JP5888065B2 - Coloring composition for color filter and color filter - Google Patents

Description

  The present invention relates to a color liquid crystal display device, a color composition for a color filter used for producing a color filter used for a color image pickup tube element, and the like, and a color filter including a filter segment formed using the same. It is.

  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. By providing a color filter between the two polarizing plates, color display becomes possible, and since it has recently been used in televisions and personal computer monitors, it has higher brightness, higher contrast, The demand for color reproducibility is increasing.

  A color filter is a surface of a transparent substrate such as glass, in which two or more kinds of fine band (striped) filter segments of different hues are arranged in parallel or crossing each other, or fine filter segments are arranged vertically and horizontally. It is made up of those arranged in In general, it is often formed from filter segments of three colors of red, green, and blue. Each of these segments is as fine as several microns to several hundred microns, and is arranged in a predetermined arrangement for each hue. ing.

  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, a high temperature treatment of generally 200 ° C. or higher, preferably 230 ° C. or higher is required in the production process for forming the color filter. Therefore, at present, a method called a pigment dispersion method using a pigment having excellent light resistance and heat resistance as a colorant is mainly used for color filters.

  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.

  In order to achieve high brightness and high contrast of the color filter, the pigment contained in the filter segment is often used after being refined. However, various pigments (similarly called crudes having a particle size of 10 to 100 μm produced by chemical reaction, which are made into a mixture of primary particles and aggregated secondary particles by pigmentation treatment) Even if the particles are refined by the refinement treatment method, the pigments whose primary particles or secondary particles have been refined generally tend to agglomerate. When the refinement is too advanced, a huge lump of pigment solid is formed. End up. Furthermore, even if the pigment that has been refined further is dispersed in a pigment carrier containing a resin or the like, and the secondary particles of the pigment are stabilized as close as possible to the primary particles, a stable coloring composition is obtained. It is very difficult.

  In addition, it is difficult to disperse pigments that have been refined into a pigment carrier containing a resin or the like, and it is difficult to disperse pigments stably at high concentrations. It is known to cause various problems.

  For example, pigment compositions containing pigments composed of fine particles often exhibit high viscosity, making it difficult to remove and transport the product from a disperser, and in the worst case, cause gelation during storage, It may even be difficult to use. Furthermore, regarding the surface of the color-developed product of the pigment composition, a poor state such as a decrease in gloss and poor leveling occurs. When different types of pigments are used in combination, color unevenness due to aggregation or phenomena such as sedimentation may cause uneven color and a marked reduction in coloring power.

  Therefore, in general, a resin-type dispersant is used in order to keep the dispersion state good. The resin-type dispersant has a structure of a part that is adsorbed to the pigment and a part that has a high affinity for the solvent as the dispersion medium, and the performance is determined by the balance of these two functional parts. Various types of resin-type dispersants are used according to the surface state of the pigment to be dispersed.

  A resin-type dispersant having a block-type structure (Patent Document 1) or a comb-shaped structure (Patent Document 2) is known to have excellent pigment dispersibility. In either case, since the pigment has been made finer in recent years and the surface area has increased, it tends to be added in a large amount to ensure dispersion stability. Non-image area after development due to decrease in solubility in developer due to increase in amount of dispersant, poor solubility of developer in developer, development failure within specified time, or development possible In some cases, the undissolved product of the colored resin composition tends to remain. Furthermore, when the undissolved material of the colored resin composition remains on the non-pixel portion on the substrate, the obtained color filter causes a decrease in transmittance and contrast, and when it remains on the pattern edge portion, Such a situation may affect the subsequent process such as peeling or deterioration of the sealing property in the liquid crystal cell forming process.

  In the case of a comb-shaped structure, a comb tooth portion having a functional group such as a carboxyl group or an acryloyl group is grafted to a polyamine compound having a primary or secondary amino group, and the remaining primary or secondary amine is present on the pigment surface. However, primary or secondary amines are not preferred because they have active hydrogen with high reactivity.

  As described above, the color filter is required to have not only high contrast but also high brightness. In general, in order to obtain high brightness, when dispersing the pigment in the pigment carrier, the transparency of the dispersion is increased to close to the primary particles, and the spectral spectrum of the dispersion has high transmittance, thereby increasing the brightness. It has gained.

  In order to solve such problems, attempts have been made to improve the structure and acid value of acrylic block copolymers and improve pigment dispersibility by adding a small amount (see Patent Documents 3, 4, 5, and 6). ) But not enough.

JP 2002-31713 A Japanese Patent Laid-Open No. 11-1515 JP 2006-265528 A JP 2006-321979 A JP 2009-25813 A Special table 2010-506016 gazette

  The present invention provides a coloring composition for a color filter which has excellent brightness (Y value), contrast ratio (CR value), dispersibility, and excellent sensitivity, linearity, pattern shape, resolution, development resistance and chemical resistance. The purpose is to provide a high brightness, high contrast ratio filter segment and a high quality color filter.

  As a result of intensive research to solve the above problems, the present inventors have obtained a coloring composition containing a pigment, a binder resin (B) having a specific structure, and a specific resin-type dispersant (C). It has been found that the above problems can be solved.

That is, the present invention relates to a color filter coloring composition containing a pigment (A), a binder resin (B), and a resin-type dispersant (C).
The binder resin (B) contains 2 to 60 mol% of repeating units having the structure (b1) represented by the following general formula (1),
An AB block copolymer or a B-A-B block in which the resin-type dispersant (C) is composed of an A block having a solvophilic group and an aromatic ring group, and a B block having a functional group containing a nitrogen atom A copolymer comprising:
A block is a repeating unit represented by the following general formula (2) as a solvophilic group, 4 to 40 mol% in the copolymer, and a repeating unit represented by the following general formula (3) as an aromatic ring group, 4-30 mol% in the copolymer,
B block contains a repeating unit represented by the following general formula (4),
In addition, the present invention relates to a coloring composition for a color filter, which is a (meth) acrylic block copolymer having an amine value of 10 mgKOH / g or more and 99 mgKOH / g or less in terms of effective solid content.

[In general formula (1), a represents a carbon-carbon bond which is a single bond or a double bond. ]

[In General Formula (2), n1 represents an integer of 1 to 10, R1 represents a hydrogen atom or a methyl group, and R2 represents an alkyl group having 1 to 10 carbon atoms which may be branched. ]

[In general formula (3), R3 represents a hydrogen atom or a methyl group. n2 is an integer of 0 or 1, and φ represents an aromatic ring which may have a plurality of different substituents and may contain a 5- to 6-membered nitrogen atom. ]

[In General Formula (4), R4 represents a hydrogen atom or a methyl group, and R5 represents an alkylene group having 1 or more carbon atoms. n3 is an integer of 0 or 1, and R6 to R8 have a cyclic or chain alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. Represents an aralkyl group which may be present, and X1 represents a counter anion when n3 = 1. ]

In the present invention, the binder resin (B) further contains 2 to 80 mol% of repeating units having the structure (b2) represented by the following general formula (6) and 2 repeating units having a carboxyl group (b3). It is related with the coloring composition for said color filters characterized by containing -70 mol%.

[In General Formula (6), R9 is one or more substituents which may be different from each other, and is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a benzene ring. Moreover, you may have a cyclic structure containing the 1 or more saturated or unsaturated heterocyclic ring which may have a substituent adjacent to a benzene ring in the broken-line part in General formula (6). ]

  In addition, the present invention further includes at least one photopolymerization initiator (D1) selected from the group consisting of acetophenone compounds, phosphine compounds, imidazole compounds, and oxime ester compounds. It is related with the coloring composition for filters.

  The present invention also relates to a color filter comprising a filter segment formed on the base material from the color filter coloring composition.

The coloring composition for a color filter of the present invention is a stable coloring composition for a color filter having excellent fluidity and developability. By using the coloring composition for a color filter, a high contrast ratio and a high brightness are obtained. Each color filter segment can be formed.
Therefore, a high quality color filter can be obtained by using the coloring composition for a color filter of the present invention.

First, various components of the coloring composition for a color filter of the present invention will be described.
In the present application, the case where “(meth) acryloyl”, “(meth) acryl”, “(meth) acrylic acid”, “(meth) acrylate”, or “(meth) acrylamide” is particularly described. Unless otherwise indicated, “acryloyl and / or methacryloyl”, “acrylic and / or methacrylic”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, or “acrylamide and / or methacrylamide”, respectively. It shall represent.

<Pigment (A)>
As the pigment (A) of the present invention, for example, when forming each color filter segment, various color pigments such as a red pigment, a blue pigment, a green pigment, a yellow pigment, a purple pigment, an orange pigment, and a brown pigment are used. be able to. Examples of the chemical structure include organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene. In addition, various inorganic pigments can be used.

Specific examples of pigments that can be used are shown below. The following “CI” means a color index (CI).
Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 , 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267 268, 269, 270, 271, 272, 273, 274, 275, 276, and the like. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, or 254, more preferably C.I. I. Pigment Red 177, 209, 224, 242, or 254.

  Examples of blue pigments include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 and the like. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, or 15: 6, and more preferably C.I. I. Pigment Blue 15: 6.

  Examples of the green pigment include C.I. I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55 or 58. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment Green 7, 36 or 58.

  Examples of yellow pigments include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202 , 203, 204, 205, 206, 207, 208, and the like. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, or 185, more preferably C.I. I. Pigment yellow 83, 138, 139, 150, or 180.

  Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment violet 19 or 23, more preferably C.I. I. Pigment Violet 23.

  Examples of orange pigments include C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79 and the like. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment Orange 38 or 71.

  A plurality of the above-mentioned various pigments can be used in combination. For example, in order to adjust the chromaticity, a green pigment and a yellow pigment can be used in combination, or a blue pigment and a violet pigment can be used in combination.

  The content of the pigment (A) in the colored composition of the present invention is usually 1% by weight or more, preferably 5% by weight or more, and usually 95% by weight or less, preferably 85% by weight in 100% by weight of the total solid content. % Or less. If the ratio of the pigment is too small, the film thickness with respect to the color density becomes too large, which may adversely affect the gap control or the like when forming a liquid crystal cell. On the other hand, if the ratio of the pigment is too large, it may be difficult to obtain dispersion stability.

[Miniaturization of pigment]
The pigment used in the present invention can be used after being refined. There are no particular limitations on the method of miniaturization. For example, any of wet grinding, dry grinding, and dissolution precipitation can be used. As exemplified in the present invention, salt milling by a kneader method, which is one type of wet grinding. The primary particle diameter of the pigment can be set in the range of 20 to 50 nm by performing treatment or the like. When the average primary particle size is less than 20 nm, pigment dispersion may be difficult. On the other hand, if the average primary particle diameter exceeds 50 nm, the contrast ratio and the brightness may be lowered. That is, when the average primary particle size is increased, the light of the backlight is scattered and leakage light is generated when the polarizing plate is crossed, leading to a reduction in contrast ratio. Further, since the transmittance decreases, it also affects the decrease in brightness.

  In addition, the average primary particle diameter of the pigment was measured by a method of directly measuring the size of the primary particle from an electron micrograph of the pigment by 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 approximated to a cube having the obtained particle diameter to obtain an average volume, and the length of one side of the cube having this average volume is determined as the average primary The particle size.

  Salt milling is a process in which a mixture of pigment, water-soluble inorganic salt and water-soluble organic solvent is heated using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, or sand mill. After 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.

<Binder resin (B)>
The binder resin (B) contained in the coloring composition for a color filter of the present invention is a repeating unit having a structure (b1) represented by the following general formula (1), based on all repeating units (100 mol%), It is characterized by containing 2 to 60 mol%.

[In general formula (1), a represents a carbon-carbon bond which is a single bond or a double bond. ]

Preferably, the binder resin (B) further has 2 to 80 mol% of repeating units having the structure (b2) represented by the following general formula (6) and a repeating unit having a structural unit (b3) having a carboxyl group. The unit contains 2 to 70 mol%.

