JP2019109487A - Colored composition for color filter and color filter - Google Patents

Abstract

To provide a colored composition for a color filter exhibiting remarkable effects on a low contrast ratio, dispersion stability, heat resistance and solvent resistance properties, and deposition of foreign matter on a coated film when using quinacridone pigment.SOLUTION: The colored composition for a color filter, for which quinacridone pigment (A) is used as coloring agent, includes dye derivative (B), basic dispersant (C) containing an acrylic block copolymer and binder resin (D).SELECTED DRAWING: None

Description

  The present invention relates to a color filter used for a solid-state imaging device represented by a color liquid crystal display device, C-MOS (complementary metal oxide semiconductor: C-MOS), CCD (charge coupled device), etc. The present invention relates to a coloring composition for color filter to be used in the production of the present invention, and a color filter provided with a filter segment formed using the same.

  Generally, in a color liquid crystal display device, a transparent electrode for driving the liquid crystal is formed on the color filter by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is further formed thereon. There is. In order to sufficiently obtain the performance of the transparent electrode and the alignment film, a high temperature treatment of 200 ° C. or more, preferably 230 ° C. or more is generally required in the manufacturing process of forming the color filter. For this reason, at present, a method called a pigment dispersion method in which a pigment having excellent light fastness and heat resistance is used as a colorant is the mainstream of 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 or the like. That is, the display device in the ON state and the OFF state because the light leaks when the light has to be blocked (OFF state) and the transmitted light is attenuated when the light has to be transmitted (ON state). There is a problem that the above luminance ratio (contrast ratio) is low.

  Therefore, in recent years, in order to realize high brightness and high contrast of the color filter, the pigment contained in the filter segment is often used after being subjected to miniaturization processing. However, there are various types of pigments (what is called crude having a particle diameter of 10 to 100 μm produced by a chemical reaction to a mixture of primary particles and secondary particles in which the particles are aggregated by pigmentation). Even if the size is reduced by the size reduction method, pigments in which the size reduction of primary particles or secondary particles has progressed generally tend to aggregate, and when the size reduction progresses too much, a large lump of pigment solid is formed. I will. Further, the pigment which has been finely divided is dispersed in a pigment carrier containing a resin or the like, and a stable colored composition is obtained even if it is attempted to stabilize the secondary particles of the pigment as much as possible to the primary particles again. It is very difficult.

  Therefore, it is excellent in dispersibility and storage stability by a structure-controlled one having a comb structure (patent document 1), a resin type dispersant such as a polyester dispersant having a specific structure (patent document 2), etc. There are studies of colored compositions having a contrast ratio. However, the use of these resin type dispersants is not sufficient to improve the resistance of the pigment whose surface area is increased due to the progress of the pigment fineness, and the gloss of the surface of the toner of the pigment composition In the present situation, a state failure such as a decrease in leveling or a leveling failure occurs or the stability is not sufficiently secured.

  A pigment dispersion using a quinacridone pigment has been conventionally used as a red coloring composition for a color filter, but in recent years, it has attracted attention again from the viewpoint of high color reproduction. However, although it has been difficult to ensure dispersion stability and improvements have been made from the viewpoint of dye derivatives and the like (Patent Document 3), it still has problems such as improvement of contrast ratio, viscosity stability and coarse particle foreign matter. And there was a need for improvement.

  In addition, even in a solid-state imaging device using a color filter, there is a problem in that the color reproducibility is degraded due to noise due to color mixing. In particular, it is known that the image quality is deteriorated due to "cobb" (hereinafter referred to as "cobb") in which the transmissivity around 530 nm locally increases in the red filter. Therefore, in order to eliminate bumps around 530 nm, a technique using pigment red 166 is disclosed (see Patent Document 4). However, simply eliminating this hump using pigment red 166 is not practical because the transmittance at 600 nm to 700 nm is low, which causes the sensitivity of the solid-state imaging device to be lowered. Moreover, in the spectrum of the red filter, the floating of the spectrum of 400 to 450 nm causes color mixing with blue, which causes a problem that the color reproducibility of blue is deteriorated.

