a thermoplastic resin, a thermosetting resin or a photosensitive resin, a photopolymerizable monomer, a photopolymerization initiator, A pigment is dispersed in a composition containing a solvent.

  The photosensitive coloring composition of the present invention comprises a three-roll mill, a two-roll mill by mixing a colorant (A), a resin (B), and, if necessary, a dispersion aid, a solvent, and an additive. The pigment dispersion is prepared by dispersing the pigment in the resin solution by dispersing with a kneader, horizontal sand mill, vertical sand mill, annular bead mill, or attritor, and then photopolymerization is performed. It can be adjusted by mixing the polymerizable monomer (C), the photopolymerization initiator (D), and, if necessary, a solvent, other dispersion aids, additives and the like.

  The photopolymerization initiator (D) may be added at the stage of preparing the photosensitive coloring composition, or may be added later to the prepared photosensitive coloring composition.

(Dispersing aid)
When dispersing the colorant in the colorant carrier, a dispersion aid such as a pigment derivative, a resin-type dispersant, and a surfactant can be appropriately used. Since the dispersion aid is excellent in dispersion of the colorant and has a great effect of preventing reaggregation of the colorant after dispersion, a coloring composition obtained by dispersing the colorant in the pigment carrier using the dispersion aid is used. If so, a color filter with high spectral transmittance can be obtained.

Examples of the dye derivative include a compound in which a basic substituent, an acidic substituent, or an optionally substituted phthalimidomethyl group is introduced into an organic pigment, anthraquinone, acridone, or triazine.
In the present invention, a pigment derivative is particularly preferable, and the structure thereof is a compound represented by the following general formula (2).

P-Ln Formula (2)
(However, P: organic pigment residue, anthraquinone residue, acridone residue or triazine residue, L: basic substituent, acidic substituent, or optionally substituted phthalimidomethyl group, n: 1 It is an integer of ~ 4)

Examples of the organic pigment constituting the organic pigment residue of P include, for example, diketopyrrolopyrrole pigments; azo pigments such as azo, disazo and polyazo; phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine and metal-free phthalocyanine Anthraquinone pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone; quinacridone pigments; dioxazine pigments; perinone pigments; perylene pigments; thioindigo pigments; Indoline pigments; isoindolinone pigments; quinophthalone pigments; selenium pigments; metal complex pigments.

  Examples of the dye derivative are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, and the like. What is currently used can be used, These can be used individually or in mixture of 2 or more types.

  The blending amount of the pigment derivative is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, most preferably 3 parts by weight or more with respect to 100 parts by weight of the colorant (A) from the viewpoint of improving dispersibility. is there. Further, from the viewpoint of heat resistance and light resistance, the amount is preferably 40 parts by weight or less, and most preferably 35 parts by weight or less with respect to 100 parts by weight of the colorant (A).

  The resin-type dispersant has a pigment-affinity part having a property of adsorbing to the colorant and a part compatible with the colorant carrier, and adsorbs to the colorant to disperse the colorant to the colorant carrier. It works to stabilize. Specific examples of resin-type 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 alkylamine salts. , Polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amides formed by reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group, and salts thereof Oil-soluble dispersants such as, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Resin, water-soluble polymer, polyester, modified poly Acrylate-based, 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, not necessarily limited thereto.

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, and 170 manufactured by Big Chemie Japan. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155 or Anti-Terra-U, 203, 204, or BYK- P104, P104S, 220S, 6919, or SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 1600 manufactured by Nihon Lubrizol Corporation, such as Lactimon, Lactimon-WS, or Bykumen. 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc. EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, manufactured by Japan 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 75 4,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

  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 Anionic surfactants such as lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines, and these may be used alone or in admixture of two or more, but are not necessarily limited thereto.

  When a resin-type dispersant and a surfactant are added, the amount is preferably 0.1 to 55 parts by weight, more preferably 0.1 to 45 parts by weight with respect to 100 parts by weight of the colorant. When the blending amount of the resin-type dispersant and the surfactant is less than 0.1 parts by weight, it is difficult to obtain the added effect. When the blending amount is more than 55 parts by weight, the dispersion is affected by an excessive dispersant. May affect.

<Leveling agent>
In order to improve the leveling property of the photosensitive coloring composition on the transparent substrate, it is preferable to add a leveling agent to the photosensitive coloring composition of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by Big Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. In general, the leveling agent is preferably used in an amount of 0.003 to 0.5% by weight in 100% by weight of the photosensitive coloring composition.