[In General Formula (6), R9 is one or more substituents which may be different from each other, and is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a benzene ring. Moreover, you may have a cyclic structure containing the 1 or more saturated or unsaturated heterocyclic ring which may have a substituent adjacent to a benzene ring in the broken-line part in General formula (6). ]

  Below, a structural unit (b1), a structural unit (b2), a structural unit (b3), and another structural unit are demonstrated in order. The mol% in the description is a value in all repeating units (100 mol%) that bring each constituent unit to the binder resin (B).

[Repeating unit having structure (b1) represented by general formula (1)]
The structure (b1) represented by the general formula (1) is a cyclic structure based on an aliphatic ring group, and functions as an affinity site for a pigment or a resin-type dispersant and as a hydrophobic site for an alkali developer. Based on the total repeating units of the binder resin (B) (100 mol%), the repeating unit having the structure (b1) is 2 to 60 mol% from the viewpoints of developability, filter segment quality and dispersion stability. . If it is less than 2 mol%, the affinity site for the pigment or resin-type dispersant is insufficient, resulting in a problem that a high-quality color filter cannot be obtained, and the storage stability of the color filter coloring composition is deteriorated, Since the hydrophobicity at the time of development is insufficient, there is a problem of pattern peeling or chipping in the pixel portion. If it exceeds 60 mol%, the dissolution rate in an alkali developer will be slow, the development time will be long, and the productivity of the color filter will deteriorate.

  In the dicyclopentane moiety of the structure (b1) represented by the general formula (1), the ring does not take a planar structure and gives a steric hindrance to the mutual aggregation state of the molecules in the filter segment. Can be expected.

[In general formula (1), a represents a carbon-carbon bond which is a single bond or a double bond. ]

  Examples of the precursor of the repeating unit having the structure (b1) include an ethylenically unsaturated monomer represented by the following general formula (7).

[In General Formula (7), R13 is a hydrogen atom or a methyl group, R14 is an alkylene group having 2 or 3 carbon atoms, and n5 is an integer of 0 to 2. a represents a carbon-carbon bond which is a single bond or a double bond. ]

Examples of the ethylenically unsaturated monomer represented by the general formula (7) in which a is a single bond include:
FANCLIL manufactured by Hitachi Chemical Co., Ltd. FA-513A [dicyclopentanyl acrylate, R13: hydrogen atom, R14: none, n5 = 0], or FA-513M [dicyclopentanyl methacrylate, R13: hydrogen atom, R14: none, n5 = 0] and the like, but are not limited to these, and two or more types may be used in combination.

Examples of the ethylenically unsaturated monomer represented by the general formula (7) in which a is a double bond include:
FANCLIL manufactured by Hitachi Chemical Co., Ltd. FA-511A [dicyclopentenyl acrylate, R13: hydrogen atom, R14: none, n5 = 0], FA-512A [dicyclopentenyloxyethyl acrylate, R13: hydrogen atom, R14: ethylene group, n5 = 1], FA-512M [dicyclopentenyloxyethyl methacrylate, R13: methyl group, R14: ethylene group, n5 = 1], or FA-512MT [dicyclopentenyloxyethyl methacrylate, R13: methyl group, R14: An ethylene group, n5 = 1] and the like are exemplified, but the present invention is not limited thereto, and two or more kinds may be used in combination.

[Repeating unit having structure (b2) represented by general formula (6)]
The structure (b2) represented by the general formula (6) is a cyclic structure having an aromatic ring group, and functions as an affinity site for the pigment or the resin-type dispersant. Based on all repeating units of the binder resin (B) (100 mol%), the repeating unit having the structure (b2) is 20 to 80 mol% from the viewpoint of developability and filter segment quality. If it is less than 20 mol%, there may be a problem in that the affinity site for the pigment or the resin-type dispersant is insufficient, resulting in a problem that a high-quality color filter cannot be obtained and the resistance of the filter segment is deteriorated. If it exceeds 1, the dissolution rate in an alkaline developer will be slow, and the development time may be long and the productivity of the color filter may deteriorate.

[In General Formula (6), R9 is one or more substituents which may be different from each other, and is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a benzene ring. Moreover, you may have a cyclic structure containing the 1 or more saturated or unsaturated heterocyclic ring which may have a substituent adjacent to a benzene ring in the broken-line part in General formula (6). ]

  Examples of the precursor of the repeating unit having the structural unit (b2) include styrene, α-methylstyrene, divinylbenzene, indene, acetylnaphthene, benzyl acrylate, benzyl methacrylate, bisphenol A diglycidyl ether di (meth) acrylate, and methylolated melamine. Monomers (oligomers) such as (meth) acrylic acid esters, or ethylenically unsaturated monomers represented by the general formula (8).

[In General Formula (8), R10 is a hydrogen atom or a methyl group, R11 is an alkylene group having 2 or 3 carbon atoms, and R12 is one or more substituents which may be different from each other, It is a C1-C20 alkyl group which may have a hydrogen atom or a benzene ring, and n4 is an integer of 1-15. ]

As the ethylenically unsaturated monomer represented by the general formula (8), for example,
New Frontier CEA [EO-modified cresol acrylate, R10: hydrogen atom, R11: ethylene group, R12: methyl group, n4 = 1 or 2,], NP-2 [n-nonylphenoxypolyethylene glycol acrylate, R10: hydrogen atom, R11: ethylene group, R12: n-nonyl group, n4 = 2], N-177E [n-nonylphenoxypolyethylene glycol acrylate, R10: hydrogen atom, R11: ethylene group, R12: n-nonyl group N4 = 16-17], or PHE [phenoxyethyl acrylate, R10: hydrogen atom, R11: ethylene group, R12: hydrogen atom, n4 = 1],
Daicel, IRR169 [ethoxylated phenyl acrylate (EO 1 mol), R10: hydrogen atom, R11: ethylene group, R12: hydrogen atom, n4 = 1], or Ebecryl110 [ethoxylated phenyl acrylate (EO 2 mol), R10: hydrogen Atom, R11: ethylene group, R12: hydrogen atom, n4 = 2],
Aronix M-101A (phenol EO modified (n4≈2) acrylate, R10: hydrogen atom, R11: ethylene group, R12: hydrogen atom, n4≈2], M-102 [phenol EO modified (n4≈4) manufactured by Toagosei Co., Ltd. ) Acrylate, R10: hydrogen atom, R11: ethylene group, R12: hydrogen atom, n4≈4], M-110 [paracumylphenol EO modified (n4≈1) acrylate, R10: hydrogen atom, R11: ethylene group, R12 : Paracumyl, n4≈1], M-111 [n-nonylphenol EO-modified (n4≈1) acrylate, R10: hydrogen atom, R11: ethylene group, R12: n-nonyl group, n4≈1], M-113 [ n-nonylphenol EO-modified (n4≈4) acrylate, R10: hydrogen atom, R11: ethylene group, R12: n-no N-group, n4≈4], or M-117 [n-nonylphenol PO-modified (n4≈2.5) acrylate, R10: hydrogen atom, R11: propylene group, R12: n-nonyl group, n4≈2.5] ,
Kyoeisha light acrylate PO-A [phenoxyethyl acrylate, R10: hydrogen atom, R11: ethylene group, R12: hydrogen atom, n4 = 1], P-200A [phenoxypolyethylene glycol acrylate, R10: hydrogen atom, R11: ethylene group , R12: hydrogen atom, n4≈2], NP-4EA [nonylphenol EO adduct acrylate, R10: hydrogen atom, R11: ethylene group, R12: n-nonyl group, n4≈4], or NP-8EA [nonylphenol EO Adduct acrylate, R10: hydrogen atom, R11: ethylene group, R12: n-nonyl group, n4≈8], or light ester PO [phenoxyethyl methacrylate, R10: methyl group, R11: propylene group, R12: hydrogen atom, n4 = 1],
NIPPON BLEMER ANE-300 [nonylphenoxypolyethylene glycol acrylate, R10: hydrogen atom, R11: ethylene group, R12: n-nonyl group, n4≈5], ANP-300 [nonylphenoxypolypropylene glycol acrylate, R10: hydrogen Atom, R11: propylene group, R12: n-nonyl group, n4≈5], 43ANEP-500 [nonylphenoxy-polyethylene glycol-polypropylene glycol-acrylate, R10: hydrogen atom, R11: ethylene group and propylene group, R12: n -Nonyl group, n4≈5 + 5], 70ANEP-550 [nonylphenoxy-polyethylene glycol-polypropylene glycol-acrylate, R10: hydrogen atom, R11: ethylene group and propylene group, R12: n -Nonyl group, n4≈9 + 3], 75ANEP-600 [nonylphenoxy-polyethylene glycol-polypropylene glycol-acrylate, R10: hydrogen atom, R11: ethylene group and propylene group, R12: n-nonyl group, n4≈5 + 2], AAE -50 [phenoxypolyethylene glycol acrylate, R10: hydrogen atom, R11: ethylene group, R12: hydrogen atom, n4 = 1], AAE-300 [phenoxypolyethylene glycol acrylate, R10: hydrogen atom, R11: ethylene group, R12: hydrogen Atom, n4≈5.5], PAE-50 [phenoxypolyethyleneglycol methacrylate, R10: methyl group, R11: ethylene group, R12: hydrogen atom, n4 = 1], PAE-100 [phenoxypolyethyleneglycol Acrylate, R10: methyl group, R11: ethylene group, R12: hydrogen atom, n4 = 2], or 43PAPE-600B [phenoxy-polyethylene glycol-polypropylene glycol-methacrylate, R10: methyl group, R11: ethylene group and propylene group, R12: hydrogen atom, n4≈6 + 6],
NK ESTER AMP-10G [phenoxyethylene glycol acrylate (EO 1 mol), R10: hydrogen atom, R11: ethylene group, R12: hydrogen atom, n4 = 1], AMP-20G [phenoxyethylene glycol acrylate (EO 2 mol), manufactured by Shin-Nakamura Chemical Co., Ltd. , R10: hydrogen atom, R11: ethylene group, R12: hydrogen atom, n4≈2], AMP-60G [phenoxyethylene glycol acrylate (EO 6 mol), R10: hydrogen atom, R11: ethylene group, R12: hydrogen atom, n4≈ 6], PHE-1G [phenoxyethylene glycol methacrylate (EO 1 mol), R10: methyl group, R11: ethylene group, R12: hydrogen atom, n4 = 1],
Biscoat # 192 [phenoxyethyl acrylate, R10: hydrogen atom, R11: ethylene group, R12: hydrogen atom, n4 = 1] manufactured by Osaka Organic Chemical Co., Ltd.
SR-339A manufactured by Nippon Kayaku [2-phenoxyethylene glycol acrylate, R10: hydrogen atom, R11: ethylene group, R12: hydrogen atom, n4 = 1], or SR-504 (ethoxylated nonylphenol acrylate, R10: hydrogen atom, R11: ethylene group, R12: n-nonyl group] and the like, but not limited thereto, two or more kinds may be used in combination.

  In the ethylenically unsaturated monomer represented by the general formula (8), the alkyl group of R12 has 1 to 20 carbon atoms, and more preferably 1 to 10 carbon atoms. The alkyl group includes not only a linear alkyl group but also a branched alkyl group and an alkyl group having a benzene ring as a substituent. When the carbon number of the alkyl group of R12 is 1 to 10, the alkyl group becomes an obstacle and suppresses the approach between the resins and promotes adsorption / orientation to the pigment. The hindrance effect becomes high and shows a tendency to prevent even the adsorption / orientation of the benzene ring to the pigment. This tendency becomes more prominent as the carbon chain length of the alkyl group of R12 becomes longer. When the carbon number exceeds 20, the adsorption / orientation of the benzene ring is extremely lowered. Examples of the alkyl group having a benzene ring represented by R12 include a benzyl group and a 2-phenyl (iso) propyl group. By increasing one side chain benzene ring, solvent affinity and pigment orientation are further improved, and not only dispersibility but also developability is improved.

