JP5367956B2 - Photosensitive coloring composition and color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored composition for color filters which inhibits the aggregation of a pigment and has excellent stability of a dispersion, and a high contrast color filter using the same. <P>SOLUTION: The photosensitive colored composition for color filters comprises: a polyester dispersant (S) obtained by reacting a hydroxyl group in a vinyl polymer (a) having two hydroxyl groups at one terminal with an acid anhydride group in an aromatic tetracarboxylic acid anhydride, wherein the vinyl polymer (a) is prepared by radically polymerizing 40-60 wt.% of benzyl methacrylate as an ethylenically unsaturated monomer and 40-60 wt.% of n-butyl methacrylate, based on a total amount of all monomers, in the presence of a compound having two hydroxyl groups and one thiol group within a molecule; a pigment; and a pigment carrier containing an ethylenically unsaturated monomer. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention is obtained using a photosensitive coloring composition for a color filter used for forming a filter segment constituting a color filter used for a color liquid crystal display device and a solid-state imaging device, and the photosensitive coloring composition for the color filter. It relates to a color filter.

  In the liquid crystal display device, a liquid crystal layer sandwiched between two polarizing plates controls the amount of light passing through the first polarizing plate by controlling the degree of polarization of light passing through the first polarizing plate. The type using twisted nematic (TN) type liquid crystal is the mainstream. A liquid crystal display device is capable of color display by providing a color filter between two polarizing plates, and has recently been used in televisions, personal computer monitors, and the like. There is an increasing demand for contrast.

  A color filter has two or more kinds of fine band (striped) filter segments arranged in parallel or intersecting with each other on the surface of a transparent substrate such as glass, or the fine filter segments are arranged in a fixed arrangement. It is made up of arranged ones. 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.

  Generally, in a color liquid crystal display device, a transparent electrode for driving a liquid crystal is formed on a color filter by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is further formed thereon. Yes. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, it is necessary to form them generally at a high temperature of 200 ° C. or higher, preferably 230 ° C. or higher. For this reason, at present, as a method for producing a color filter, a method called a pigment dispersion method using a pigment having excellent light resistance and heat resistance as a colorant is mainly used.

  However, in general, a color filter in which a pigment is dispersed has a problem that the degree of polarization controlled by the liquid crystal is disturbed due to light scattering by the pigment. That is, since light leaks when light must be blocked (OFF state) or transmitted light attenuates when light must be transmitted (ON state), display devices in the ON state and the OFF state There is a problem that the upper luminance ratio (contrast ratio) is low.

  The filter segment is formed by using a color resist coating solution in which an initiator or an ethylenically unsaturated monomer is mixed in the pigment dispersion. To achieve high brightness and high contrast of the color filter, the filter segment is formed. First, it is necessary to prepare a dispersion in which the pigment contained in the filter segment is refined and the refined pigment is stably dispersed in a pigment carrier containing a resin or the like (Patent Document 1 and 2). However, when the aggregation of the pigment is strong and cannot be dispersed, the brightness and contrast ratio of the color filter are reduced by going through the pigment refinement process. Also, when the dispersion stability is low, the aggregation of pigment particles progresses over time, causing the viscosity of the colored composition to increase and poor fluidity. When forming a filter segment, the coating liquid is spin-coated on a glass substrate. A coating film having a uniform film thickness cannot be obtained due to poor spin coatability and leveling failure.

  In order to stabilize dispersions using such fine pigments, dispersion formulation optimization using pigment derivatives and resin-type dispersants has been carried out, and pigment derivatives, resin-type dispersants and binder resins have also been improved. I have been. However, there is an insufficient part to fully demonstrate the performance of recent high-quality fine pigments.

Even when a fine pigment dispersion can be produced and a high-contrast filter segment can be formed, the filter segment is 230 ° C. in the process of forming a color filter (formation of a transparent electrode and an alignment film) as described above. There are some cases where a phenomenon occurs in which the pigment dispersion system collapses and the contrast ratio decreases due to exposure to the above high temperatures.
JP-A-10-130547 JP 2005-181383 A

  Therefore, an object of the present invention is to provide a coloring composition for a color filter that suppresses pigment aggregation and is excellent in dispersion stability, and to provide a high-contrast color filter using the same.

  In the present invention, in the presence of a compound having two hydroxyl groups and one thiol group in the molecule, 40 to 60% by weight of benzyl methacrylate and the whole monomer as an ethylenically unsaturated monomer A hydroxyl group in vinyl polymer (a) having two hydroxyl groups at one end, and an acid anhydride in an aromatic tetracarboxylic acid anhydride, obtained by radical polymerization of 40 to 60% by weight of n-butyl methacrylate. The present invention relates to a photosensitive coloring composition for a color filter, comprising a polyester dispersant (S) obtained by reacting a group, a pigment, and a pigment carrier containing an ethylenically unsaturated monomer.

  Furthermore, this invention relates to the said photosensitive coloring composition for color filters, wherein the weight average molecular weight of a polyester dispersing agent (S) is 7000-10000, and an acid value is 20-60.

  Furthermore, this invention relates to the color filter characterized by providing the filter segment formed from the said photosensitive coloring composition on a transparent substrate.

  Furthermore, the present invention relates to a color filter comprising a black matrix formed from the photosensitive coloring composition on a transparent substrate.

  The photosensitive coloring composition for a color filter of the present invention can provide a coloring composition for a color filter that suppresses aggregation of pigments and has excellent dispersion stability, and a high-contrast color filter using the same.

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

  The photosensitive coloring composition of the present invention comprises 40 to 60% by weight of benzyl as an ethylenically unsaturated monomer in the presence of a compound having two hydroxyl groups and one thiol group in the molecule. Hydroxyl group in vinyl polymer (a) having two hydroxyl groups at one end formed by radical polymerization of methacrylate and 40-60% by weight of n-butyl methacrylate based on the whole monomer, and aromatic tetracarboxylic acid anhydride It comprises a polyester dispersant (S) obtained by reacting an acid anhydride group in the product, a pigment, and a pigment carrier containing an ethylenically unsaturated monomer. In particular, the greatest feature is that it contains the polyester dispersant (S). By using the polyester dispersant (S), it is possible to provide a coloring composition for a color filter that suppresses the aggregation of the pigment and is excellent in the stability of the dispersion, and a high-contrast color filter using the same.