Unexamined-Japanese-Patent No. 11-1515 gazette WO 2008/007776 pamphlet JP, 2008-038061, A JP, 2010-085457, A

  The problems to be solved by the present invention are problems such as low contrast ratio, low transmittance, dispersion stability, heat resistance, solvent resistance, and foreign matter deposition on a coating film, which were conventionally problems when using quinacridone pigments. is there.

  The inventors of the present invention conducted intensive studies to solve the above problems, and as a result, a coloring composition for a color filter comprising a quinacridone pigment, a pigment derivative, a specific basic dispersant, and a binder resin. I found that I could solve it.

  That is, the present invention contains a quinacridone pigment (A), a pigment derivative (B), a basic dispersant (C) containing an acrylic block copolymer, and a binder resin (D). The present invention relates to a coloring composition for color filters, which is characterized.

  Further, according to the present invention, the quinacridone pigment (A) is C.I. I. Pigment red 122, C.I. I. Pigment red 202, C.I. I. Pigment red 207 and C.I. I. The present invention relates to the coloring composition for a color filter, which is at least one selected from the group consisting of C.I. Pigment Red 209.

  The present invention also relates to the coloring composition for color filters, wherein the dye derivative (B) is a sulfonated dye derivative, or a metal salt or an amine salt of a sulfonated dye derivative.

  The present invention also relates to the coloring composition for a color filter, wherein the dye skeleton of the dye derivative (B) is at least one selected from the group consisting of quinacridone dyes, isoindoline dyes, quinophthalone dyes, and anthraquinone dyes.

In the present invention, the basic dispersant (C) containing an acrylic block copolymer is a repeating unit represented by the following general formula (1), a repeating unit represented by the following general formula (2), and The present invention relates to the coloring composition for a color filter, which has a block having at least one selected from the group consisting of repeating units represented by the following general formula (3).
(In the general formula (1), R _{1 to} R ₃ each independently represent a hydrogen atom or a chain or cyclic hydrocarbon group which may have a substituent, and R _{1 to} R ₃ Two or more of them may be bonded to each other to form a cyclic structure, R ₄ represents a hydrogen atom or a methyl group, X represents a divalent linking group, and Y − represents a counter anion.
(In the general formula (2), R ₅ and R ₆ are, independently of each other, hydrogen atom, or a substituted indicates also good chain or cyclic hydrocarbon group, R ₅ and R ₆ R ₄ may be bonded to each other to form a cyclic structure, R ₄ represents a hydrogen atom or a methyl group, and X represents a divalent linking group.
(In the general formula (3), R ₇ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an acyl group, an oxy radical group, or OR represents _12, R ₁₂ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group or an acyl group, having 7 to 12 carbon atoms, R _8, R _9, R ₁₀ and R ₁₁ each independently represent a methyl group, an ethyl group, or a phenyl group, R ₄ represents a hydrogen atom or a methyl group, and X represents a divalent linking group.

  Further, the present invention relates to the coloring composition for color filter, which further comprises a photopolymerizable monomer (D) and a photopolymerization initiator (E).

  The present invention also relates to a color filter comprising a red filter segment formed using the coloring composition for color filter.

  Further, the present invention relates to a liquid crystal display device characterized by comprising the color filter.

  The present invention also relates to a solid-state imaging device comprising the color filter.

  The present invention is a coloring composition for color filters capable of forming a red pixel which is excellent in dispersion stability, is free from foreign matter deposition on a coating film, and is further excellent in contrast ratio, heat resistance and solvent resistance by a quinacridone pigment, It is an object of the present invention to provide a color filter having a red filter segment, and a liquid crystal display or a solid-state imaging device having the same.

Hereinafter, the present invention will be described in detail.
In the present specification, when “(meth) acryloyl”, “(meth) acrylic”, “(meth) acrylic acid”, “(meth) acrylate” or “(meth) acrylamide” is described, it is particularly described Unless there is any, respectively, "acryloyl and / or methacryloyl", "acrylic and / or methacrylic", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", or "acrylamide and / or methacrylamide" Represent. Also, in the present specification, "C.I." means color index (C.I.).