  In the ethylenically unsaturated monomer represented by the general formula (8), n4 is preferably an integer of 1 to 15. When n4 exceeds 15, the hydrophilicity increases and the effect of solvation decreases, the viscosity of the vinyl resin increases, and the viscosity of the colored composition using this increases, which affects the fluidity. There is. From the viewpoint of solvation, n4 is particularly preferably 1 to 4.

  As a precursor of the repeating unit having the structure (b2), styrene, α-methylstyrene, benzyl acrylate, benzyl methacrylate, or a general formula from the viewpoint of copolymerization with other precursors and the viewpoint of pigment dispersibility. The ethylenically unsaturated monomer represented by (8) is preferred. By introducing a benzene ring into the side chain of the binder resin (B), the side chain benzene ring is oriented to the pigment, thereby promoting the resin adsorption to the pigment and further suppressing the aggregation of the pigment. Furthermore, benzyl acrylate and / or benzyl methacrylate are most preferred from the viewpoints of developability and dispersion stability.

[Repeating unit having carboxyl group (b3)]
The carboxyl group (b3) functions as an alkali-soluble site during development. In all the repeating units (100 mol%) of the binder resin (B), the repeating unit having a carboxyl group (b3) is 2 to 70 mol% from the viewpoint of developability and dispersion stability. If it is less than 2 mol%, the removability of the unexposed portion by the alkaline developer becomes insufficient, and the dispersion stability may deteriorate. On the other hand, if it exceeds 70 mol%, the dissolution rate in an alkali developer increases, and the exposed portion may be dissolved.

  Examples of the precursor of the repeating unit having a carboxyl group (b3) include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, or α-chloroacrylic acid, and unsaturated dicarboxylic acids such as maleic acid or fumaric acid. And compounds containing a carboxyl group such as an acid and having an ethylenically unsaturated double bond. Moreover, what half-esterified the anhydride of unsaturated dicarboxylic acid, such as maleic anhydride, with the (meth) acrylic compound which has hydroxyl groups, such as hydroxyalkyl (meth) acrylate, can also be used. Among these, (meth) acrylic acid is more preferable, and methacrylic acid is most preferable from the viewpoint of polymerizability (ease of control of molecular weight and the like). These can be used alone or in combination of two or more.

  Even if it is a precursor containing a carboxyl group at the raw material stage, the structure having a carboxyl group (b3) in this specification when the carboxyl group is changed to an ester bond or the like in the process of forming the binder resin (B) Does not fall into units.

[Other repeat units]
Other repeating units are repeating units other than the repeating unit having the structure (b1), the repeating unit having the structure (b2), and the repeating unit having the carboxyl group (b3).

Examples of other repeating unit precursors include:
Methyl (meth) methacrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (Meth) acrylate, pentyl (meth) acrylate, isopentyl acrylate, neopentyl (meth) acrylate, t-pentyl (meth) acrylate, 1-methylbutyl (meth) acrylate, hexyl (meth) acrylate, hepta (meth) acrylate, octyl (Meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, Alkyl or alkenyl (meth) acrylates such as rohexyl (meth) acrylate, allyl (meth) acrylate, or oleyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, β-carboxyethyl (Meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) Acrylate, pentaerythritol tri (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di Various acrylic and methacrylic esters such as (meth) acrylate, dipentaerythritol hexa (meth) acrylate, isobornyl (meth) acrylate, ester acrylate, epoxy (meth) acrylate, urethane acrylate, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol Divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile, dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, diethyl- 2,2 '-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2'-[oxybis (methylene)] bis-2- Examples of monomers and oligomers such as propenoate and dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate include, but are not limited to, other ethylenically unsaturated monomers. Can be selected, and two or more types can be used in combination.

Examples of other ethylenically unsaturated monomers include:
(Meth) acrylates having a heterocyclic substituent such as tetrahydrofurfuryl (meth) acrylate or 3-methyloxetanyl (meth) acrylate;
Alkoxypolyalkylene glycol (meth) acrylates such as methoxypolypropylene glycol (meth) acrylate or ethoxypolyethylene glycol (meth) acrylate; or
(Meth) acrylamides such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, or acryloylmorpholine Etc.

Examples of the precursor other than the acrylic repeating unit include:
Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether; or
Examples include vinyl acetate, and fatty acid vinyls such as vinyl propionate. The structural unit other than the acrylic structural unit may be used in combination with the acrylic structural unit.

[Introduction of ethylenically unsaturated double bond]
Moreover, in order to introduce an ethylenically unsaturated double bond by the following method (i) or method (ii), an ethylenically unsaturated monomer having an epoxy group or an ethylenically unsaturated monomer having a hydroxyl group The body can also be used. Since these may be structural units other than other structural units depending on modification, the final repeating unit having the structure (b1), the repeating unit having the structure (b2), the carboxyl group (b3) It is necessary to consider the molar ratio of the repeating unit having a repeating unit having.

[Method (i)]
As the method (i), for example, the side of the copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group and one or more other ethylenically unsaturated monomers Addition reaction of a carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond to the chain epoxy group, and further reacting a polybasic acid anhydride to the generated hydroxyl group, an ethylenically unsaturated double bond There is a method of introducing a carboxyl group having the function of a photosensitive resin and introducing an alkali-soluble function.

  Since the carboxyl group of the unsaturated monobasic acid used in this step forms an ester bond after the addition reaction to the epoxy group, the repeating unit having the carboxyl group (b3) of the binder resin (B) in this specification includes Not applicable, corresponds to other structural units, and since the polybasic acid anhydride forms a carboxyl group after reaction with a hydroxyl group, the repeating unit having the carboxyl group (b3) of the binder resin (B) in this specification It corresponds to.

Examples of the ethylenically unsaturated monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, and 2-glycidoxyethyl (meth).
An acrylate, 3,4 epoxy butyl (meth) acrylate, and 3,4 epoxy cyclohexyl (meth) acrylate are mentioned, These may be used independently or may use 2 or more types together. 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 the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride and the like.
More than one type may be used together. 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 be hydrolyzed. Moreover, when an etrahydrophthalic anhydride or maleic anhydride having an ethylenically unsaturated double bond is used as the polybasic acid anhydride, the ethylenically unsaturated double bonds can be further increased.

As a method similar to the method (i), for example, a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group and one or more other ethylenically unsaturated monomers. There is a method of introducing an ethylenically unsaturated double bond and a carboxyl group by adding an ethylenically unsaturated monomer having an epoxy group to a part of the side chain carboxyl group of the coalescence.
In this case, only the structural unit corresponding to the carboxyl group that is not used for the addition reaction with the epoxy group corresponds to the repeating unit having the carboxyl group (b3) of the binder resin (B) in this specification.

[Method (ii)]
As the method (ii), an ethylenically unsaturated monomer having a hydroxyl group is used, and an unsaturated monobasic acid having another carboxyl group or another ethylenically unsaturated monomer is copolymerized. There is a method of reacting the isocyanate group of an ethylenically unsaturated monomer having an isocyanate group with the side chain hydroxyl group of the obtained copolymer.

  Examples of the ethylenically unsaturated monomer 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 ethylenically unsaturated 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.

  The weight average molecular weight (Mw) of the binder resin (B) is preferably in the range of 5,000 to 100,000, more preferably in the range of 5,000 to 80,000, and still more preferably 5,000 to 30,000. 000 range. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.

  When the weight average molecular weight (Mw) of the binder resin (B) exceeds 100,000, the interaction between the resins becomes strong, and the viscosity of the color filter coloring composition is increased, which makes it difficult to handle. Further, if the weight average molecular weight (Mw) is less than 5,000, problems may occur in developability and adhesion to a substrate such as glass.

  Here, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are TPCgel columns (manufactured by Tosoh Corporation), GPC equipped with RI detector (manufactured by Tosoh Corporation, HLC-8120GPC), and THF as a developing solvent. It is the molecular weight in terms of polystyrene measured by using.

  The content of the binder resin (B) is preferably used in an amount of 30 parts by weight or more with respect to 100 parts by weight of the pigment (A) because the film formability and various resistances are good, and the colorant concentration is high. Since good color characteristics can be expressed, it is preferably used in an amount of 500 parts by weight or less. More preferably, it is used in an amount of 50 to 250 parts by weight.

<Other resins>
The colored composition of the present invention may further contain other resins other than the binder resin (B). The other resin is preferably 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. Other resins include thermoplastic resins, thermosetting resins, and photosensitive resins, and these can be used alone or in admixture of two or more.

  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.

  Examples of the photosensitive resin include (meth) acrylic compounds having a reactive substituent such as an isocyanate group, an aldehyde group, and an epoxy group on a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, or an amino group, A resin obtained by reacting an acid and introducing a photocrosslinkable group such as a (meth) acryloyl group or a styryl group into the linear polymer is used. Further, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is converted into a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. Half-esterified products are also used.

<Resin type dispersant (C)>
The resin-type dispersant (C) in the present invention is an AB block copolymer or B-A comprising an A block having a solvophilic group and an aromatic ring group, and a B block having a functional group containing a nitrogen atom. -B block copolymer,
A block is a repeating unit represented by the following general formula (2) as a solvophilic group, 4 to 40 mol% in the copolymer, and a repeating unit represented by the following general formula (3) as an aromatic ring group, 4-30 mol% in the copolymer,
B block contains a repeating unit represented by the following general formula (4),
In addition, it is a (meth) acrylic block copolymer having an amine value of 10 mgKOH / g or more and 99 mgKOH / g or less in terms of effective solid content.
[In General Formula (2), n1 represents an integer of 1 to 10, R1 represents a hydrogen atom or a methyl group, and R2 represents an alkyl group having 1 to 10 carbon atoms which may be branched. ]

[In general formula (3), R3 represents a hydrogen atom or a methyl group. n2 is an integer of 0 or 1, and φ represents an aromatic ring which may have a plurality of different substituents and may contain a 5- to 6-membered nitrogen atom. ]

[In General Formula (4), R4 represents a hydrogen atom or a methyl group, and R5 represents an alkylene group having 1 or more carbon atoms. n3 is an integer of 0 or 1, and R6 to R8 have a cyclic or chain alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. Represents an aralkyl group which may be present, and X1 represents a counter anion when n3 = 1. ]

  The resin-type dispersant has a colorant-affinity part having the 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. However, since the pigment adsorbing groups are randomly arranged in the random type dispersant, the viscosity tends to increase by crosslinking. On the other hand, in the block copolymer, the pigment adsorbing groups are arranged at high density, so that the adsorption to the pigment is strong and there is no crosslinking. For this reason, the block copolymer can ensure higher dispersion stability. Further, when the amine value is 10 mgKOH / g or more and 99 mgKOH / g or less, the solubility in the developer is improved, the development process can be performed within a predetermined time, and the non-pixel portion on the substrate is colored. The undissolved material of the resin composition does not remain. More preferably, it is 50-90 mgKOH / g.

  Further, by including the repeating unit represented by the general formula (2) in the A block, solvophilicity is imparted and dispersibility is improved, and hydrophilicity is imparted and solubility in a developer is improved. On the other hand, when the repeating unit represented by the general formula (3) is further included, the compatibility with the binder resin is increased, and the dispersion stability is improved.

[Repeating unit represented by general formula (2)]
[In General Formula (2), n1 represents an integer of 1 to 10, R1 represents a hydrogen atom or a methyl group, and R2 represents an alkyl group having 1 to 10 carbon atoms which may be branched. ]
4 to 40 mol% of the repeating unit represented by the general formula (2) is contained in all repeating units (100 mol%) of the copolymer.