  In still another preferred embodiment of the polyester dispersant (S) according to the present invention, the weight average molecular weight is 7,000 to 10,000.

  The polyester dispersant (S) of the present invention comprises a first step for producing a vinyl polymer (a) having two hydroxyl groups at one end, the vinyl polymer (a) and an aromatic tetracarboxylic acid anhydride. It can be obtained from the second step of reacting.

  First, the first step for producing a vinyl polymer (a) having two hydroxyl groups at one end will be described. The vinyl polymer (a) having two hydroxyl groups at one end is obtained by using the entire monomer as an ethylenically unsaturated monomer in the presence of a compound having two hydroxyl groups and one thiol group in the molecule. It can be obtained by radical polymerization of 40 to 60% by weight of benzyl methacrylate and 40 to 60% by weight of n-butyl methacrylate based on the whole monomer.

  Examples of the compound having two hydroxyl groups and one thiol group in the molecule include 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2- Propanediol (thioglycerin), 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1- Examples include mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, 2-mercaptoethyl-2-ethyl-1,3-propanediol, and the like.

  A compound having two hydroxyl groups and one thiol group in the molecule is mixed with an ethylenically unsaturated monomer and optionally a polymerization initiator in accordance with the molecular weight of the target vinyl polymer (a). The vinyl polymer (a) can be obtained by heating. Preferably, bulk polymerization or solution polymerization is performed using a compound having two hydroxyl groups and one thiol group in the molecule of 1 to 30 parts by weight per 100 parts by weight of the ethylenically unsaturated monomer. The reaction temperature is 40 to 150 ° C., preferably 50 to 110 ° C., and the reaction time is 3 to 30 hours, preferably 5 to 20 hours.

  In the polymerization, 0.001 to 5 parts by weight of a polymerization initiator can be used with respect to 100 parts by weight of the ethylenically unsaturated monomer. As the polymerization initiator, azo compounds and organic peroxides can be used. Examples of the azo compounds include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile), 2 , 2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate) 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), 2,2′-azobis [2- (2-imidazolin-2-yl) Propane] and the like. Examples of organic peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxy Examples thereof include dicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, and diacetyl peroxide. These polymerization initiators can be used alone or in combination of two or more.

  In the case of solution polymerization, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone and the like are used as the polymerization solvent, but are not particularly limited thereto. These polymerization solvents may be used as a mixture of two or more.

  Next, the second step of reacting the vinyl polymer (a) having two hydroxyl groups at one end with the aromatic tetracarboxylic anhydride will be described. The polyester dispersant (S) of the present invention comprises a hydroxyl group in the vinyl polymer (a) having two hydroxyl groups at one end obtained in the first step, and an anhydride group in the aromatic tetracarboxylic acid anhydride. It is obtained by reacting.

  The aromatic tetracarboxylic anhydride used in the second step is pyromellitic anhydride, ethylene glycol ditrimellitic anhydride ester, propylene glycol ditrimellitic anhydride ester, butylene glycol ditrimellitic anhydride ester 3,3 ′, 4,4′-benzophenone tetracarboxylic acid anhydride, 3,3 ′, 4,4′-biphenylsulfone tetracarboxylic acid anhydride, 1,4,5,8-naphthalene tetracarboxylic acid anhydride 2,3,6,7-naphthalenetetracarboxylic acid anhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic acid anhydride, 3,3 ′, 4,4′-dimethyldiphenylsilanetetracarboxylic acid Anhydride, 3,3 ′, 4,4′-tetraphenylsilanetetracarboxylic anhydride, 1,2,3,4-Frante Lacarboxylic acid anhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide anhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone anhydride, 4,4′- Bis (3,4-dicarboxyphenoxy) diphenylpropane anhydride, 3,3 ′, 4,4′-perfluoroisopropylidenediphthalic anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic anhydride Bis (phthalic acid) phenylphosphine oxide anhydride, p-phenylene-bis (triphenylphthalic acid) anhydride, m-phenylene-bis (triphenylphthalic acid) anhydride, bis (triphenylphthalic acid) -4 , 4′-diphenyl ether anhydride, bis (triphenylphthalic acid) -4,4′-diphenylmethane anhydride, 9,9-bis ( , 4-Dicarboxyphenyl) fluorenic anhydride, 9,9-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluorenic anhydride, 3,4-dicarboxy-1,2,3,4 -Tetrahydro-1-naphthalene succinic anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene succinic anhydride, etc. are mentioned.

  As the catalyst used in the second step, which is the production of the polyester of the present invention, a known catalyst can be used. The catalyst is preferably a tertiary amine compound such as triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1, 5-diazabicyclo- [4.3.0] -5-nonene and the like.

  The polyester dispersant (S) of the present invention can be produced using only the raw materials listed above, but a solvent is used to avoid problems such as high viscosity and non-uniform reaction. preferable. As the solvent used, known solvents can be used. For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, toluene, xylene, acetonitrile and the like can be mentioned. The solvent used for the reaction can be removed by an operation such as distillation after the completion of the reaction, or can be used as a part of the product as it is.

  The polyester dispersant (S) of the present invention can be obtained by reacting a vinyl polymer (a) having two hydroxyl groups at one end and an aromatic tetracarboxylic acid anhydride. The molar ratio of the acid anhydride group in the aromatic tetracarboxylic acid anhydride to the vinyl polymer (a) is preferably (b) / (a) = 0.3 to 1.2, more preferably (b ) / (A) = 0.5 to 1.0, most preferably (b) / (a) = 0.6 to 0.8. When the reaction is carried out under (b) / (a)> 1, the remaining acid anhydride group may be hydrolyzed with a necessary amount of water and used. If it is less than 0.3, the acid anhydride residue as the pigment adsorbing portion may be decreased, and the acid value of the resin may be decreased. On the other hand, if it exceeds 1.2, the polyester will have a high molecular weight, and when used as a colored composition, the interaction between the resins will be strong and the viscosity may increase.

  The reaction temperature is 80 ° C to 180 ° C, preferably 90 ° C to 160 ° C. When the reaction temperature is 80 ° C. or lower, the reaction rate is slow, and when it is 180 ° C. or higher, the carboxyl group undergoes an esterification reaction, which may cause a decrease in acid value or gelation. Ideally, the reaction is stopped until the absorption of the acid anhydride is eliminated by infrared absorption, but the reaction is performed when the acid value of the polyester is in the range of 5 to 200, preferably in the range of 20 to 60. May be stopped.