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, having a hydrophilic group but low solubility in water, and when added to a coloring composition, It has the characteristics of low surface tension reduction ability, and it is useful to have good wettability to the glass plate despite its low surface tension reduction ability. Those that can sufficiently suppress the chargeability can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. Any of linear block copolymer types in which they are alternately and repeatedly bonded may be used. Dimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. -2207, but is not limited thereto.

  An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used.

  Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium, 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 Examples include esters.

  Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And amphoteric surfactants such as alkyl dimethylamino acetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.

<Curing agent, curing accelerator>
Moreover, in order to assist hardening of a thermosetting resin, the photosensitive coloring composition of this invention may contain the hardening | curing agent, the hardening accelerator, etc. as needed. As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but are not particularly limited to these, and thermosetting resins. Any curing agent may be used as long as it can react with the. Among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine curing agent are preferable. Examples of the curing accelerator include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl). -N, N-dimethylbenzylamine etc.), quaternary ammonium salt compounds (eg triethylbenzylammonium chloride etc.), blocked isocyanate compounds (eg dimethylamine etc.), imidazole derivative bicyclic amidine compounds and salts thereof (eg Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2- D Ru-4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), guanamine compounds (eg, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (eg, 2,4-diamino-6) -Methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine / isocyanuric acid adduct, 2,4-diamino-6 Methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc.) can be used. These may be used alone or in combination of two or more. As content of the said hardening accelerator, 0.01-15 weight part is preferable with respect to 100 weight part of thermosetting resins.

<Other additive components>
The colored composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity of the composition over time. Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained.

  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 storage stabilizer can be used in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the colorant (A).

  Examples of the adhesion improver include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino Ethyl) γ-aminopropyltrie Xisilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Examples include silane coupling agents such as aminosilanes such as -γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the colorant (A).

<Removal of coarse particles>
The photosensitive coloring composition of the present invention is a coarse particle having a size of 5 μm or more, preferably a coarse particle having a size of 1 μm or more, more preferably a coarse particle having a size of 0.5 μm or more. It is preferable to remove the mixed dust. Thus, it is preferable that a coloring composition does not contain a particle | grain of 0.5 micrometer or more substantially. More preferably, it is 0.3 μm or less.
<Color filter>
Next, the color filter using the photosensitive coloring composition of this invention and the manufacturing method of a color filter are demonstrated.

  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. The said filter segment is formed on a base material by apply | coating the photosensitive coloring composition of this invention by a spin coat system or a die coat system.

  As the base material of the color filter, glass plates such as soda-lime glass, low alkali borosilicate glass, non-alkali aluminoborosilicate glass, etc. with high transmittance for visible light, polycarbonate, polymethyl methacrylate, polyethylene terephthalate, etc. A transparent substrate such as a resin plate or a reflective substrate can be used. These substrates may be subjected to appropriate pretreatments such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition and the like. In addition, a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate for driving the liquid crystal after forming the panel.

  If a black matrix is formed in advance before forming the filter segments on these transparent or reflective substrates, the contrast of the liquid crystal display panel can be further increased. Examples of the black matrix include, but are not limited to, a chromium, chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, and a resin film in which a light-shielding agent is dispersed. Alternatively, a thin film transistor (TFT) formed in advance on the transparent substrate or the reflective substrate may be used as a driving substrate for a thin film transistor (TFT) type color liquid crystal display device, and then a filter segment may be formed. By forming the filter segment on the TFT substrate, the aperture ratio of the liquid crystal display panel can be increased and the luminance can be improved.

  Here, a method for forming a colored layer on the TFT substrate will be described. First, on the surface of the TFT substrate or on the surface of the substrate on which a passivation film such as a silicon nitride film is formed on the surface of the driving substrate, a light shielding layer is formed so as to divide the pixel forming portion as necessary. After forming and applying the photosensitive coloring composition on the substrate, pre-baking is performed to evaporate the solvent, thereby forming a coating film. Next, this coating film is exposed through a photomask, and then developed using an alkali developer to dissolve and remove the unexposed portions of the coating film, and then post-baked, whereby the pixel pattern has a predetermined arrangement. An arranged pixel array is formed. The photomask used at that time is provided with a pattern for forming a through hole or a U-shaped depression in addition to a pattern for forming a pixel.

  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. An antifoaming agent or a surfactant can also be added to the developer.

  As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied. Of these, the shower development method or the spray development method is preferable from the viewpoint of achieving both a good profile angle, contact and hole opening.

  In order to increase the UV exposure sensitivity, the photosensitive coloring composition is applied and dried, and then a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to prevent polymerization inhibition due to oxygen. However, it is not preferable to apply a resin or the like on the coating film of the colored composition because it is difficult to open contact holes if the sensitivity is too high because polymerization inhibition is prevented. .