[Repeating unit represented by general formula (3)]
[In general formula (3), R3 represents a hydrogen atom or a methyl group. n2 is an integer of 0 or 1, and φ represents an aromatic ring which may have a plurality of different substituents and may contain a 5- to 6-membered nitrogen atom. ]

  Examples of the precursor of the repeating unit represented by the general formula (3) include styrene monomers such as styrene and α-methylstyrene, benzyl (meth) acrylate, and the like.

  4-30 mol% is contained in the repeating unit represented by General formula (3) in all the repeating units (100 mol%) of a copolymer.

[Other repeat units]
The ethylenically unsaturated monomer that is a precursor of other repeating units of the A block having solvophilicity is represented by a repeating unit precursor represented by the general formula (2) and a general formula (3). There is no particular limitation as long as it does not have a repeating unit and other functional group containing a nitrogen atom such as an amino group and can be copolymerized with the ethylenically unsaturated monomer constituting the B block.

  For example, methyl (meth) acrylate, ethyl (meth) acrylate (propyl) (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, 2- (meth) acrylate 2- (Meth) acrylate monomers such as ethylhexyl, glycidyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl ethyl acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate; (meth) acrylic chloride (Meth) acrylate monomers such as: vinyl acetate monomers; polymer structures obtained by copolymerizing comonomers such as glycidyl ether monomers such as allyl glycidyl ether and glycidyl ether crotonic acid That.

  Among them, the A block includes a polyalkylene glycol (meth) acrylate such as polyethylene glycol (meth) acrylate and polypropylene glycol (meth) acrylate as a copolymer component (that is, a repeating unit derived from polyalkylene glycol (meth) acrylate). Are preferred).

  The B block having a functional group containing a nitrogen atom preferably has a primary to quaternary amino group as the functional group. The content ratio of the primary to quaternary amino groups is preferably 10 mol% or more, more preferably 40 mol% or more of the entire nitrogen atom-containing functional group in all repeating units (100 mol%) of the copolymer. .

  The amino group is preferably -NR6R7, or -NR6R7R8 + · X1- (wherein NR6, R7 and R8 each independently has a cyclic or chain-like alkyl group which may have a substituent, or a substituent. An aryl group which may be substituted, or an aralkyl group which may have a substituent, and X1 represents a counter anion when R8 is present to form a quaternary amino group. What is preferable as a repeating unit containing this is represented, for example by a following formula.

[In General Formula (4), R4 represents a hydrogen atom or a methyl group, and R5 represents an alkylene group having 1 or more carbon atoms. n3 is an integer of 0 or 1, and R6 to R8 have a cyclic or chain alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. Represents an aralkyl group which may be present, and X1 represents a counter anion when n3 = 1. ]

  Among them, R6 to R8 are preferably a methyl group, an ethyl group, a benzyl group, X1- is preferably Cl-, R5 is preferably a methylene group, an ethylene group, and R4 is preferably a hydrogen atom or a methyl group.

  Two or more repeating units containing an amino group as described above may be contained in one B block. In that case, the repeating unit containing 2 or more types of amino groups may be contained in the B block in any form of random copolymerization or block copolymerization. In addition, a repeating unit not containing an amino group may be partially contained in the B block as long as the effects of the present invention are not impaired. Examples of such a repeating unit include (meth) acrylic acid esters. Examples thereof include repeating units derived from a monomer. The content of the repeating unit not containing an amino group in the entire repeating unit (100 mol%) of the copolymer is preferably 0 to 60 mol%, more preferably 0 to 20 mol%. Most preferably, the group-free repeating unit is not contained in the B block.

That is, the acrylic block copolymer of the present invention is a copolymer of the repeating unit represented by the general formula (2) in the solvophilic A block from the viewpoint of improving dispersibility and developer solubility. 5 to 40 mol% in all repeating units (100 mol%) and 5 to 30 mol% of the repeating units represented by the general formula (3) in all repeating units (100 mol%) of the copolymer, nitrogen It is preferable that the B block having a functional group containing an atom contains a repeating unit represented by the general formula (4).
When the repeating unit represented by the general formula (4) is n3 = 1, the repeating unit may be included in the A block.

  The content of the (meth) acrylic block copolymer is preferably 1 to 70 parts by weight, more preferably 10 to 60 parts by weight with respect to 100 parts by weight of the pigment (A). When the amount of the (meth) acrylic block copolymer is 1 part by weight or more, the pigment dispersibility effect is easily obtained. Moreover, if it is 70 weight part or less, when producing the pixel pattern of a color filter by this photolithographic method using this coloring composition, alkali developability will become favorable.

<Other resin-type dispersant>
In addition to the resin-type dispersant (C), the color composition for color filter of the present invention may further contain other resin-type dispersant. Examples of the resin-type dispersant that can be used in combination include polyurethane, poly Polycarboxylic acid ester such as acrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) amine salt, polycarboxylic acid ammonium salt, polycarboxylic acid alkylamine salt, polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group -Containing polycarboxylic acid esters, their modified products, oil-based dispersants such as amides and salts thereof formed by the reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group, (meth) acrylic acid-styrene Copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-male Phosphate copolymers, polyvinyl alcohol, water-soluble resin or a water-soluble polymer compounds such as polyvinyl pyrrolidone, polyester, modified polyacrylate, ethylene oxide / propylene oxide adduct can be used phosphate ester-based or the like.

  Examples of commercially available resin-type dispersants that can be used in the present invention include DIsperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, manufactured by Big Chemie. 165, 166, 167, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 9076, 9077, or BYK-LPN6919, 21324, 21407, or AntI-Terra-U, 203, 204, Or BYK-P104, P104S, 220S, or SOLPERSE-3000, 9000, 13240, 13650, 13940, 17000, 1800 manufactured by Nihon Lubrizol Corporation, such as LactImon, LactImon-WS, or Bykumen 20,000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32600, 34750, 36600, 38500, 41000, 41090, 53095, 76500, etc., EFKA-46, 47, 48, manufactured by Fuka Chemicals 452, LP4008, 4009, LP4010, LP4050, LP4055, 400, 401, 402, 403, 450, 451, 453, 4540, 4550, LP4560, 120, 150, 1501, 1502, 1503, 4300, 4330, etc. Examples include Addispar PA111, PB711, PB821, PB822, and PB824 manufactured by the company.

<Pigment derivative>
The coloring composition for a color filter of the present invention may further contain an organic pigment acidic derivative or a pigment derivative that is a metal salt thereof. An acidic derivative of an organic pigment or a metal salt thereof has a great effect of preventing reaggregation of the pigment after dispersion because it further promotes the pigment adsorption of the pigment and the resin-type dispersant and improves the dispersibility of the pigment. Therefore, when a colored composition obtained by dispersing a pigment in a pigment carrier using an acidic derivative of an organic pigment or a metal salt thereof, a color filter having excellent stability can be obtained. Furthermore, a resin-type dispersant which is an AB block copolymer or a B-A-B block copolymer, comprising an A block having solvophilicity and a B block having a functional group containing a nitrogen atom, Dispersibility improves more by using it simultaneously. This is considered to promote the pigment adsorption of the dispersant by the acid-base interaction between the acidic substituent of the derivative arranged near the pigment and the basic substituent of the dispersant.

The structure of an acidic derivative of an organic pigment or a metal salt thereof is a compound represented by the following general formula (5).
P-Lx General formula (5)
(However,
P: organic pigment residue,
L: acidic substituent,
x: A hydrogen atom or a metal ion. )

  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; copper phthalocyanine, halogenated copper phthalocyanine, zinc phthalocyanine, halogenated zinc phthalocyanine, Phthalocyanine pigments such as metal-free phthalocyanine; Anthraquinone pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone; quinacridone pigment; dioxazine pigment; perinone pigment; Thioindigo pigments; isoindoline pigments; isoindolinone pigments; selenium pigments; quinophthalone pigments; dioxazine pigments; metal complex pigments.

  In the present invention, the total amount of the organic pigment acid derivative or the metal salt thereof is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, and most preferably 3 parts by weight with respect to 100 parts by weight of the colorant (A). It is more than part by weight. When the amount is less than 0.5 part by weight, the contrast ratio may decrease due to a process involving high heat during the production of the color filter. Moreover, it is preferably 40 parts by weight or less, and most preferably 20 parts by weight or less. If it exceeds 40 parts by weight, the light resistance may deteriorate.

  The acidic derivative of an organic pigment or a metal salt thereof may be used alone or may contain both an acidic derivative and a metal salt, and each of them may be used in combination of two or more or other pigment derivatives.

  Examples of the pigment derivative that can be used in combination with an acidic derivative of the organic pigment or a metal salt thereof include, for example, JP-A 63-305173, JP-B 57-15620, JP-B 59-40172, Examples thereof include those described in JP-A 63-17102, JP-B-5-9469 and the like.

<Solvent>
As the solvent, the pigment (A) is sufficiently dispersed in the binder resin (B) together with the resin-type dispersant (C), and the color composition of the present invention is dried on a substrate such as a glass substrate with a dry film thickness of 0.2 to 0.2. It is used to make it easy to form a filter segment by coating to 5 μm.
As the solvent, 1,2,3-trichloropropane, 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-propyl acetate, N- Methylpyrrolidone, 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 Recall monomethyl 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 Pill 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-acetate Chill, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.
These solvents can be used singly or in combination of two or more at any ratio as required.

  The content of the solvent is 800 to 4000 parts by weight with respect to 100 parts by weight of the pigment (A), so that the coloring composition is adjusted to an appropriate viscosity, and a desired filter segment having a uniform film thickness is obtained. It is preferable because it can be formed.

<Photopolymerization initiator (D)>
In the colored composition of the present invention, the composition is cured by ultraviolet irradiation and a photopolymerization initiator (D) is added to form a filter segment by a photolithography method, and a solvent development type or alkali development type photosensitivity is added. It can be prepared in the form of a colored composition.

As photopolymerization initiator (D), 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl Acetophenone compounds such as 1- [4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether Or benzoin compounds such as benzyldimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3 Benzophenone compounds such as', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4- Thioxanthone compounds such as diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-me Xylphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloro Methyl) -s-triazine, 2,4-bis (trichloromethyl) -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, or 2,4-trichloromethyl- Triazine compounds such as (4′-methoxystyryl) -6-triazine; ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3 Yl]-, 1- (0-acetyloxime), 1,2-octadion-1- [4- (phenylthio)-, 2- (O-benzoyloxime)] and the like; bis (2,4 , 6-trimethylbenzoyl) phenylphosphine oxide or phosphine compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; Compounds: carbazole compounds; imidazole compounds; or titanocene compounds.
These photoinitiators can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

Among these, the photopolymerization initiator (D) includes at least one photopolymerization initiator (D1) selected from the group consisting of acetophenone compounds, phosphine compounds, imidazole compounds, and oxime ester compounds. It is preferable.
By including these photopolymerization initiators (D1), the pattern shape and linearity of the filter segment become better.

  The content of the photopolymerization initiator (D) is preferably 5 to 200 parts by weight with respect to 100 parts by weight of the pigment (A), and 10 to 150 parts by weight from the viewpoint of photocurability and developability. Is more preferable.

<Sensitizer (E)>
Furthermore, the coloring composition for a color filter of the present invention can contain a sensitizer.
Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapirazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphyrin derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 ', or 4,4'-tetra (t-butylperoxycarbonyl) benzopheno And 4,4′-diethylaminobenzophenone.
These sensitizers can be used singly or in combination of two or more at any ratio as necessary.

  More specifically, edited by Shin Okawara et al., “Dye Handbook” (1986, Kodansha), edited by Shin Okawara et al., “Chemistry of Functional Dye” (1981, CMC), edited by Tadasaburo Ikemori et al. Examples include, but are not limited to, sensitizers described in "Special Functional Materials" (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.