  The weight average molecular weight of the obtained polyester dispersant (S) is preferably 7000 to 10,000. If the weight average molecular weight is less than 7000, the stability of the photosensitive coloring composition may be lowered. If the weight average molecular weight is more than 10,000, the interaction between the resins becomes strong, and the photosensitive coloring composition may be thickened. . Moreover, as for the acid value of the obtained polyester dispersing agent, 20-60 are preferable. If the acid value is less than 20, the pigment adsorbing ability may be lowered and there may be a problem in pigment dispersibility. If the acid value exceeds 60, the interaction between resins becomes strong and the viscosity of the pigment dispersion composition may be increased.

  The content of the polyester dispersant (S) in the photosensitive coloring composition is preferably 0.01 to 100 parts by weight, more preferably 0.01 to 40 parts by weight, and still more preferably 1 to 100 parts by weight with respect to 100 parts by weight of the pigment. 30 parts by weight. When the content of the polyester dispersant (S) is less than 0.01 parts by weight, the dispersion effect is insufficient, and when it exceeds 100 parts by weight, the dispersibility may be deteriorated.

  As a pigment contained in the photosensitive coloring composition of the present invention, organic or inorganic pigments can be used alone or in admixture of two or more. Among the pigments, pigments having high color developability and high heat resistance, particularly pigments having high heat decomposition resistance are preferred, and organic pigments are usually used. Below, the specific example of the organic pigment which can be used for the photosensitive coloring composition of this invention is shown with a color index number.

  Examples of the red photosensitive coloring composition for forming the red filter segment include C.I. I. Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 97, 122, 123, 146, 149, 168, 177, 178, 179, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 246, 254, 255, Red pigments such as H.264, 272, and 279 can be used. A yellow pigment and an orange pigment can be used in combination with the red photosensitive coloring composition.

  Examples of the yellow photosensitive coloring composition for forming the yellow filter segment include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 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, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 1 Yellow pigments such as 75, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214 can be used.

  Examples of the orange photosensitive coloring composition for forming the orange filter segment include C.I. I. Orange pigments such as Pigment Orange 36, 43, 51, 55, 59, 61, 71, 73 can be used.

  Examples of the green photosensitive coloring composition for forming the green filter segment include C.I. I. Green pigments such as Pigment Green 7, 10, 36, and 37 can be used. A yellow pigment can be used in combination with the green photosensitive coloring composition.

  Examples of the blue photosensitive coloring composition for forming the blue filter segment include C.I. I. Blue pigments such as Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, and 80 can be used. The blue photosensitive coloring composition includes 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.

  Examples of the cyan photosensitive coloring composition for forming the cyan filter segment include C.I. I. Blue pigments such as Pigment Blue 15: 1, 15: 2, 15: 4, 15: 3, 15: 6, 16, and 81 can be used.

  Examples of the magenta color photosensitive coloring composition for forming the magenta color filter segment include C.I. I. Pigment Violet 1, 19, C.I. I. Purple pigments such as Pigment Red 81, 144, 146, 177, 169, and red pigments can be used. A yellow pigment can be used in combination with the magenta photosensitive coloring composition.

  Examples of the black photosensitive coloring composition for forming the black matrix include carbon black, aniline black, anthraquinone black pigment, perylene black pigment, specifically C.I. I. Pigment Black 1, 6, 7, 12, 20, 31, etc. can be used. For the black photosensitive coloring composition, a mixture of a red pigment, a blue pigment, and a green pigment can also be used. As the black pigment, carbon black is preferable from the viewpoint of price and light shielding properties, and the carbon black may be surface-treated with a resin or the like. Moreover, in order to adjust a color tone, a blue pigment and a purple pigment can be used together in a black photosensitive coloring composition.

Carbon black having a specific surface area of 50 to 200 m ² / g by the BET method is preferable from the viewpoint of the shape of the black matrix. When carbon black having a specific surface area of less than 50 m ² / g is used, the black matrix shape is deteriorated. When carbon black of more than 200 m ² / g is used, the dispersion aid is excessively adsorbed on the carbon black. This is because it is necessary to add a large amount of a dispersion aid in order to express various physical properties.

  Carbon black preferably has an oil absorption of dibutyl phthalate (hereinafter referred to as “DBP”) of 120 ml / 100 g or less from the viewpoint of sensitivity. Furthermore, it is preferable that the average primary particle diameter of carbon black is 20-50 nm. Carbon black having an average primary particle diameter of less than 20 nm is difficult to disperse at a high concentration, and it is difficult to obtain a photosensitive black composition having good stability over time. This is because the matrix shape may be deteriorated.

  Inorganic pigments include barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean [red iron (III) oxide], cadmium red, ultramarine, bitumen, chromium oxide green, cobalt green, amber, titanium black. Examples thereof include metal oxide powders such as synthetic iron black, titanium oxide, and iron tetroxide, metal sulfide powders, and metal powders. Inorganic pigments are used in combination with organic pigments in order to ensure good coatability, sensitivity, developability and the like while maintaining a balance between saturation and lightness. The photosensitive coloring composition of the present invention may contain a dye within a range that does not reduce heat resistance for color matching.

  The pigment carrier containing an ethylenically unsaturated monomer contained in the photosensitive coloring composition for a color filter of the present invention is an ethylenically unsaturated monomer alone or an ethylenically unsaturated monomer and a transparent resin. Consists of a mixture. In the present invention, the ethylenically unsaturated monomer means a compound having an ethylenically unsaturated double bond that is cured by irradiation with active energy rays to produce a transparent resin, Includes a low polymer having an average molecular weight of less than 1000, generally called an oligomer, and having an ethylenically unsaturated double bond.

  Examples of the ethylenically unsaturated monomer include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, and 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, neope Nylglycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, epoxy (meth) acrylate, urethane acrylate and other acrylic esters and methacrylic acid Esters, (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, etc. It is done. These can be used alone or in admixture of two or more.

  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. Examples of the transparent resin include thermoplastic resins, thermosetting resins, and photosensitive resins.

  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, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene, 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 photosensitive resin, a (meth) acrylic compound or cinnamic acid having a reactive substituent such as an isocyanate group, an aldehyde group or an epoxy group on a polymer having a reactive substituent such as a hydroxyl group, a carboxyl group or an amino group is used. Resins in which a photocrosslinkable group such as a (meth) acryloyl group or a styryl group is introduced into the polymer by reaction are used. Further, a polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is half-esterified with a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. A modified version is also used.