  The dry thickness of the coating thickness when forming the filter segment on the transparent substrate or the reflective substrate is preferably 0.1 to 5 μm, more preferably 0.5 to 3 μm.

  In particular, when the colored composition of the present invention is used in a COA system, insulation is required to prevent crosstalk occurring between the gate electrode and the transparent electrode, and a thick film is preferable. It is preferable to use a film thickness of 0.1 to 10 μm, more preferably 0.5 to 5 μm.

  An overcoat film, a columnar spacer, a transparent conductive film, a liquid crystal alignment film, and the like are formed on the color filter as necessary.

  The color filter is bonded to the counter substrate using a sealant, and after injecting liquid crystal from the injection port provided in the seal part, the injection port is sealed, and if necessary, a polarizing film or a retardation film is placed outside the substrate. A liquid crystal display panel is manufactured by bonding.

  Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically convented bend (OCB). It can be used in a liquid crystal display mode in which colorization is performed using a color filter such as the above.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples, “part” represents “part by weight”, and “%” represents “% by weight”.

  Moreover, the polymerization average molecular weight (Mw) of the acrylic resin was measured by using TSKgel column (manufactured by Tosoh Corporation) and GPC (manufactured by Tosoh Corporation, HLC-8120GPC) equipped with an RI detector using THF as a developing solvent. It is a weight average molecular weight (Mw) in terms of polystyrene.

(Measurement method of acid value)
To 0.5 to 1 part of the resin solution, 80 ml of acetone and 10 ml of water are added and stirred to dissolve uniformly, and a 0.1 mol / L aqueous KOH solution is used as a titrant, and an automatic titrator (“COM-555” Hiranuma Sangyo) The acid value of the resin solution was measured. Then, the acid value per non-volatile content of the resin was calculated from the acid value of the resin solution and the non-volatile content concentration of the resin solution.

  First, a method for producing an acrylic resin solution, a method for preparing a resin-type dispersant solution, and a method for producing a pigment dispersion used in Examples and Comparative Examples will be described.

<Method for producing acrylic resin solution>
70.0 parts of propylene glycol monomethyl ether acetate was charged into a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer in a separable four-necked flask, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. Thereafter, 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.) 7 A mixture of 0.4 part and 0.4 part of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight of 26000. After cooling to room temperature, about 2 parts of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Propylene glycol monomethyl was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. An acrylic resin solution was prepared by adding ether acetate.

<Preparation Method of Resin Type Dispersant Solution>
A commercially available resin type dispersant, “EFKA4300” manufactured by Ciba Japan Co., Ltd., and ethylene glycol monomethyl ether acetate were used to prepare a solution having a nonvolatile content of 40% by weight and used as a resin type dispersant solution.

<Method for producing pigment dispersion>
(Preparation of blue pigment dispersion)
ε-type copper phthalocyanine pigment (CI Pigment Blue 15: 6) (“Heiogen Blue L-6700F” manufactured by BASF) 9.7 parts, dioxazine violet pigment (CI Pigment Violet 23) (“Fast Violet RL” manufactured by Clariant) A mixture of 1.1 parts, 8.3 parts of the resin-type dispersant solution, 18.9 parts of the acrylic resin solution, and 62.0 parts of ethylene glycol monomethyl ether acetate was uniformly stirred and mixed, and then the diameter was 0.5 mm. Using a zirconia bead, the mixture was dispersed for 5 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan), and then filtered with a 5.0 μm filter to prepare a blue pigment dispersion.

(Preparation of red pigment dispersion)
As a pigment component in the preparation of the blue pigment dispersion, 7.9 parts of a diketopyrrolopyrrole pigment (CI Pigment Red 254) (“Irgafour Red B-CF” manufactured by Ciba Japan), a nickel azo complex pigment (CI Pigment Yellow 150) A red pigment dispersion was prepared in the same manner except that it was replaced with 3.0 parts.

(Production of green pigment dispersion)
As a pigment component in the preparation of the blue pigment dispersion, 7.9 parts of a zinc halide phthalocyanine green pigment (CI Pigment Green 58), a nickel azo complex pigment (CI Pigment Yellow 150) (“E4GN” manufactured by LANXESS) 3.0 A green pigment dispersion was produced in the same manner except that the part was replaced with the part.