  The content of the sensitizer is preferably 3 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator (D) contained in the colored composition, and 5 to 5 from the viewpoint of photocurability and developability. More preferably, it is 50 parts by weight.

<Photopolymerizable compound (H)>
The photopolymerizable compound used in the present invention includes a monomer or oligomer that forms a resin by being cured by ultraviolet rays or heat.
Examples of the photopolymerizable compound include methyl (meth) acrylate, ethyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and cyclohexyl (meth) acrylate. , Β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylol Propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (Meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, (meth) acrylic acid ester of methylolated melamine, epoxy Various acrylic and methacrylic esters such as (meth) acrylate and urethane acrylate, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N- Examples thereof include hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile and the like. These can be used alone or in admixture of two or more.
These photopolymerizable compounds can be used singly or in combination of two or more at any ratio as required.

  The content of the photopolymerizable monomer (H) is preferably 10 to 300 parts by weight with respect to 100 parts by weight of the pigment (A), and 10 to 200 parts by weight from the viewpoint of photocurability and developability. More preferably.

<Multifunctional thiol (F)>
The coloring composition of the present invention can contain a polyfunctional thiol (F). A polyfunctional thiol is a compound having two or more thiol (SH) groups.
When the polyfunctional thiol is used together with the above-mentioned photopolymerization initiator (D), a thiyl radical that acts as a chain transfer agent and is less susceptible to polymerization inhibition by oxygen is generated in the radical polymerization process after light irradiation. The coloring property composition has high sensitivity. In particular, a polyfunctional aliphatic thiol in which an SH group is bonded to an aliphatic group such as methylene or ethylene group is preferable.

Examples of the polyfunctional thiol include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, and ethylene glycol bisthiopropioate. , Trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolethane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), trimethylolpropane tris (3- Mercaptopropionate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakis (3-mercaptopropioate) Dipentaerythritol hexakis (3-mercaptopropionate), trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s -Triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s-triazine and the like.
These polyfunctional thiols can be used singly or in combination of two or more in any ratio as necessary.

The content of the polyfunctional thiol is preferably 0.05 to 100 parts by weight, more preferably 1.0 to 50.0 parts by weight with respect to 100 parts by weight of the pigment (A).
By using 0.05 part by weight or more of polyfunctional thiol, better development resistance can be obtained. When a monofunctional thiol having one thiol (SH) group is used, such an improvement in development resistance cannot be obtained.

<Ultraviolet absorber (G)>
The photosensitive coloring composition of the present invention can contain an ultraviolet absorber. By containing the ultraviolet absorber, the shape and resolution of the pattern can be controlled.

Examples of the ultraviolet absorber include 2- [4-[(2-hydroxy-3- (dodecyl and tridecyl) oxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl). -1,3,5-triazine, 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine, etc. Hydroxyphenyltriazine, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, Benzotriazoles such as 2- (3-tbutyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2,4- Benzophenone series such as hydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, salicylate series such as phenyl salicylate, p-tert-butylphenyl salicylate, Cyanoacrylates such as ethyl-2-cyano-3,3′-diphenylacrylate, 2,2,6,6, -tetramethylpiperidine-1-oxyl (triacetone-amine-N-oxyl), bis (2, 2,6,6-tetramethyl-4-piperidyl) -sebacate, poly [[6-[(1,1,3,3-tetrabutyl) amino] -1,3,5-triazine-2,4-diyl] And hindered amines such as [(2,2,6,6-tetramethyl-4-piperidinyl) imino].
These ultraviolet absorbers can be used singly or in combination of two or more at any ratio as required.

Content of a ultraviolet absorber is 0.01-20 weight part with respect to 100 weight part of pigments (A), Preferably it can be used in the quantity of 0.05-10 weight part.
By using 0.01 part by weight or more of the ultraviolet absorber, better resolution can be obtained.

<Polymerization inhibitor>
The photosensitive coloring composition of the present invention can contain a polymerization inhibitor. By containing a polymerization inhibitor, the shape and resolution of the pattern can be controlled.

Examples of the polymerization inhibitor include hydroquinone such as methyl hydroquinone, t-butyl hydroquinone, 2,5-di-t-butyl hydroquinone, 4-benzoquinone, 4-methoxyphenol, 4-methoxy-1-naphthol, and t-butylcatechol. Derivatives and phenolic compounds, amine compounds such as phenothiazine, bis- (1-dimethylbenzyl) phenothiazine, 3,7-dioctylphenothiazine, copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate, manganese diphenyldithiocarbamate, etc. And manganese salt compounds, 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine, N-nitrosophenylhydroxylamine Nitroso compounds and their ammonium salts or aluminum salts and the like.
These polymerization inhibitors can be used singly or as a mixture of two or more at any ratio as required.

The content of the polymerization inhibitor can be used in an amount of 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight with respect to 100 parts by weight of the pigment (A).
Better resolution can be obtained by using 0.01 parts by weight or more of the polymerization inhibitor.

<Storage stabilizer (J)>
The coloring composition of the present invention can contain a storage stabilizer. By containing a storage stabilizer, the viscosity with time of the composition can be stabilized.
Examples of the storage stabilizer include 2,6-bis (1,1-dimethylethyl) -4-methylphenol, pentaerystyryl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl). Propionate], hindered phenols such as 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) 1,3,5-triazine, tetraethylphosphine, tri Organic phosphines such as phenylphosphine and tetraphenylphosphine, phosphites such as zinc dimethyldithiophosphate, zinc dipropyldithiophosphate and molybdenum dibutyldithiophosphate, sulfurs such as dodecyl sulfide and benzothiophene, benzyltrimethyl chloride, Quaternary ammonium chloride such as diethylhydroxyamine , Lactic acid, and organic acids and their methyl ethers such as oxalic acid.
These storage stabilizers can be used singly or as a mixture of two or more at any ratio as required.

The content of the storage stabilizer can be used in an amount of 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight with respect to 100 parts by weight of the pigment (A).
By using 0.01 part by weight or more of the storage stabilizer, the temporal stability of the coloring composition is improved.

<Other ingredients>
The coloring composition of the present invention may contain an adhesion improver such as a silane coupling agent or an amine compound that has a function of reducing dissolved oxygen in order to improve adhesion to a transparent substrate or the like. it can.

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 ( Aminoethyl) γ-aminopropyl Reethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N Examples include silane coupling agents such as aminosilanes such as -phenyl-γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane.
These adhesion improvers can be used singly or in combination of two or more at any ratio as required.

  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 pigment (A).

Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4 -2-ethylhexyl dimethylaminobenzoate, N, N-dimethyl paratoluidine, etc. are mentioned.
These amine compounds can be used singly or in combination of two or more at any ratio as required.

<The manufacturing method of a coloring composition>
The coloring composition of the present invention comprises a three-roll mill, a two-roll mill, and a pigment (A) in a colorant carrier and / or solvent such as a binder resin (B), preferably together with a resin-type dispersant (C). The pigment dispersion is finely dispersed using various dispersing means such as a sand mill, a kneader, and an attritor, and a photopolymerization initiator (D), a binder resin (B), and a photopolymerizable compound are produced. (H), optionally sensitizer (E), polyfunctional thiol (F), ultraviolet absorber (G), polymerization inhibitor, storage stabilizer (J), solvent, and other components are mixed and stirred for production. Can do. In addition, a coloring composition containing two or more pigments is prepared by mixing each pigment dispersion separately in a colorant carrier and / or a solvent, and further mixing a photopolymerization initiator (D) or photopolymerization. It can be produced by mixing and stirring a functional compound or the like.

<Removal of coarse particles>
The colored composition is removed by means of centrifugal separation, sintering filter, membrane filter, etc. to remove coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more and coarse particles It is preferable to carry out.

<Color filter>
Next, the color filter of the present invention will be described.
The color filter of the present invention is provided with a filter segment formed on the base material from the coloring composition for a color filter of the present invention. For example, a black matrix and red, green, and blue filter segments are provided. Can be provided. The filter segment may further include a magenta filter segment, a cyan filter segment, and a yellow filter segment.

  As a substrate such as a transparent substrate, a glass plate such as soda lime glass, low alkali borosilicate glass or non-alkali aluminoborosilicate glass, or a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate is used. 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 in order to drive the liquid crystal after forming the panel.

  The dry film thickness of the filter segment is preferably 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.

  The formation of each color filter segment by photolithography is performed by the following method. That is, the photosensitive coloring composition prepared as a solvent developing type or alkali developing type colored resist material has a dry film thickness of 0. 0 on a transparent substrate by a coating method such as spray coating, spin coating, slit coating or roll coating. It apply | coats so that it may become 2-10 micrometers. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film.

  Thereafter, the filter segment can be formed by immersing in a solvent or an alkaline developer, or spraying the developer with a spray or the like to remove the uncured portion to form a desired pattern. Furthermore, in order to accelerate the polymerization of the filter segment formed by development, heating can be performed as necessary. According to the photolithography method, a filter segment with higher accuracy than the printing method can be formed.

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.
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.
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. After forming, UV exposure can also be performed.

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

  The colored composition of the present invention can be used in any of the methods described above, but is most suitable for the photolithography method.

  A black matrix can be formed in advance before forming each color filter segment on a transparent substrate or a reflective substrate. As the black matrix, a chromium, chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but is not limited thereto. In addition, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then each color filter segment may be formed. 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 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, “parts” and “%” represent “parts by weight” and “% by weight”, respectively. “PGMAC” means propylene glycol monomethyl ether acetate.

  The weight average molecular weight (Mw) of the resin, the acid value of the resin or resin-type dispersant, the amine value of the resin-type dispersant, and the contrast ratio of the coating film are as follows.

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

<Acid value of resin or resin type dispersant>
The acid value was determined by potentiometric titration using a 0.1N potassium hydroxide / ethanol solution. An acid value shows the acid value of solid content.

<Amine value of resin-type dispersant>
The amine value was determined by potentiometric titration using a 0.1N aqueous hydrochloric acid solution, and then converted to an equivalent of potassium hydroxide. The amine value indicates the amine value (mgKOH / g) of the solid content.

<Contrast ratio of coating film>
The light emitted from the backlight unit for liquid crystal display passes through the polarizing plate, is polarized, passes through the dried coating film of the colored composition applied on the glass substrate, and reaches the polarizing plate. If the polarizing planes of the polarizing plate and the polarizing plate are parallel, light is transmitted through the polarizing plate, but if the polarizing plane is perpendicular, the light is blocked by the polarizing plate. However, when the light polarized by the polarizing plate passes through the dried coating film of the colored composition, scattering by the pigment particles occurs, resulting in deviation in a part of the polarization plane. When the amount of light transmitted through the plate is reduced and the polarizing plate is perpendicular, part of the light is transmitted through the polarizing plate. This transmitted light was measured as the luminance on the polarizing plate, and the ratio (contrast ratio) between the luminance when the polarizing plate was parallel and the luminance when it was orthogonal was calculated.
(Contrast ratio) = (Luminance when parallel) / (Luminance when direct)
A color luminance meter ("BM-5A" manufactured by Topcon Corporation) was used as the luminance meter, and a polarizing plate ("NPF-G1220DUN" manufactured by Nitto Denko Corporation) was used as the polarizing plate. In the measurement, a black mask with a 1 cm square hole was applied to the measurement portion in order to block unnecessary light.

  Then, the manufacturing method of the resin-type dispersing agent, binder resin solution, pigment derivative, refinement | purification pigment, and pigment dispersion which were used by the Example and the comparative example is demonstrated. Resin-type dispersant C1-2 and later were produced with reference to the synthesis method disclosed in Patent Document 6, but may be synthesized by other production methods of the same document or the method of C1-1 as necessary.