  Moreover, when forming a filter segment by alkali development using the photosensitive coloring composition for color filters of the present invention, the pigment carrier preferably contains an alkali-soluble non-photosensitive resin. The alkali-soluble non-photosensitive resin is a resin that dissolves in an alkaline aqueous solution and does not crosslink with radicals. For example, the weight-average molecular weight having an acidic functional group such as a carboxyl group or a sulfone group is 1,000 to 500,000, preferably 5,000 to 100,000. These resins are mentioned. Specific examples of the alkali-soluble non-photosensitive resin include an acrylic resin having an acidic functional group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / (anhydrous) maleic acid copolymer, and a styrene / styrene sulfone. Examples thereof include an acid copolymer, an ethylene / (meth) acrylic acid copolymer, and an isobutylene / (anhydrous) maleic acid copolymer. Among them, at least one selected from an acrylic resin having an acidic functional group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / (anhydrous) maleic acid copolymer, and a styrene / styrene sulfonic acid copolymer. Resins, particularly acrylic resins having an acidic functional group, are preferably used because of their high heat resistance and transparency.

  The photosensitive coloring composition of the present invention comprises a pigment composition composed of a pigment or two or more pigments in a three-roll mill, two-roll mill, sand mill, kneader in the pigment carrier and solvent together with the polyester dispersant (S). It can be produced by finely dispersing using various dispersing means such as an attritor. Moreover, the photosensitive coloring composition containing 2 or more types of pigments can also be manufactured by mixing each pigment separately finely dispersed in a pigment carrier and a solvent. When the pigment is dispersed in the pigment carrier and the solvent, a dispersion aid such as a resin-type pigment dispersant, a surfactant, and a pigment derivative can be appropriately contained. Since the dispersion aid is excellent in dispersing the pigment and has a great effect of preventing re-aggregation of the pigment after dispersion, a photosensitive coloring composition obtained by dispersing the pigment in a pigment carrier and a solvent using the dispersion aid. When used, a color filter excellent in transparency can be obtained.

  The dispersion aid can be used in an amount of 0.1 to 40 parts by weight, preferably 0.1 to 30 parts by weight, with respect to 100 parts by weight of the pigment in the coloring composition.

  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 adsorbs to the pigment to stabilize the dispersion of the pigment on the pigment carrier. It works. 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 alkyleneimines) 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 polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, lauryl sulfate monoethanolamine, lauryl Anionic surfactants such as triethanolamine sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate;
Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate;
Chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts;
Examples include alkylbetaines such as alkyldimethylaminoacetic acid betaine, and amphoteric surfactants such as alkylimidazoline, and these can be used alone or in admixture of two or more.

  The photosensitive coloring composition for a color filter of the present invention is further selected from the group consisting of a pigment derivative having a basic group, an anthraquinone derivative having a basic group, an acridone derivative having a basic group, and a triazine derivative having a basic group. It is preferable to contain at least one basic derivative. The pigment derivative is obtained by introducing a specific substituent into the organic pigment residue described in the color index. In the present invention, a pigment derivative having a basic group can be used. By including a basic derivative, a pigment that is difficult to disperse without a basic derivative (particularly, in the case of an organic pigment) is preferable because a pigment composition excellent in dispersibility, fluidity, and storage stability can be obtained. With the synergistic effect of the polyester dispersant (S) and the basic derivative, the pigment can be effectively made into a pigment composition excellent in dispersibility, fluidity and storage stability.

  The basic derivative of the present invention is selected from the group of an anthraquinone derivative having a basic group, an acridone derivative having a basic group, and a triazine derivative having a basic group. The basic group of the basic derivative of the present invention is at least one selected from the group represented by the following general formulas (1), (2), (3) and (4).

  General formula (1)

一般式（２）

General formula (2)

一般式（３）

General formula (3)

式（４）

Formula (4)

一般式（５）

General formula (5)

一般式（６）

General formula (6)

In the general formulas (1) to (6),
X, X ¹ and X ² represent —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ — or a direct bond.

  m represents an integer of 1 to 10.

R ¹ , R ² Each independently represents an optionally substituted alkyl group, alkenyl group, or phenyl group. R ¹ and R ² may be combined to form a heterocyclic ring. However, the heterocycle may contain further nitrogen, oxygen or sulfur atoms.

R ³ Represents an alkyl group, an alkenyl group or a phenyl group which may be substituted.
R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represents a hydrogen atom, an optionally substituted alkyl group, an alkenyl group or a phenyl group.

Y represents —NR ⁸ —Z—NR ⁹ — or a direct bond.

R ⁸ and R ⁹ each independently represents a hydrogen atom, an optionally substituted alkyl group, an alkenyl group or a phenyl group.

  Z represents an alkylene group, an alkenylene group, or a phenylene group, which may be substituted.

  P represents a substituent represented by the general formula (5) or a substituent represented by the general formula (6).

  Q represents a hydroxyl group, an alkoxyl group, a substituent represented by the general formula (5) or a substituent represented by the general formula (6).

  Examples of the amine component used for forming the substituents represented by the general formulas (1) to (4) include dimethylamine, diethylamine, methylethylamine, N, N-ethylisopropylamine, N, N-ethyl. Propylamine, N, N-methylbutylamine, N, N-methylisobutylamine, N, N-butylethylamine, N, N-tert-butylethylamine, diisopropylamine, dipropylamine, N, N-sec-butylpropylamine , Dibutylamine, di-sec-butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine, diisoamylamine, dihexylamine, dicyclohexylamine, di (2-ethylhexyl) amine, dioctylamine, N, N-methyloctadeci Amine, didecylamine, diallylamine, N, N-ethyl-1,2-dimethylpropylamine, N, N-methylhexylamine, dioleylamine, distearylamine, N, N-dimethylaminomethylamine, N, N-dimethylamino Ethylamine, N, N-dimethylaminoamylamine, N, N-dimethylaminobutylamine, 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-diisobutylaminopen Ruamine, N, N-methyl-laurylaminopropylamine, N, N-ethylhexylaminoethylamine, N, N-distearylaminoethylamine, N, N-dioleylaminoethylamine, N, N-distearylaminobutylamine, Piperidine, 2-Pipecoline, 3-Pipecoline, 4-Pipecoline, 2,4-Lupetidine, 2,6-Lupetidine, 3,5-Lupetidine, 3-Piperidinmethanol, Pipecolic acid, Isonipecotic acid, Methyl isonicopetic acid, Isonicopetic acid Ethyl, 2-piperidineethanol, pyrrolidine, 3-hydroxypyrrolidine, N-aminoethylpiperidine, N-aminoethyl-4-pipecholine, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl-2-pipecholine, -Aminopropyl-4-pipecholine, N-aminopropylmorpholine, N-methylpiperazine, N-butylpiperazine, N-methylhomopiperazine, 1-cyclopentylpiperazine, 1-amino-4-methylpiperazine, 1-cyclopentylpiperazine, etc. Can be mentioned.