[Example 1]
Photopolymerization initiator: 1.53 parts by weight of 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone and bis (2, After dissolving 0.27 parts by weight of 4,6-trimethylbenzoyl) -phenylphosphine oxide in 53.35 parts by weight of solvent: ethyl 3-ethoxypropionate, 13.45 parts by weight of acrylic resin solution, monomer: dipenta 2.7 parts by weight of erythritol hexaacrylate, 2.7 parts by weight of a succinic anhydride adduct of a mixture of pentaerythritol triacrylate and dipentaerythritol triacrylate, and 26.0 parts by weight of the pigment dispersion were mixed, and 30 parts were mixed with a disper. After stirring for a minute, the mixture was filtered through a 1 μm filter to obtain a red colored composition.

[Examples 2 to 16 and Comparative Examples 1 to 11]
Except having changed each raw material into the kind and quantity of Tables 1-4, it carried out similarly to Example 1 and the blue, red, or green coloring composition was obtained.

Abbreviations in Tables 1 to 4 are shown below.
Monomer 1: caprolactone-modified dipentaerythritol hexaacrylate (“KAYARAD DPCA-30” manufactured by Nippon Kayaku Co., Ltd.)
Monomer 2: Dipentaerythritol hexaacrylate (“Aronix M-402” manufactured by Toagosei Co., Ltd.)
Monomer 3: Carboxyl group-containing polyfunctional monomer (C1-1): Succinic anhydride adduct of a mixture of pentaerythritol triacrylate and dipentaerythritol triacrylate (“Aronix M-520” manufactured by Toagosei Co., Ltd.) Acid value: 30 mg KOH / g)
Monomer 4: carboxyl group-containing polyfunctional monomer (C1-2): a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate and a succinic acid derivative of dipentaerythritol pentaacrylate (manufactured by Toagosei Co., Ltd.) TO-1382 ”acid value: 29 mg KOH / g)
Monomer 5: carboxyl group-containing polyfunctional monomer (C1-3): a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate and a succinic acid derivative of dipentaerythritol pentaacrylate (manufactured by Toagosei Co., Ltd.) TO-2349 ”acid value: 68 mg KOH / g)
Photopolymerization initiator 1: acetophenone series: 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (manufactured by BASF “ IRGACURE 379 ")
-Photopolymerization initiator 2: Acylphosphine oxide series: Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide ("IRGACURE 819" manufactured by BASF)
Photopolymerization initiator 3: Acetophenone series: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one ("IRGACURE 907" manufactured by BASF)
Photopolymerization initiator 4: Oxime ester series: 1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] (BASF's “IRGACURE OXE 01”)
Solvent 1: Propylene glycol monomethyl ether acetate Solvent 2: Ethyl 3-ethoxypropionate

<Adhesion, resolution, profile angle, taper length>
Using the spin coater, the color filter coloring compositions obtained in the examples and comparative examples were formed on a substrate in which a silicon nitride film was formed on the surface of a TFT liquid crystal driving substrate having a thickness of 100 mm × 100 mm and a thickness of 0.7 mm. The film was coated at a rotational speed such that the film thickness after drying was 3.0 μm, dried under reduced pressure, and then exposed to ultraviolet light using an ultrahigh pressure mercury lamp through a photomask with an integrated light amount of 50 mJ and an illuminance of 20 mW. Thereafter, a 0.2 wt% sodium carbonate aqueous solution was used as a developer, and an uncured portion of the coating film was removed by a shower development method at a developer pressure of 0.1 mPa to remove a regular octagonal through hole with a diameter of 30 μm and a line width of 50 μm. A pattern containing fine lines was formed. Thereafter, post-baking was performed at 230 ° C. for red: 60 minutes, green: 40 minutes, blue: 20 minutes, and an evaluation substrate was prepared.
Using the prepared substrate, adhesion, resolution, and cross-sectional shape were evaluated according to the following criteria.
Moreover, about the thing with bad adhesiveness, resolution and cross-sectional shape evaluation were not performed.
The results are shown in Table 5.

(Adhesion)
Visual evaluation was performed in three stages according to the following criteria. △ ○ is a practical level.
○: No pattern peeling is observed Δ: Pattern peeling is slightly recognized ×: Pattern peeling is recognized

(Resolution)
The hole diameter was measured with analysis software (Image-Pro, manufactured by Planetron Co., Ltd.) using an optical microscope, and evaluated according to the following criteria. △ ○ is a practical level.
○: A hole of 25 μm or more can be formed for a mask hole diameter of 30 μm. Δ: A hole of 15 μm or more to less than 25 μm can be formed for a mask hole diameter of 30 μm. X: A hole of 15 μm or more cannot be formed for a mask hole diameter of 30 μm.