<Method for producing resin-type dispersant>
(Resin Dispersant Solution C1-1)
In a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube and a condenser, 80 parts of methyl ethyl ketone, 2.8 parts of sparteine, 1.9 parts of ethyl bromoisobutyrate, and n-butyl methacrylate 12. Eight parts, 13.7 parts of 2-ethylhexyl methacrylate, 25.6 parts of methyl methacrylate, 17.1 parts of benzyl methacrylate, and 13.7 parts of ethyl triglycol methacrylate were charged and heated to 40 ° C. under a nitrogen stream. 1.1 parts of cuprous chloride was added and the temperature was raised to 75 ° C. to initiate polymerization. After polymerization for 3 hours, the polymerization solution was sampled, and after confirming that the polymerization progressed by 95% or more by H-NMR, 23.9 parts of dimethylaminoethyl methacrylate and 20.0 parts of methyl ethyl ketone were added as B block components. Further, polymerization was performed. After 2 hours, it was confirmed that the polymerization yield was 97% or more from the solid content of the polymerization solution, and the polymerization was stopped by cooling to room temperature. 100 parts of the resulting resin solution was diluted with 100 parts of methyl ethyl ketone, 60 parts of cation exchange resin “Diaion PK228LH (Mitsubishi Chemical Corporation)” was added and stirred at room temperature for 1 hour. 6 parts of 500SN (manufactured by Kyowa Chemical Industry Co., Ltd.) was added and stirred for 30 minutes. The polymerization catalyst residue was removed by removing the cation exchange resin and the adsorbent by filtration. Further, the resin-type dispersant solution was concentrated and replaced with propylene glycol monomethyl ether acetate to obtain a resin-type dispersant solution C1-1 having a solid content of 50% by weight (amine value 94 mgKOH / g). The weight average molecular weight (Mw) was 7750.

(Resin Dispersant Solution C1-2)
In a four-necked separable flask equipped with a thermometer, stirrer, distillation tube, and condenser, 30 parts of 2-methoxypropanol, 3 parts of BlocBuilder (curing rate control agent, manufactured by Arkema), and n-butyl as an A block component 13.1 parts of methacrylate, 12.1 parts of 2-ethylhexyl methacrylate, 21.5 parts of methyl methacrylate, 9.7 parts of benzyl methacrylate, and 10.6 parts of ethyl triglycol methacrylate were charged and heated to 120 ° C. under a nitrogen stream. After confirming that the polymerization progressed by 95% or more by H-NMR, 22.4 parts of dimethylaminoethyl methacrylate, 75% of 2- (acryloyloxy) -N, N, N-trimethylethaneaminium chloride were used as the B block component. The aqueous solution was added with 22.4 parts in terms of solid content and 20.0 parts of 2-methoxypropanol, and further polymerized. After 2 hours, it was confirmed that the polymerization yield was 97% or more from the solid content of the polymerization solution, and the polymerization was stopped by cooling to room temperature. The solvent was replaced with propylene glycol monomethyl ether acetate to obtain a resin-type dispersant solution C1-2 having a solid content of 50% by weight (amine value 56 mgKOH / g). The weight average molecular weight (Mw) was 8960.

(Resin type dispersant solutions C1-3 to C1-9, C2-1 to C2-4)
Resin-type dispersants (resin-type dispersant solutions C1-3 to C1-9, C2- 1 to C2-4) were synthesized.

(Resin Dispersant Solution C2-5)
In a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, 50 parts of 2-methoxypropanol, 3 parts of BlocBuilder (curing rate control agent, manufactured by Arkema), and n-butyl methacrylate 11.5 Parts, 2-ethylhexyl methacrylate 10.7 parts, methyl methacrylate 24.9 parts, benzyl methacrylate 11.8 parts, ethyl triglycol methacrylate 8.3 parts, dimethylaminoethyl methacrylate 19.0 parts, 2- (methacryloyloxy)- 13.8 parts of an N, N, N-trimethylethaneaminium chloride 75% aqueous solution in terms of solid content was charged and heated to 120 ° C. under a nitrogen stream. It was confirmed by H-NMR that the polymerization had progressed by 97% or more, and the polymerization was stopped by cooling to room temperature. The solvent was replaced with propylene glycol monomethyl ether acetate to obtain a resin type dispersant solution C2-5 (amine value 76 mgKOH / g) which is a random copolymer having a solid content of 50% by weight. The weight average molecular weight (Mw) was 8530.

  The composition of each resin type dispersant (mol% in all repeating units (100 mol%) bringing each constituent unit to the resin type dispersant), the amine value (mg KOH / g) in terms of effective solid content, and the weight average molecular weight are shown. Summarized in 1.

<Production method of fine pigment>
(Preparation of red pigment 1)
Diketopyrrolopyrrole red pigment C.I. I. 200 parts of Pigment Red 254 (“IRGAZIN RED 2030” manufactured by Ciba Japan), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of red pigment 1 were obtained.

(Preparation of red pigment 2)
Diketopyrrolopyrrole red pigment C.I. I. Pigment Red 254 and red pigment C.I. I. A red pigment 2 was obtained in the same procedure as the preparation of the red pigment 1 except that it was replaced with CI Pigment Red 177 (“Chromophthal Red A2B” manufactured by Ciba Specialty Chemicals).

(Preparation of green pigment 1)
Diketopyrrolopyrrole red pigment C.I. I. Pigment Red 254 is a halogenated zinc phthalocyanine green pigment, C.I. I. Green pigment 1 was obtained by the same procedure as the preparation of red pigment 1, except that it was replaced with CI Pigment Green 58 (“FASTOGEN GREEN A110” manufactured by DIC Corporation).

(Preparation of blue pigment 1)
Diketopyrrolopyrrole red pigment C.I. I. Pigment Red 254 is a phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 (“LIONOL BLUE ES” manufactured by Toyo Ink Manufacturing Co., Ltd.) was used, except that Green Pigment 1 was obtained in the same procedure as the preparation of Red Pigment 1.

(Preparation of yellow pigment 1)
Diketopyrrolopyrrole red pigment C.I. I. Pigment Red 254 is changed to yellow pigment C.I. I. A yellow pigment 1 was obtained by the same procedure as the preparation of the red pigment 1 except that it was replaced with CI Pigment Yellow 138 (BASF “Pariotol Yellow L 0962 HD”).

(Preparation of purple pigment 1)
Diketopyrrolopyrrole red pigment C.I. I. Pigment Red 254 is changed to yellow pigment C.I. I. Purple pigment 1 was obtained in the same procedure as the preparation of red pigment 1, except that it was replaced with CI Pigment Violet 23 ("LIONOGEN VIOLET RL" manufactured by Toyo Ink Manufacturing Co., Ltd.).

<Method for producing binder resin solution>
[Resin solution (B1-1)]
(Stage 1: Polymerization of resin main chain)
Place 100 parts of propylene glycol monomethyl ether acetate (PGMAC) in a reaction vessel equipped with a thermometer, cooling tube, nitrogen gas inlet tube, and stirrer in a separable four-necked flask, and heat to 120 ° C while injecting nitrogen gas into the vessel. At the same temperature, 16.2 parts of styrene, 35.5 parts of glycidyl methacrylate, 41.0 parts of dicyclopentanyl methacrylate, and azobisisobutyronitrile 1 as a catalyst required for the combination of the precursors at this stage 0.0 part of the mixture was added dropwise over 2.5 hours to carry out the polymerization reaction.
(Step 2: Compounding to epoxy group)
Next, the inside of the flask was purged with air, and 17.0 parts of acrylic acid and 0.3 part of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added as a catalyst required for the combination of the precursors at this stage. Reaction was performed for 5 hours, and the resin solution whose weight average molecular weight is about 12000 (measurement by GPC) was obtained. The added acrylic acid is ester-bonded to the end of the epoxy group of the glycidyl methacrylate structural unit, so that no carboxyl group is generated in the resin structure.
(Step 3: Compound to hydroxyl group)
Further, 30.4 parts of tetrahydrophthalic anhydride and 0.5 part of triethylamine were added as a catalyst required for the combination of the precursors at this stage, and the mixture was reacted at 120 ° C. for 4 hours. In the added tetrahydrophthalic anhydride, one of two carboxyl groups generated by cleavage of the carboxylic anhydride moiety is ester-bonded to a hydroxyl group in the resin structure, and the other produces a carboxyl group terminal.
(Step 4: Adjustment of nonvolatile content)
Propylene glycol monomethyl ether acetate was added so that the nonvolatile content was 40% to obtain a resin solution (B1-1).

  The molar ratio of the structural unit in the resin solution (B1-1) is as follows: tetrahydrophthalic anhydride as the structural unit (b1); 25.4%, styrene as the structural unit (b2); 19.8%, as the structural unit (b3) Dicyclopentanyl methacrylate: 23.7%, the total of glycidyl methacrylate as the other structural unit and acrylic acid ester-bonded to the glycidyl terminus; 31.1%.

[Resin solution (B1-2)]
Synthetic reaction in the same manner as the resin solution (B1-1) except that dicyclopentanyl methacrylate in the resin solution (B1-1) was changed to dicyclopentenyl methacrylate and the mixing ratio of each raw material was changed as shown in Table 2. And a resin solution (B1-2) was obtained.

[Resin solution (B1-3)]
Except that the dicyclopentanyl methacrylate in the resin solution (B1-1) was changed to dicyclopentenyloxyethyl methacrylate and the blending ratio of each raw material was changed as shown in Table 2, the same method as the resin solution (B1-1) was used. A synthetic reaction was performed to prepare a resin solution (B1-3).

[Resin solution (B1-4)]
370 parts of PGMEA was charged into a separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirring device, heated to 80 ° C., and the atmosphere in the flask was replaced with nitrogen. 18 parts of phenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toa Gosei Co., Ltd.), 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2.0 parts of 2,2′-azobisisobutyronitrile Was added dropwise over 2 hours. After dropping, the reaction was further carried out at 100 ° 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 100 ° C. for 1 hour. Next, the inside of the container was replaced with air, 0.5 parts of trisdimethylaminophenol and 0.1 part of hydroquinone were added to 9.3 parts of acrylic acid (equivalent of epoxy group), and 6 parts at 120 ° C. The reaction was continued for a while, and the reaction was terminated when the acid value of the solid content reached 0.5 to obtain an acrylic resin solution. Further, 19.5 parts of tetrahydrophthalic anhydride (equivalent of generated hydroxyl group) and 0.5 parts of triethylamine were added and reacted at 120 ° C. for 3.5 hours to obtain an acrylic resin solution.
After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and PGMAC was added to the previously synthesized resin solution so that the nonvolatile content was 20 wt%. Thus, an acrylic resin solution (B1-4) was prepared. The weight average molecular weight (Mw) was 19000.

[Resin solutions (B1-5 to 15) and (B2-1 to 3)]
The resin solutions (B1-5) to (B1-15) and (B2-1) to (B2-3)] were adjusted in the same manner as the resin solution (B1-1).

  That is, in the production method of the resin solution (B1-1), the precursors corresponding to the structural units (b1) to (b3) and other structural units, and the compounding amount (mol%) were replaced according to Table 2. In the case of a resin solution in which no GMA-AA or GMA-MAA is present in the table, all the precursors are mixed and only the production steps 1 and 4 are carried out. When GMA-AA or GMA-MAA is present in the table, and THPA is present, first, GMA and structural units (b2) and (b3) and GMA-AA or GMA-MAA in other structural units are excluded. Stage 1 of the production is performed by mixing the precursors, then stage 2 of the production is carried out with the addition of AA or MAA equal to the epoxy equivalent of GMA as a precursor, and the stage of the production with addition of THPA as the precursor. 3. Perform step 4 When GMA-AA or GMA-MAA is present and THPA is not present in the table, first, precursors excluding GMA-AA or GMA-MAA in GMA, structural units (b1) to (b3) and other structural units The body is mixed and stage 1 of manufacturing is performed, then stage 2 of manufacturing is performed by adding the epoxy equivalent of AA or MAA of GMA as a precursor, and stage 4 is further performed. The number of catalyst parts required for each stage is mixed in proportion to the total number of precursors mixed in each stage.