  Examples of organic dyes constituting pigment derivatives having a basic group include diketopyrrolopyrrole dyes, azo dyes such as azo, disazo, polyazo, phthalocyanine dyes, diaminodianthraquinone, anthrapyrimidine, flavantrons, anthanthrones. Anthraquinone dyes such as indanthrone, pyranthrone, violanthrone, quinacridone dyes, dioxazine dyes, perinone dyes, perylene dyes, thioindigo dyes, isoindoline dyes, isoindolinone dyes, quinophthalone dyes, sulene dyes It is a dye such as a dye or a metal complex dye. In addition, anthraquinone derivatives having a basic group and acridone derivatives having a basic group include alkyl groups such as methyl and ethyl groups, amino groups, nitro groups, hydroxyl groups or methoxy groups, alkoxy groups such as ethoxy groups, chlorine, etc. It may have a substituent such as halogen.

  Triazines constituting triazine derivatives having basic groups are alkyl groups (methyl group, ethyl group, butyl group, etc.), amino groups, alkylamino groups (dimethylamino group, diethylamino group, dibutylamino group, etc.), nitro Group, hydroxyl group, alkoxy group (methoxy group, ethoxy group, butoxy group, etc.), halogen (chlorine, bromine, etc.), phenyl group (alkyl group, amino group, alkylamino group, nitro group, hydroxyl group, alkoxy group, halogen, etc.) And a substituent such as a phenylamino group (which may be substituted with an alkyl group, amino group, alkylamino group, nitro group, hydroxyl group, alkoxy group, halogen, etc.) It is also a good 1,3,5-triazine.

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

Formula (7) —SO ₂ Cl
Formula (8) -COCl
Formula (9) —CH ₂ NHCOCH ₂ Cl
Equation (10) -CH ₂ Cl

  During the reaction of the formulas (7) to (10) and the amine component, a part of the formulas (7) to (10) may be hydrolyzed so that chlorine is substituted with a hydroxyl group. In that case, the formula (7) and the formula (8) are respectively a sulfonic acid group and a carboxylic acid group, but both may be a free acid, or a salt with a monovalent metal or a monoamine as described above. There may be.

  Further, when the organic dye is an azo dye, the substituent represented by the general formulas (1) to (4) is introduced into the diazo component or the coupling component in advance, and then the coupling reaction is performed, thereby performing the azo pigment. Derivatives can also be produced.

  The triazine derivative having a basic group of the present invention can be synthesized by various synthetic routes. For example, an amine component starting from cyanuric chloride and forming 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 can be obtained by reacting methylpiperazine or the like and then reacting the remaining chlorine of cyanuric chloride with various amines or alcohols.

  In the photosensitive coloring composition for a color filter of the present invention, the amount of the basic derivative is preferably 1 to 50 parts by weight, more preferably 3 to 30 parts by weight, and most preferably 5 to 25 parts by weight based on 100 parts by weight of the pigment. Parts by weight. When the basic derivative is less than 1 part by weight relative to 100 parts by weight of the pigment, the dispersibility may be deteriorated, and when it exceeds 50 parts by weight, the heat resistance and light resistance may be deteriorated.

  The photosensitive coloring composition for a color filter of the present invention is mixed with various solvents, resins, additives, etc. as necessary, and dispersed in a horizontal sand mill, vertical sand mill, annular bead mill, attritor, etc. A pigment dispersion obtained by dispersing the product in a varnish can be prepared. Pigments, basic derivatives, acrylic pigment dispersants, other resins, and additives may be dispersed after mixing all components, but initially only the pigment and basic derivative, or basic derivatives And only the acrylic pigment dispersant, or only the pigment, the basic derivative, and the acrylic pigment dispersant may be dispersed, and then another component may be added and dispersed again.

  Specific examples of the pigment derivative having a basic group of the present invention are shown below with compound numbers, but are not limited thereto.

  Derivative (1)

誘導体（２）

Derivative (2)

誘導体（３）

Derivative (3)

誘導体（４）

Derivative (4)

誘導体（５）

Derivative (5)

誘導体（６）

Derivative (6)

誘導体（７）

Derivative (7)

誘導体（８）

Derivative (8)

誘導体（９）

Derivative (9)

誘導体（１０）

Derivative (10)

誘導体（１１）

Derivative (11)

誘導体（１２）

Derivative (12)

誘導体（１３）

Derivative (13)

誘導体（１４）

Derivative (14)

誘導体（１５）

Derivative (15)

誘導体（１６）

Derivative (16)

誘導体（１７）

Derivative (17)

誘導体（１８）

Derivative (18)

誘導体（１９）

Derivative (19)

誘導体（２０）

Derivative (20)

誘導体（２１）

Derivative (21)

誘導体（２２）

Derivative (22)

誘導体（２３）

Derivative (23)

誘導体（２４）

Derivative (24)

誘導体（２５）

Derivative (25)

誘導体（２６）

Derivative (26)

誘導体（２７）

Derivative (27)

誘導体（２８）

Derivative (28)

誘導体（２９）

Derivative (29)

誘導体（３０）

Derivative (30)

誘導体（３１）

Derivative (31)

誘導体（３２）

Derivative (32)

誘導体（３３）

Derivative (33)

誘導体（３４）

Derivative (34)

誘導体（３５）

Derivative (35)

誘導体（３６）

Derivative (36)

誘導体（３７）

Derivative (37)

誘導体（３８）

Derivative (38)

誘導体（３９）

Derivative (39)

誘導体（４０）

Derivative (40)

誘導体（４１）

Derivative (41)

誘導体（４２）

Derivative (42)

誘導体（４３）

Derivative (43)

誘導体（４４）

Derivative (44)

誘導体（４５）

Derivative (45)

誘導体（４６）

Derivative (46)

誘導体（４７）

Derivative (47)

誘導体（４８）

Derivative (48)

誘導体（４９）

Derivative (49)

誘導体（５０）

Derivative (50)

  In the photosensitive coloring composition for a color filter of the present invention, a pigment is sufficiently dispersed in a pigment carrier and coated on a transparent substrate such as glass so that the dry film thickness is 0.2 to 5 μm. In order to make it easier to form, a solvent can be included. 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 can be used alone or in combination.