  The coloring composition for color filters of the present invention uses a quinacridone pigment (A) as a coloring agent, and further contains a dye derivative (B) and a basic dispersant (C) containing an acrylic block copolymer. And a binder resin (D). In the present specification, the coloring composition for color filter may be referred to as a pigment dispersion.

<Quinacridone pigment (A)>
In the present invention, it is essential to use a quinacridone pigment as the colorant. Examples of quinacridone pigments that can be used include C.I. I. Pigment violet 19, 42, C.I. I. Pigment red 122, 202, 206, 207, 209, C.I. I. And pigments such as CI pigment orange 48 and 49. Among these, from the viewpoint of hue, C.I. I. Pigment red 122, C.I. I. Pigment red 202, C.I. I. Pigment red 207, C.I. I. It is desirable to use pigment red 209.

  The quinacridone pigment used in the present invention preferably has an average primary particle diameter in the range of 10 to 50 nm in order to realize high brightness and high contrast of the color filter. The average primary particle size of the pigment can be measured by transmission electron microscopy. When the average primary particle diameter of the pigment is larger than 50 nm, the lightness and contrast of the color filter become low, and when smaller than 10 nm, the pigment dispersion is very difficult, and the flowability as a coloring composition can be secured. It will be difficult. As a result, the lightness and contrast of the color filter tend to deteriorate.

In the present invention, pigments or dyes other than quinacridone pigments may be used in combination. As a pigment which can be used for the coloring composition of this invention,
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: 81, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108, 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, 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.
Examples of orange pigments include C.I. I. Orange pigments such as CI Pigment Orange 36, 38, 43, 51, 55, 59, 61 can be used.

  The yellow pigment is, for example, C.I. I. Pigment yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, 221, or the quinophthalone-based pigments described in Japanese Patent No. 4993026, etc. There may be mentioned, but not particularly limited thereto. In addition, yellow dyes such as quinoline type, azo type, methine type, coumarin type and isoindoline type can also be used.

  Green pigments that can be used in the present invention are, for example, C.I. I. Pigment greens 7, 10, 36, 37, 58, JP 2008-19383 A, JP 2007-320986 A, JP 2004 70342 A, WO 2015/118720 pamphlet, etc. Examples thereof include, but are not particularly limited to, pigments, and the like. Further, blue-green dyes such as triarylmethanes, phthalocyanines and squaryliums can also be used.

  Blue pigments that can be used in the present invention are, for example, C.I. I. Pigment blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, JP-A-2004-333817, Although the aluminum phthalocyanine pigment etc. which are described in the patent 4893859 grade | etc., Are mentioned, it is not limited in particular in these.

  Purple pigments which can be used in the present invention are, for example, 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, 25, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like, but not limited thereto.

  The coloring composition of the present invention can also use a dye as a coloring agent. As the dye, any of acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, architectural dyes, sulfur dyes and the like can be used. In addition, these may be in the form of derivatives or laked lakes of dyes.

Furthermore, acid dyes having an acidic group such as sulfonic acid and carboxylic acid, and in the case of direct dyes, inorganic salts of acid dyes, acid dyes and quaternary ammonium salt compounds, tertiary amine compounds, secondary amine compounds, Or a salt forming compound with a nitrogen-containing compound such as a primary amine compound, or using as a salt forming compound by using a resin component having these functional groups as a salt forming compound, or using it as a sulfone amide compound In order to be excellent in resistance, it is possible to make a coloring composition excellent in fastness, which is preferable.
Further, a salt forming compound of an acid dye and a compound having an onium base is also preferable because it is excellent in fastness, and more preferably, the compound having an onium base is a resin having a cationic group in a side chain.

  In the case of the form of a basic dye, it can be used by using an organic acid or perchloric acid or a metal salt thereof to form a salt. Among them, a salt forming compound of a basic dye is preferable because it is resistant and excellent in the compatibility with the pigment, and the basic dye and organic sulfonic acid which is a counter component which works as a counter ion, organic sulfuric acid, fluorine group-containing phosphorus It is possible to use a salt-forming compound having formed a salt with an anion compound, a fluorine group-containing boron anion compound, a cyano group-containing nitrogen anion compound, an anion compound having a conjugated base of an organic acid having a halogenated hydrocarbon group, or an acid dye. It is more preferable.