  Table 2 shows the compositions and weight ratios of the obtained resin solutions (B1-1 to 15) and resin solutions (B2-1 to 2). The values in parentheses are mol% in all repeating units (100 mol%) that bring each structural unit to the binder resin (B).

Explanation of Precursors of Structural Units and Abbreviations of Structural Units in Table 2 MAA: Methacrylic acid THPA: Tetrahydrophthalic anhydride (4-cyclohexene-1,2-dicarboxylic anhydride BzMA: Benzyl methacrylate St: Styrene M110: Paracumyl Phenolethylene oxide modified acrylate DCPMA: Dicyclopentanyl methacrylate GMA: Glycidyl methacrylate GMA-AA: Acrylic acid added to the structural unit GMA and bonded GMA-MAA: A methacrylic acid added to the structural unit GMA and bonded BMA: n-butyl methacrylate

[Preparation of resin solution (B2-3)]
370 parts of cyclohexanone was put in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, 20.0 parts of methacrylic acid, 10.0 parts of methyl methacrylate, 55.0 parts of n-butyl methacrylate at the same temperature, A mixture of 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. The resin solution (B2-3) was prepared by addition. The weight average molecular weight (Mw) was 40000.

[Example 1]
(Coloring composition (DG1-1))
Production and Evaluation of Green Colored Composition A colored composition (DG1-1) was produced through Production Stage 1 and Production Stage 2, and the brightness, contrast ratio, and dispersion stability were evaluated after film formation, and are shown in Table 3.

(Creation stage 1)
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. A pigment dispersion was prepared by filtration through a filter.

Green pigment 1: 12.0 parts Yellow pigment 1: 4.0 parts Binder resin solution (B2-3): 8.0 parts Propylene glycol monomethyl ether acetate (PGMAC): 70.0 parts Resin-type dispersant solution (C1- 1): 6.0 parts

(Creation stage 2)
The following mixture was added, the following mixture was stirred and mixed so as to be uniform, and then filtered through a 5.0 μm filter to prepare a pigment dispersion.

Preparation 1 pigment dispersion: 60.0 parts Binder resin solution (B1-1): 18.0 parts Propylene glycol monomethyl ether acetate (PGMAC): 22.0 parts

(Brightness (Y value), contrast ratio (CR value) evaluation)
The obtained green coloring composition is formed on a 100 mm × 100 mm, 0.7 mm thick glass substrate so that x = 0.300 and y = 0.600 (within plus or minus 0.001) in a C light source. And dried in a hot air oven at 70 ° C. for 20 minutes, and further heated at 230 ° C. for 60 minutes to obtain a coating film. Thereafter, the brightness (Y value) and contrast ratio (CR value) of the obtained coated substrate were measured.
The chromaticity was measured with a microspectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.).

(Dispersion stability evaluation)
The initial viscosity (η0: mPa · s) and the viscosity after storage for 7 days in a constant temperature room at 40 ° C. (η7: mPa · s) were measured to determine the dispersion stability. Evaluation was made according to the following criteria.
：: η7 / η0 is less than 1.10, almost no increase in viscosity is observed, and dispersion stability is good. ◯: η7 / η0 is 1.10 or more and less than 1.20, and the viscosity is slightly increased. Is excellent in dispersion stability Δ: η7 / η0 is 1.20 or more and less than 1.50, the viscosity is slightly increased and the dispersion stability is slightly inferior ×: η7 / η0 is 1.50 or more, the viscosity Dispersion stability is inferior

[Examples 2-135]
(Coloring composition (DG1-2 to 135))
In Example 1 (colored composition (DG1-1)), the resin-type dispersant solution (C1-1) in preparation stage 1 was prepared in the same number of parts (C1-1) to (C1-9). 2 except that the main component resin solution (B1-1) 2 was replaced in the range of the same number of parts (B1-1) to (B1-15) to prepare colored compositions (DG1-2) to (DG1-135). In the same manner as in Example 1 (coloring composition (DG1-1)), coloring compositions (DG1-2 to 135) were obtained. Tables 3 to 5 show the relationship among the resin-type dispersant solution, the main component resin solution, and the evaluation results of each example.
However, Examples 1, 3, 4, 9, 10, 12, 13, 18, 19, 21, 22, 27, 28, 30, 31, 36, 37, 39, 40, 45, 46, 48, 49, 54, 55, 57, 58, 63, 64, 66, 67, 72, 73, 75, 76, 81, 82, 84, 85, 90, 91, 93, 94, 99, 100, 102, 103, 108, Reference numerals 109, 111, 112, 117, 118, 120, 121, 117, 118, 120, 121, 126, 127, 129, 130, and 135 are reference examples.

[Comparative Examples 1 to 89]
(Coloring composition (DG2-1 to 89))
In Example 1 (coloring composition (DG1-1)), the resin-type dispersant solution (C1-1) in the production stage 1 was used in the same number of parts (C1-1) to (C1-9) or (C2-1). ) To (C2-5), the same number of (B1-1) to (B1-15) or (B2-1) to (B2-) The same test as in Example 1 (colored composition (DG1-1)) was conducted except that the colored compositions (DG2-1) to (DG2-89) were produced in the range of 2). Tables 3 to 5 show the relationship among the resin-type dispersant solution, the main component resin solution, and the evaluation results of each comparative example.

[Example 201]
(Coloring composition (DB1-201))
Production and Evaluation of Blue Colored Composition Green Pigment 1 (12.0 parts) of Example 1 (Colored Composition (DG1-1)) was replaced with Blue Pigment 1 (13.0 parts), and Yellow Pigment 1 (4.0). Part) was replaced with purple pigment 1 (3.0 parts), and the main component resin solution (B1-1) in preparation stage 2 was replaced with resin solution (B1-6), and coloring composition (DG1-1) A blue colored composition (DB1-201) was obtained in the same procedure as described above.

  Except that the film thickness at the time of evaluation of brightness (Y value) and contrast ratio (CR value) was set to x = 0.150 and y = 0.060 (within plus or minus 0.001) with a C light source, the green coloring composition The blue colored composition (DB1-201) was evaluated in the same procedure as described above.

[Examples 202 to 218]
(Coloring composition (DB1-202-218))
In Example 201 (colored composition (DB1-201)), the resin-type dispersant solution (C1-1) in Preparation Step 1 was prepared in the same number of parts (C1-1) to (C1-9). 2 except that the main component resin solution (B1-6) of 2 was replaced in the range of the same number of (B1-6) to (B1-7) to prepare colored compositions (DB1-202) to (DB1-218). Colored compositions (DB1-202 to 218) were obtained in the same manner as Example 201 (colored composition (DB1-201)). Table 6 shows the relationship among the resin-type dispersant solution, the main component resin solution, and the evaluation results of each example.

[Comparative Examples 201-217]
(Coloring composition (DB2-201 to 217))
In Example 201 (coloring composition (DB1-201)), the resin-type dispersant solution (C1-1) in the preparation stage 1 was used in the same number of parts (C1-1) to (C1-9) or (C2-1). ) To (C2-5), the main component resin solution (B1-6) in the preparation stage 2 is replaced with the same number of (B1-6) to (B1-7) or (B2-1). The colored compositions (DB2-201 to 217) were obtained in the same manner as in Example 201 (colored composition (DB1-201)) except that the colored compositions (DB2-201) to (DB2-217) were produced. It was. Table 6 shows the relationship among the resin-type dispersant solution, the main component resin solution, and the evaluation results of each comparative example.

[Example 301]
(Coloring composition (DR1-301))
Preparation and Evaluation of Red Colored Composition Green Pigment 1 (12.0 parts) of Example 1 (Colored Composition (DG1-1)) was replaced with Red Pigment 1 (13.5 parts) and Yellow Pigment 1 (4.0). Part) is replaced with red pigment 2 (2.5 parts), and the main component resin solution (B1-1) in the preparation stage 2 is replaced with the resin solution (B1-6), and the coloring composition (DG1-1). A red colored composition (DR1-301) was obtained in the same procedure.

  Except that the film thickness at the time of evaluation of brightness (Y value) and contrast ratio (CR value) was set to x = 0.640 and y = 0.330 (within plus or minus 0.001) with a C light source, the green coloring composition The red coloring composition (DR1-301) was evaluated in the same procedure as described above.

[Examples 302 to 318]
(Coloring composition (DR1-302 to 318))
In Example 301 (colored composition (DR1-301)), the resin-type dispersant solution (C1-1) of preparation step 1 was prepared in the same number of parts (C1-1) to (C1-9). 2 except that the main component resin solution (B1-6) of 2 was replaced in the range of the same number of (B1-6) to (B1-7) to prepare colored compositions (DR1-302) to (DR1 -318). In the same manner as in Example 301 (coloring composition (DR1-301)), coloring compositions (DR1-302 to 318) were obtained. Table 7 shows the relationship among the resin-type dispersant solution, the main component resin solution, and the evaluation results of each example.

[Comparative Examples 301-325]
(Coloring composition (DR2-301 to 317))
In Example 301 (coloring composition (DR1-301)), the resin-type dispersant solution (C1-1) in the preparation stage 1 was used in the same number of parts (C1-1) to (C1-9) or (C2-1). ) To (C2-5), the main component resin solution (B1-6) in the preparation stage 2 is replaced with the same number of (B1-6) to (B1-7) or (B2-1). The colored compositions (DR2-301 to 317) were obtained in the same manner as in Example 301 (colored composition (DR1-301)) except that the colored compositions (DR2-301) to (DR2-317) were produced. It was. Table 7 shows the relationship among the resin-type dispersant solution, the main component resin solution, and the evaluation results of each comparative example.

  An AB block copolymer or a B-A-B block copolymer comprising an A block having a solvophilic property having a specific structure and a B block having a functional group containing a nitrogen atom, and an amine value However, the coloring composition for color filters of the present invention containing a resin type dispersant (C) which is a (meth) acrylic block copolymer having an effective solid content of 10 mgKOH / g or more and 99 mgKOH / g or less is represented by the general formula: (1) High brightness (Y value), contrast ratio (CR value) and dispersion stability in combination with a binder resin containing 2 to 60 mol% of repeating units having the structural unit (b1) represented in the resin A good result was obtained.

  In particular, the interaction between the aromatic ring component (general formula (2)) of the resin-type dispersant (C) and the structural unit (b1) in the binder resin (B) is recognized, and an appropriate amount is present in each resin composition. Then, Y value and CR value are improved. Furthermore, the aromatic component in the binder resin (B) and the structural unit (b2) are also easily imagined to have an affinity due to the π-π interaction with the aromatic component in the block copolymer, which improves the CR value. It is recognized that it has contributed. It is a necessary condition that the resin-type dispersant (C) is a block copolymer. When the resin-type dispersant (C) is a random copolymer, the performance of the coloring composition is lowered with a decrease in dispersion stability. Further, the solvophilic group (general formula (2)) in the resin-type dispersant (C), the structural unit (b3) in the binder resin (B), and the functional group containing nitrogen atom ((general formula (4)) are: It contributes to the balance of dispersion stability, and it is recognized that stability is lowered when these are lacking or too much.