  When the colored composition is cured by ultraviolet irradiation, a photopolymerization initiator or the like is added to the photosensitive colored composition for a color filter of the present invention.

  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 photopolymerization initiator can be used in an amount of 5 to 200 parts by weight, preferably 10 to 150 parts by weight, with respect to 100 parts by weight of the pigment in the photosensitive coloring composition.

  These photopolymerization initiators are used alone or in admixture of two or more. As sensitizers, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenance are used. Such as lenquinone, camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4,4′-diethylaminobenzophenone, etc. A compound can also be used in combination.

  Moreover, the photosensitive coloring composition for color filters can contain a storage stabilizer in order to stabilize the viscosity with time of the coloring 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 organic acids such as methyl ether, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Examples thereof include phosphine and phosphite. The content of the sensitizer can be used in an amount of 0.1 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator in the colored composition.

  The photosensitive coloring composition for a color filter can be prepared as a solvent developing type or alkali developing type colored resist material. A solvent development type or alkali development type colored resist material generally contains a thermoplastic resin, a thermosetting resin or a photosensitive resin, an ethylenically unsaturated monomer, a photopolymerization initiator, and an organic solvent. A pigment is dispersed in the composition.

  The photosensitive coloring composition for a color filter of the present invention is produced by finely dispersing a pigment 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. Can do. At this time, the polyester dispersant (S), pigment derivative, other resin, and additive may be dispersed after mixing all the components. First, only the pigment and the pigment derivative or the pigment derivative and the polyester dispersion are dispersed. Only the agent (S), or only the pigment, the pigment derivative, and the polyester dispersant (S) may be dispersed, and then another component may be added and dispersed again. It can also be produced by mixing several types of pigments separately dispersed on a pigment carrier. The photopolymerization initiator may be added at the stage of preparing the photosensitive coloring composition for color filter, or may be added later to the prepared photosensitive coloring composition for color filter.

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

  Next, the color filter of the present invention will be described. The color filter of the present invention comprises a filter segment or a black matrix formed from the photosensitive coloring composition of the present invention on a transparent substrate, and a general color filter has at least one red filter segment, at least It comprises one green filter segment and at least one blue filter segment, or comprises at least one magenta filter segment, at least one cyan filter segment, and at least one yellow filter segment.

  The color filter of this invention can be manufactured by forming the filter segment of each color on a board | substrate using the coloring composition of this invention by the photolithographic method. As the substrate, a glass plate having a high transmittance with respect to visible light, or a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate is used.

  The formation of each color filter segment by photolithography is performed by the following method. That is, the photosensitive coloring composition for color filter prepared as a solvent developing type or alkali developing type colored resist material is applied on a transparent substrate such as glass by a coating method such as spray coating, spin coating, slit coating, roll coating, etc. It is applied so that the dry film thickness is 0.2 to 10 μm, more preferably 0.2 to 5 μm. When drying the coating film, a vacuum dryer, a convection oven, an IR oven, a hot plate, or the like may be used. 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. Thereafter, the color filter can be manufactured by immersing in a solvent or an alkali developer or spraying the developer by spraying or the like to remove an uncured portion and forming a desired pattern.

  Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the 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 colored resist material, a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Thereafter, ultraviolet exposure can also be performed.

  If a black matrix is formed in advance before forming each color filter segment on a transparent substrate or a reflective substrate, the contrast of the liquid crystal display panel can be further increased. As the black matrix, an inorganic film such as chromium, a chromium / chromium oxide multilayer film, titanium nitride, or a resin film in which a light shielding agent is dispersed may be used. In addition, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, 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. On the color filter of the present invention, an overcoat film, a columnar spacer, a transparent conductive film, a liquid crystal alignment film, and the like are formed 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 for a liquid crystal display mode in which colorization is performed using a color filter.

  The black matrix of the present invention can be produced by forming a black filter segment on a substrate using the colored composition of the present invention by photolithography. As the substrate, a glass plate having a high transmittance with respect to visible light, or a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate is used.

  Formation of the black matrix by photolithography is performed by the following method. That is, the photosensitive coloring composition for color filter prepared as a solvent developing type or alkali developing type colored resist material is applied on a transparent substrate such as glass by a coating method such as spray coating, spin coating, slit coating, roll coating, etc. It is applied so that the dry film thickness is 0.2 to 10 μm, more preferably 0.2 to 5 μm. When drying the coating film, a vacuum dryer, a convection oven, an IR oven, a hot plate, or the like may be used. 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. Thereafter, the color filter can be manufactured by immersing in a solvent or an alkali developer or spraying the developer by spraying or the like to remove an uncured portion and forming a desired pattern.

  Furthermore, in order to accelerate the polymerization of the black matrix material, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the 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 colored resist material, a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Thereafter, ultraviolet exposure can also be performed.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples and comparative examples, “parts” means “parts by weight”.

  Prior to the examples, a method for measuring the contrast ratio of the resist-coated substrate will be described. A resist material coated substrate is sandwiched between two polarizing plates, and light is irradiated from one polarizing plate side using a backlight unit for liquid crystal display. The light emitted from the backlight unit passes through the first polarizing plate and is polarized, and then passes through the resist material-coated substrate and reaches the second polarizing plate. If the polarization planes of the first polarizing plate and the second polarizing plate are parallel, light passes through the second polarizing plate, but if the polarization plane is perpendicular, the light passes through the second polarizing plate. Are blocked by the polarizing plate. However, when the light polarized by the first polarizing plate passes through the resist material coated substrate, scattering by pigment particles or the like causes a deviation in a part of the polarization plane. When the amount of light transmitted through the second polarizing plate is reduced and the deflecting plate is perpendicular, a part of the light is transmitted through the second polarizing plate. This transmitted light is measured as the luminance on the polarizing plate, and the ratio between the luminance when the polarizing plate is parallel and the luminance when the polarizing plate is orthogonal is defined as the contrast ratio.