  Moreover, when it has a polymeric unsaturated group in pigment | dye frame | skeleton, it can be set as the dye excellent in tolerance, and it is preferable.

  The chemical structure of the dye includes, for example, azo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, anthraquinone dyes, Pyridone dyes, carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinoneimine dyes (oxazine dyes, thiazine dyes, etc.), azine dyes, polymethine dyes Dyes (oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone dyes Indigo dyes, mention may be made thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, and a dye structure derived from a dye selected from those metal complex dyes.

  Among these dye structures, azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium, from the viewpoint of color characteristics such as hue, color separation, and color unevenness. Dye structures derived from dyes selected from dyes, quinophthalone dyes, phthalocyanine dyes and subphthalocyanine dyes are preferable, and xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, phthalocyanine dyes More preferred is a dye structure derived from a dye selected from the dye series. Specific dye compounds that can form a dye structure are described in “New Dye Handbook” (Organic Synthetic Chemistry Association, edited by Maruzen, 1970), “The Society of Dyers and colourists”, “Dye Handbook” (Ogawara et al. Ed., Kodansha, 1986).

<Fined pigment>
The quinacridone pigment used in the present invention is a coloring agent for color filter by subjecting the particles to fine processing by a salt milling treatment or the like as necessary in order to obtain high brightness and high contrast when used as a coloring composition. It can be suitably used as The primary particle diameter of the colorant is preferably 10 nm or more in order to enhance the dispersibility in the colorant carrier. Further, in order to obtain a filter segment having high brightness and contrast, the thickness is preferably 50 nm or less.

  As a means to reduce the primary particle diameter of the pigment, a method of mechanically pulverizing the pigment (referred to as grinding method), the one dissolved in a good solvent is added to the poor solvent to precipitate the pigment of the desired primary particle diameter. There are a method (referred to as precipitation method) and a method of producing a pigment having a desired primary particle diameter at the time of synthesis (referred to as synthetic precipitation method). Depending on the synthesis method and the chemical properties of the pigment used, the selection can be carried out by selecting an appropriate method for each pigment. Each method is described below.

In the grinding method, the pigment is mechanically kneaded together with a grinding agent such as water-soluble inorganic salt such as sodium chloride and a water-soluble organic solvent which does not dissolve it (hereinafter, this process is salted using a ball mill, sand mill or kneader) After milling, the inorganic salt and the organic solvent are removed by washing with water and dried to obtain a pigment having a desired specific surface area. However, since crystal growth of the pigment may occur due to the salt milling process, a method of preventing crystal growth is effective by adding a solid resin which is at least partially dissolved in the water-soluble organic solvent at the time of the treatment and a dispersing aid described later. It is.
With regard to the ratio of the pigment to the inorganic salt, when the ratio of the inorganic salt is increased, the refining efficiency of the pigment is improved, but the throughput of the pigment is reduced, so that the productivity is reduced. Generally, 1 to 30 parts by mass, preferably 2 to 20 parts by mass of the inorganic salt is used based on 1 part by mass of the pigment.

In addition, the water-soluble organic solvent is added so that the pigment and the inorganic salt form a uniform mass, and although it depends on the compounding ratio of the pigment and the inorganic salt, usually an amount of 50 to 300% by mass of the pigment is used Be
To explain the grinding method in more detail, a small amount of water-soluble organic solvent is added as a wetting agent to the mixture of pigment and water-soluble inorganic salt, and the mixture is strongly kneaded with a kneader etc. The mixture is stirred with a mixer or the like to form a slurry. Next, the slurry is filtered, washed with water and dried to obtain a pigment having a desired primary particle size.

  The precipitation method is a method in which a pigment is dissolved in an appropriate good solvent and then mixed with a poor solvent to precipitate a pigment having a desired primary particle diameter, and the primary type is determined according to the type and amount of solvent, precipitation temperature, precipitation speed, etc. The size of the particle size can be controlled. Generally, since the pigment is hardly soluble in solvents, usable solvents are limited, for example, strongly acidic solvents such as concentrated sulfuric acid, polyphosphoric acid and chlorosulfonic acid or liquid ammonia, bases such as ammonia solution of sodium methylate, etc. Solvents and the like are known.