[Examples 401 to 442, Comparative Examples 401 to 420]
(Photosensitive coloring composition (RG-1 to 32, RB-1 to 15, RR-1 to 15))
Each material was mixed and stirred with the compositions and blending amounts shown in Tables 8 to 10, filtered through a 1 μm filter, and photosensitive colored compositions (RG-1 to 32, RB-1 to 15, RR-1 to 15). )

Abbreviations in Tables 8 to 10 are shown below.
<Photopolymerization initiator (D)>
Photoinitiator D1: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino
Propan-1-one
("Irgacure 907" manufactured by Ciba Japan)
Photopolymerization initiator D2: 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1
-[4- (4-morpholinyl) phenyl] -1-butanone
("Irgacure 379" manufactured by Ciba Japan)
Photopolymerization initiator D3: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxa
Id
("Lucirin TPO" manufactured by BASF)
Photoinitiator D4: 2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-teto
Raphenyl-1,2'-biimidazole
(Kurokin Kasei Co., Ltd. “Biimidazole”)
Photopolymerization initiator D5: p-dimethylaminoacetophenone
("DMA" manufactured by Daiki Fine)
Photopolymerization initiator D6: ethane-1-one, 1- [9-ethyl-6- (2-methylbenzoy)
) -9H-carbazol-3-yl], 1- (O-acetyloxime)
("Irgacure OXE02" manufactured by Ciba Japan)

<Sensitizer (E)>
Sensitizer E1: 2,4-Diethylthioxanthone
(“Kayacure DETX-S” manufactured by Nippon Kayaku Co., Ltd.)
<Photopolymerizable compound (H)>
Photopolymerizable compound H1: Dipentaerythritol hexaacrylate
("Aronix M-402" manufactured by Toagosei Co., Ltd.)
<Multifunctional thiol (F)>
Multifunctional thiol F1: trimethylolethane tris (3-mercaptobutyrate)
("TEMB" manufactured by Showa Denko KK)
<Ultraviolet absorber (G)>
UV absorber G1: 2- [4-[(2-hydroxy-3- (dodecyl and tridecyl))
Oxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis
(2,4-Dimethylphenyl) -1,3,5-triazine
("TINUVIN400" manufactured by Ciba Japan)
UV absorber G2: 2- (2H-benzotriazol-2-yl) -4,6-bis (1-
Methyl-1-phenylethyl) phenol
("TINUVIN900" manufactured by Ciba Japan)
<Storage stabilizer (J)>
Storage stabilizer J1: 2,6-bis (1,1-dimethylethyl) -4-methylphenol
("BHT" manufactured by Honshu Chemical Industry Co., Ltd.)
Storage stabilizer J2: Triphenylphosphine
("TPP" manufactured by Hokuko Chemical Co., Ltd.)
<Solvent>
PGMAC: Propylene glycol monomethyl ether acetate

[Evaluation of photosensitive coloring composition]
About the obtained photosensitive coloring composition (RG-1 to 32, RB-1 to 15, RR-1 to 15), brightness (Y value), contrast ratio (CR value), sensitivity, linearity, pattern shape, Resolution, development resistance, chemical resistance, and stability over time were evaluated by the following methods. The results are shown in Table 11. In the evaluation results, ◎ is a very good level, ◯ is a good level, Δ is a level that does not interfere with use, and x is a level that is not preferable for use.

(Brightness (Y value), contrast ratio (CR value) evaluation)
The obtained photosensitive coloring composition was post-treated on a 100 mm × 100 mm, 0.7 mm thick glass substrate with a C light source, and then x = 0.300 and y = 0.600 in the green photosensitive coloring composition. In the blue photosensitive coloring composition, x = 0.150 and y = 0.060, and in the red photosensitive coloring composition, x = 0.640 and y = 0.330 were applied so that the film thickness was 70. After drying in a hot air oven at 20 ° C. for 20 minutes, using an ultra-high pressure mercury lamp, UV exposure was performed with an integrated light quantity of 150 mJ, followed by heating at 230 ° C. for 1 hour and cooling to obtain a red coating film. Thereafter, the brightness (Y) and contrast ratio (CR) of the obtained coated substrate were measured.
The chromaticity was measured with a microspectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.).

(Sensitivity, linearity, pattern shape, resolution, development resistance, chemical resistance evaluation)
After coating the obtained photosensitive coloring composition on a 100 mm × 100 mm, 0.7 mm thick glass substrate, the solvent was removed by heating at 70 ° C. for 20 minutes in a clean oven to form a coating film of about 2 μm. Obtained. Next, the substrate was cooled to room temperature, and then exposed to ultraviolet rays through a photomask having a stripe pattern of 100 μm width (pitch 200 μm) and 25 μm width (pitch 50 μm) using an ultrahigh pressure mercury lamp. Thereafter, this substrate was spray-developed using a sodium carbonate aqueous solution at 23 ° C., washed with ion-exchanged water, air-dried, and heated at 230 ° C. for 330 minutes in a clean oven. The spray development was performed in the shortest time during which a pattern can be formed without any development remaining on the coating film of each photosensitive coloring composition, and this was set as an appropriate development time.
The film thickness of the coating film was determined using Dektak 3030 (manufactured by Nippon Vacuum Technology Co., Ltd.).

(Sensitivity evaluation)
The pattern film thickness in the 100 μm photomask portion of the filter segment formed by the above method was measured, and the minimum exposure amount that was 90% or more with respect to the film thickness after coating was evaluated. The smaller the minimum exposure, the higher the sensitivity and the better the photosensitive coloring composition.
The rank of evaluation is as follows.
○: Less than 50 mJ / cm ² Δ: 50 mJ / cm ² or more and less than 100 mJ / cm ² ×: 100 mJ / cm ² or more

(Linearity evaluation)
The pattern at the 100 μm photomask portion of the filter segment formed by the above method was evaluated by observation using an optical microscope. The rank of evaluation is as follows.
○: Good linearity △: Partially poor linearity ×: Poor linearity

(Pattern shape evaluation)
The cross section of the pattern at the 100 μm photomask portion of the filter segment formed by the above method was evaluated by observation using an electron microscope. The pattern cross section has good forward taper. The rank of evaluation is as follows.
○: Cross section is forward tapered shape ×: Cross section is reverse tapered shape

(Resolution evaluation)
The pattern in the 25 μm photomask portion of the filter segment formed by the above method was evaluated by observing with an optical microscope. The rank of evaluation is as follows. The poor resolution means that adjacent stripe patterns are connected or chipped. The rank of evaluation is as follows.
◎: Good resolution and linearity ○: Slightly inferior in linearity but good resolution △: Partially poor resolution ×: Poor resolution

(Development resistance evaluation)
During spray development, the pattern film thickness at the 100 μm photomask portion of the filter segment formed by developing at twice the appropriate time was measured and compared with the pattern film thickness formed by developing at the appropriate development time. . The rank of evaluation is as follows.
◎: Within 20% difference in film thickness ○: Over 20% difference in film thickness, within 40%

(Chemical resistance evaluation)
The filter segment formed by the above method was immersed in an N-methylpyrrolidone solution for 30 minutes, then washed with ion-exchanged water, air-dried, and the pattern on the 100 μm photomask portion was observed and evaluated using an optical microscope. The rank of evaluation is as follows.
◎: Good with no change in appearance and color ○: Some wrinkles are generated, but good with no change in color △: Slight color loss occurs ×: Peeling or color loss occurs

(Evaluation of temporal stability of colored composition)
About the obtained photosensitive coloring composition, the viscosity of the initial stage and 1 month after room temperature was measured, and the viscosity increase degree with respect to an initial stage viscosity was calculated and evaluated. The rank of evaluation is as follows.
(Change in viscosity with time) = | [(initial viscosity) − (viscosity with time)] / (initial viscosity) | × 100 (%)
◎: Viscosity increase rate is 5% or less, good ○: Viscosity increase rate is greater than 5% and less than 10% ×: Viscosity increase rate is greater than 10%

  The photosensitive coloring composition used together with the specific resin type dispersant (C) and the binder resin (B) having the structural unit (b1) in the present invention obtained high-level evaluation results in all evaluations.

Further, if the photopolymerization initiator (D) is a combination with any one of an acetophenone compound, a phosphine compound, an imidazole compound, and an oxime ester compound, the sensitivity, linearity, and resolution are better.
Furthermore, the photosensitive coloring composition containing polyfunctional thiol was more excellent in development resistance.
Further, the photosensitive coloring composition further containing an ultraviolet absorber was superior in resolution.
Further, the photosensitive coloring composition further containing a storage stabilizer was superior in stability over time.

(Manufacture of color filters)
The photosensitive coloring composition (RR-1) was applied on a 100 mm × 100 mm glass substrate with a die coater to a thickness of about 2 μm, and the solvent was removed and dried in an oven at 70 ° C. for 20 minutes. Subsequently, stripe pattern exposure was performed with ultraviolet rays using an exposure apparatus. The exposure amount was 100 mJ / cm ² . Furthermore, after spray development with a developer composed of an aqueous sodium carbonate solution to remove unexposed portions, the substrate is washed with ion-exchanged water, and this substrate is heated at 230 ° C. for 30 minutes to form a red filter segment having a line width of about 50 μm. did. Then, by the same operation, the green filter segment is used with the green photosensitive coloring composition (RG-1) next to the red filter segment, and then the blue filter segment is used with the blue photosensitive coloring composition (RB-1). A color filter having three color filter segments on the same glass substrate was obtained.
When the coloring composition for a color filter in the present invention is used, a high-definition color filter having a red filter segment having excellent color characteristics in a wide chromaticity range and good heat resistance can be produced.

Claims (4)

In the color filter coloring composition containing the pigment (A), the binder resin (B), and the resin-type dispersant (C),
The binder resin (B) contains 2 to 60 mol% of repeating units having the structure (b1) represented by the following general formula (1),
An AB block copolymer or a B-A-B block in which the resin-type dispersant (C) is composed of an A block having a solvophilic group and an aromatic ring group, and a B block having a functional group containing a nitrogen atom A copolymer comprising:
A block is a repeating unit represented by the following general formula (2) as a solvophilic group, 4 to 40 mol% in the copolymer, and a repeating unit represented by the following general formula (3) as an aromatic ring group, 4-30 mol% in the copolymer,
B block contains a repeating unit represented by the following general formula (4),
The coloring composition for color filters is an (meth) acrylic block copolymer having an amine value of 10 mgKOH / g or more and 99 mgKOH / g or less in terms of effective solid content.


[In general formula (1), a represents a carbon-carbon bond which is a single bond or a double bond. ]


[In General Formula (2), n1 represents an integer of 1 to 10, R1 represents a hydrogen atom or a methyl group, and R2 represents an alkyl group having 1 to 10 carbon atoms which may be branched. ]


[In general formula (3), R3 represents a hydrogen atom or a methyl group. n2 is an integer of 0 or 1, and φ represents an aromatic ring which may have a plurality of different substituents and may contain a 5- to 6-membered nitrogen atom. ]


[In General Formula (4), R4 represents a hydrogen atom or a methyl group, and R5 represents an alkylene group having 1 or more carbon atoms. n3 is an integer of 1 , and R6 to R8 have a cyclic or chain alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. Represents an aralkyl group, and X1 represents a counter anion . ] The binder resin (B) further comprises 2 to 80 mol% of repeating units having the structure (b2) represented by the following general formula (6) and 2 to 70 mol% of repeating units having a carboxyl group (b3). It contains, The coloring composition for color filters of Claim 1 characterized by the above-mentioned.

Structure (b2):

[In General Formula (6), R9 is one or more substituents which may be different from each other, and is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a benzene ring. Moreover, you may have a cyclic structure containing the 1 or more saturated or unsaturated heterocyclic ring which may have a substituent adjacent to a benzene ring in the broken-line part in General formula (6). ] Furthermore, at least 1 type of photoinitiator (D1) chosen from the group which consists of an acetophenone type compound, a phosphine type compound, an imidazole type compound, and an oxime ester type compound is included, The claim 1 or 2 characterized by the above-mentioned. Coloring composition for color filter. A color filter comprising a filter segment formed on the base material from the colored composition for color filter according to any one of claims 1 to 3.