Contrast ratio = (Luminance when parallel) / (Luminance when direct)
Accordingly, when scattering occurs due to the pigment in the resist material coating film, the luminance when parallel is lowered and the luminance when perpendicular is increased, and the contrast ratio is lowered. The luminance meter was a color luminance meter BM-5A manufactured by Topcon Corporation, and the polarizing plate was a polarizing film LLC2-92-18 manufactured by Sanritsu. In the measurement, in order to block unnecessary light, measurement was performed by applying a black mask having a 1 cm square hole in the measurement portion.

  First, preparation of the acrylic resin solution and polyester dispersant (S) used in Examples and Comparative Examples will be described. The molecular weight of the resin is a weight average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography).

[Production Example 1] Preparation of acrylic resin solution 370 parts of cyclohexanone was placed in a reaction vessel, heated to 80 ° C while injecting nitrogen gas into the vessel, and 20.0 parts of methacrylic acid and 10.0 parts of methyl methacrylate at the same temperature. , A mixture of 55.0 parts of n-butyl methacrylate, 15.0 parts of 2-hydroxyethyl methacrylate and 4.0 parts of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour to carry out a polymerization reaction. . After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A resin solution was obtained.

  After cooling to room temperature, about 2 g of acrylic resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Cyclohexanone was added to the previously synthesized acrylic resin solution so that the nonvolatile content was 20% by weight. Added. The weight average molecular weight of the obtained acrylic resin was 40000.

[Production Example 2] Polyester dispersant 1
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 80 parts of n-butyl methacrylate and 120 parts of benzyl methacrylate were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 80 ° C., and a solution prepared by dissolving 0.1 part of 2,2′-azobisisobutyronitrile in 12 parts of 3-mercapto-1,2-propanediol was added. Reacted for hours. It was confirmed that 95% had reacted by solid content measurement. 30 parts of pyromellitic anhydride, 242 parts of cyclohexanone, and 0.40 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added and reacted at 120 ° C. for 7 hours. By measuring the acid value, it was confirmed that 98% or more of the acid anhydride had been half-esterified, and the reaction was terminated to obtain a polyester dispersant (S) 1.

[Production Examples 3 to 8]
Synthesis was performed in the same manner as in Production Example 2 except that the raw materials and preparation amounts shown in Table 1 were used, and polyester dispersants (S) 2 to 7 were obtained.

PMA: pyromellitic anhydride (manufactured by Daicel Chemical Industries)
BPDA: 3,3 ′, 4,4′-biphenyltetracarboxylic anhydride (Mitsubishi Chemical Corporation)
BPAF: 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride (manufactured by JFE Chemical Co., Ltd.)

[Example 1]
After stirring and mixing a mixture having the following composition uniformly, using a zirconia bead having a diameter of 1 mm, the mixture was dispersed for 2 hours with an Eiger mill ("Mini Model M-250 MK-II" manufactured by Eiger Japan), and then filtered with a 5 μm filter. Filtration was performed to prepare a red pigment dispersion 1. The polyester dispersant (S) 1 was added in advance dissolved in cyclohexanone.

Red pigment 1: “Irgafore Red B-CF” (CI Pigment Red 254) manufactured by Ciba Specialty Chemicals 10.00 parts Polyester dispersant (S) 1: 1.00 parts Derivative 5: 0.50 Parts Acrylic resin solution 1: 37.50 parts Cyclohexanone: 51.00 parts

  Next, a mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain a red resist composition.

Red pigment dispersion 1: 40.00 parts Acrylic resin solution 1: 10.50 parts Monomer: “NK ester ATMPT” (trimethylolpropane triacrylate) manufactured by Shin-Nakamura Chemical Co., Ltd. 4.50 parts Photopolymerization initiator: Ciba Specialty・ "Irgacure 907" manufactured by Chemicals
2.00 parts Sensitizer: "EAB-F" manufactured by Hodogaya Chemical Co., Ltd .: 0.20 part Cyclohexanone: 42.80 parts

[Examples 2 to 12, Comparative Examples 1 to 6]
The pigment, dispersant, resin, and monomer were blended in the proportions (weight ratio) shown in Table 2, and each color resist composition was obtained in the same manner as in Example 1. The solid polyester dispersant (S) was added in advance dissolved in cyclohexanone.

Red pigment 2: “chromophthaled red A2B” (CI Pigment Red 177) manufactured by Ciba Specialty Chemicals
Red pigment 3: “Irgafore Red B-CF” manufactured by Ciba Specialty Chemicals
6.50 parts
“Chromophthaled Red A2B” manufactured by Ciba Specialty Chemicals
2.50 parts
LANXESS "E4GN-GT"
(CI Pigment Yellow 150) 1.00 parts Green Pigment 1: “Lionol Green 6YK” manufactured by Toyo Ink Co., Ltd.
(C.I. Pigment Green 36) 5.80 parts
LANXESS "E4GN-GT"
(CI Pigment Yellow 150) 4.20 parts Pigment for Green 2: “Lionol Green 6YK” manufactured by Toyo Ink Co., Ltd.
(C.I. Pigment Green 36) 5.80 parts
BASF "Pariotor Yellow K0961HD"
(C.I. Pigment Yellow 138) 4.20 parts Blue Pigment 1: “Heliogen Blue L-6700F” manufactured by BASF (C.I. Pigment Blue 15: 6)
Yellow pigment 1: “Pariotol Yellow K0961HD” manufactured by BASF (CI Pigment Yellow 138)
Yellow Pigment 2: “E4GN-GT” (CI Pigment Yellow 150, manufactured by LANXESS)
Monomer: “NK ESTER ATMPT” (trimethylolpropane triacrylate) manufactured by Shin-Nakamura Chemical Co., Ltd.
Initiator: Photopolymerization initiator “Irgacure 907” manufactured by Ciba Specialty Chemicals
Sensitizer: “EAB-F” manufactured by Hodogaya Chemical Co., Ltd.
Solvent: Cyclohexanone Derivatives 5, 12, 13, 42: Pigment derivatives exemplified with compound numbers in the specification Comparative dispersant 1: “PB-821” manufactured by Ajinomoto Fine Techno Co., Ltd.
Comparative dispersant 2: "BYK111" manufactured by Big Chemie
Comparative dispersant 3: Lubrizol "Solspers 41000"

[Viscosity stability]
About each color resist composition obtained by the Example and the comparative example, the viscosity stability was evaluated by the following method.