(Profile angle)
Cut the fine line portion of the pattern together with the substrate, and use a scanning electron microscope (SEM) to take a pattern cross-section photograph from the direction of the substrate cut surface at a magnification of 10,000 times. The formed angle (θ) was evaluated. (If the pattern cross section is curved, the angle formed by the substrate and the straight line connecting the outer and substrate contacts)

(Taper length)
Cut the fine line part of the pattern together with the substrate, and use a scanning electron microscope (SEM) to take a cross-sectional picture of the pattern from the direction of the substrate cut surface at a magnification of 10000 times. The distance from the intersection with the substrate when vertically lowered from the portion toward the substrate was evaluated.
○: The distance is less than 7 μm Δ: The distance is 7 μm or more and less than 10 μm x: The distance is 10 μm or more

<Developer solubility>
About the obtained coloring composition for color filters, four coating substrates were produced so that a film thickness might be set to 3.0 micrometers on a 10 cm x 10 cm glass substrate using a spin coater, and the board | substrate dried under reduced pressure was 0.00. It was dissolved in 50 g of a developer composed of a 2% by weight aqueous sodium carbonate solution. The solution was allowed to stand and the presence or absence of a precipitate after one day was confirmed.
○: No sediment even after standing for 1 day x: There is sediment after standing for 1 day

<Voltage holding ratio (VHR)>
Each alkali-developable green resist material was applied to a glass substrate (10 cm × 10 cm) with a spin coater so that the dry film thickness was 1.8 μm and exposed at an exposure amount of 50 mJ / cm ^2. Spray development was carried out with a 0.2 wt% sodium carbonate aqueous solution at 30 ° C. for 30 seconds, followed by baking at 230 ° C. in an oven to obtain a coated substrate of each resist material. After removing 0.05 parts of the resist coating film from the obtained coated substrate, it was immersed in 1.5 parts of liquid crystal (MLC-2041 manufactured by Merck Co., Ltd.), aged in a 120 ° C. oven for 60 minutes, and 4000 rpm. After centrifuging for 15 minutes, a supernatant liquid was collected to prepare a resist extraction liquid crystal sample liquid.

On the other hand, two glass substrates having an ITO transparent electrode with an effective electrode size of 10 mm × 10 mm are arranged facing each other so that the ITO transparent electrode surfaces face each other, and a small cell is produced using a sealing agent so that the cell gap becomes 9 μm. did. A resist-extracted liquid crystal sample solution is injected into the small cell between the cell gaps, a voltage of 5 V is applied at 60 ° C. for 60 μsec, and the cell voltage [V ₁ ] after 16.67 msec has elapsed after the voltage release, Measured with Toyo Technica VHR-1S. The measurement was repeated 5 times, and the measured cell voltages were averaged. And the voltage holding rate (%) was calculated | required from the following formula using the obtained cell voltage.

Voltage holding ratio (%) = ([V ₁ ] / 5) × 100
The evaluation criteria for the voltage holding ratio (%) are as follows. Δ to ◎ are practical levels.
A: 95% or more B: 90% or more and less than 95% Δ: 85% or more and less than 90% x: less than 85% Evaluation results are shown in Table 5.

The color filters formed from the photosensitive coloring compositions of Examples 1 to 16 had better evaluation results than the comparative examples, and were able to achieve both characteristics. In addition, the profile angle is in the optimum range, and a color filter suitable for the COA method was obtained.

Claims (5)

A photosensitive coloring composition comprising a colorant (A), a resin (B), a monomer (C), and a photopolymerization initiator (D),
The monomer (C) includes at least a polyfunctional monomer (C1) having an acidic group,
The monomer (C) is 20 to 45 % by weight in 100% by weight of the nonvolatile content of the photosensitive coloring composition, and the photopolymerization initiator (D) is an acetophenone-based compound and an acylphosphine oxide-based compound. A photosensitive coloring composition comprising an acetophenone compound / acylphosphine oxide compound at a ratio of 60/40 to 90/10.   The photosensitive coloring composition according to claim 1, wherein the acetophenone compound and the acylphosphine oxide compound are contained in an amount of 3 to 20% by weight in 100% by weight of the nonvolatile content of the photosensitive coloring composition.   The photosensitive coloring composition according to claim 1 or 2, wherein the polyfunctional monomer (C1) having an acidic group is contained in an amount of 30 to 60% by weight in 100% by weight of the monomer (C). Color filter characterized by comprising the claims 1-3 filter segment made formed from the photosensitive coloring composition according to any one. A color comprising a filter segment in which a colored layer is formed on a driving substrate of a thin film transistor (TFT) type color liquid crystal display device using the photosensitive coloring composition according to any one of claims 1 to 3. filter.