  Using an E-type viscometer (“ELD type viscometer” manufactured by Toki Sangyo Co., Ltd.), the initial viscosity of the next day after the preparation of each color resist composition and the time-lapse viscosity accelerated at 40 ° C. for 1 week is 25 ° C. The measurement was performed under the condition of a rotational speed of 20 rpm. From the values of the initial viscosity and the viscosity with time, the rate of change with time in viscosity was calculated by the following formula.

  (Change in viscosity over time) = | [(initial viscosity) − (viscosity over time)] / (initial viscosity) | × 100

[Contrast ratio]
Each color resist composition obtained in Examples and Comparative Examples was applied on a glass substrate having a thickness of 100 mm × 100 mm and a thickness of 1.1 mm using a spin coater at a rotation speed of 500 rpm, 1000 rpm, 1500 rpm, and a film thickness of 3 levels. A resist-coated substrate was obtained. The coated substrate was dried at 70 ° C. for 20 minutes, exposed to ultraviolet light with an integrated light amount of 150 mJ using an ultrahigh pressure mercury lamp, heated at 230 ° C. for 1 hour, allowed to cool, and then measured for the contrast ratio. Next, the chromaticity (Y, x, y) of the coating film with a C light source was measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). From the contrast ratio and chromaticity measurement results of the substrate with a film thickness of 3 levels, x = 0.64 for the red coating, y = 0.14 for the blue coating, y = 0.60 for the green coating, yellow For the coating film, the contrast ratio at x = 0.48 was determined by an approximation method.

  The above results are shown in Table 3.

  The photosensitive coloring compositions for color filters obtained in Examples 1 to 12 were superior in stability over time as compared with those obtained in Comparative Examples 1 to 6. Furthermore, the photosensitive coloring composition for color filters using the polyester dispersant (S) of the present invention has a feature that the contrast ratio of the coating film is high.

[Example 13]
After uniformly stirring and mixing a mixture having the following composition, the mixture was dispersed for 1.5 hours with an Eiger mill (“Mini Model M-250 MK-II” manufactured by Eiger Japan) using zirconia beads having a diameter of 1 mm. It filtered with the filter and the black pigment dispersion 1 was produced. The polyester dispersant (S) 1 was added in advance dissolved in cyclohexanone.

Carbon black: Mitsubishi Chemical “# 47” 20.00 parts Polyester dispersant (S) 1: 1.00 Derivative 12: 0.50 parts Acrylic resin solution 1: 25.00 parts Cyclohexanone: 53.50 parts

  Next, a mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain a black resist composition.

Black pigment dispersion 1: 50.00 parts Acrylic resin solution 1: 10.00 parts Monomer: “NK ESTER ATMPT” (trimethylolpropane triacrylate) manufactured by Shin-Nakamura Chemical Co., Ltd. 5.00 parts Photopolymerization initiator: Ciba Specialty・ "Irgacure 907" manufactured by Chemicals
4.00 parts Sensitizer: "EAB-F" manufactured by Hodogaya Chemical Co., Ltd .: 0.20 parts Cyclohexanone: 30.80 parts Derivative 12: Pigment derivative exemplified with compound number in the specification Comparative dispersant 1: “PB-821” manufactured by Ajinomoto Fine Techno Co., Ltd.

[Example 14, Comparative Examples 7 and 8]
The pigment, dispersant, resin, and monomer were blended in the proportions (weight ratio) shown in Table 4, and a black resist composition was obtained in the same manner as in Example 13.

[Viscosity stability]
The viscosity stability of the black resist compositions obtained in Examples 13 and 14 and Comparative Examples 7 and 8 was evaluated by the following method. The results are shown in Table 5.

  Using an E-type viscometer (“ELD type viscometer” manufactured by Toki Sangyo Co., Ltd.), the initial viscosity of the next day after the black resist composition was prepared and the time-lapse viscosity accelerated at 40 ° C. for 1 week were measured at 25 ° C. The measurement was performed under the condition of a rotational speed of 20 rpm. From the values of the initial viscosity and the viscosity with time, the rate of change with time in viscosity was calculated by the following formula.

  (Change in viscosity over time) = | [(initial viscosity) − (viscosity over time)] / (initial viscosity) | × 100

[Shading (optical density (OD))]
After coating a black resist on a 10 cm × 10 cm glass substrate by spin coating, a coating film having a dry film thickness of about 1 μm is formed by drying at 70 ° C. for 15 minutes, and heated at 230 ° C. for 1 hour. Was measured. The optical density (OD) of the coated substrate thus obtained was measured with a Macbeth densitometer (GRETAG D200-II), the measured optical density (OD) was divided by the measured film thickness, and the unit film thickness was measured. The optical density (OD / μm) was determined.

  The photosensitive coloring compositions for color filters obtained in Examples 13 and 14 were superior in stability over time as compared with those obtained in Comparative Examples 7 and 8. Furthermore, the photosensitive coloring composition for color filters using the polyester dispersant (S) of the present invention has a characteristic that the light shielding property of the coating film is high.

Claims (4)

  In the presence of a compound having two hydroxyl groups and one thiol group in the molecule, 40 to 60% by weight of benzyl methacrylate as an ethylenically unsaturated monomer and 40 to 60% of the whole monomer are used. Reaction of a hydroxyl group in a vinyl polymer (a) having two hydroxyl groups at one end and an acid anhydride group in an aromatic tetracarboxylic acid anhydride, which is obtained by radical polymerization with n-butyl methacrylate in weight percent. A photosensitive coloring composition for a color filter, comprising: a polyester dispersant (S) obtained, a pigment, and a pigment carrier containing an ethylenically unsaturated monomer.   The photosensitive coloring composition for a color filter according to claim 1, wherein the polyester dispersant (S) has a weight average molecular weight of 7000 to 10,000 and an acid value of 20 to 60.   A color filter comprising a filter segment formed from the photosensitive coloring composition according to claim 1 or 2 on a transparent substrate.   A color filter comprising a black matrix formed from the photosensitive coloring composition according to claim 1 on a transparent substrate.