  As a typical example of the precipitation method, there is an acid pasting method in which a solution in which a pigment is dissolved in an acidic solvent is poured into another solvent and reprecipitated to obtain fine particles. Industrially, the method of injecting a sulfuric acid solution into water is general from the viewpoint of cost. Although the sulfuric acid concentration is not particularly limited, 95 to 100% by mass is preferable. The amount of sulfuric acid used with respect to the pigment is not particularly limited, but if it is small, the solution viscosity is high and the handling is poor, and if it is too large, the pigment processing efficiency is reduced. It is preferable to use The pigment does not have to be completely dissolved. The temperature at the time of dissolution is preferably 0 to 50 ° C., below which the sulfuric acid may be frozen and the solubility also decreases. If the temperature is too high, side reactions are likely to occur. The temperature of the water to be injected is preferably 1 to 60 ° C. When the injection is started above this temperature, it boils due to the heat of solution of sulfuric acid and the work is dangerous. It freezes at the temperature below this. The time for injection is preferably 0.1 to 30 minutes per part of the pigment.

  The control of the primary particle diameter of the pigment can be performed in consideration of the degree of particle size regulation by selecting a method combining precipitation method such as acid pasting method and grinding method such as salt milling method. Is more preferable because the fluidity as a dispersion can be secured at this time. At the time of salt milling or acid pasting, in order to prevent the aggregation of the pigment accompanied by the control of the primary particle diameter, it is also possible to use a dispersing aid such as a dye derivative, a resin type dispersing agent or a surfactant described later. Further, by performing primary particle diameter control in the form of coexistence of two or more types of pigments, even a pigment which is difficult to disperse alone can be finished as a stable dispersion.

The synthetic precipitation method is a method of synthesizing a pigment and simultaneously precipitating a pigment having a desired primary particle size. However, when the produced finely divided pigment is taken out of the solvent, secondary aggregation usually occurs because filtration, which is a general separation method, becomes difficult unless the pigment particles are aggregated to form large secondary particles. It is applied to pigments such as azo pigments that are synthesized with easy aqueous systems.
Furthermore, as a means to control the primary particle diameter of the pigment, the primary particle diameter of the pigment is reduced and dispersed simultaneously by dispersing the pigment for a long time with a high speed sand mill or the like (so-called dry milling method of pulverizing the pigment). It is also possible.

<Dye derivative (B)>
In the present invention, it is essential to use a dye derivative having a dye skeleton as a dispersion aid. Examples of dye derivatives include organic pigments, anthraquinones, acridones or triazines, compounds having a basic substituent, an acid substituent, or a phthalimidomethyl group which may have a substituent, for example, 63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, JP-A 2001-335717, JP-A 2003- No. 128669, JP-A 2004-091497, JP-A 2007-156395, JP-A 2008-094873, JP-A 2008-094986, JP-A 2008-095007, JP-A 2008-195916 It is possible to use those described in Japanese Patent No. 4585581 etc. These may be used alone or in combination of two or more.

  Among them, dye derivatives having an acidic functional group are preferable from the viewpoint of the interaction with the block copolymer / basic dispersant of the present invention. In particular, metal salts or amine salts of sulfonated dye derivatives or sulfonated dye derivatives are preferred.

Examples of metals that constitute metal salts include sodium, potassium, calcium, barium, iron,
Various metals such as magnesium, aluminum, nickel, cobalt and strontium may be mentioned. Among these, when an aluminum salt is used, it is possible not only to be excellent in isolation in production and dispersibility as a pigment dispersant, but also to obtain a coloring composition most excellent in low viscosity, flow characteristics and temporal viscosity stability. .

  Examples of the amine constituting the amine salt include ammonia, dimethylamine, trimethylamine, diethylamine, triethylamine, hydroxyethylamine, dihydroxyethylamine, 2-ethylhexylamine, N, N-dimethylaminopropylamine, N, N-diethylaminopropylamine, N, Lower amines such as N-dibutylaminopropylamine, long-chain alkyl amines having an alkyl group having 2 or more carbon atoms such as laurylamine, oleylamine, palmitylamine, stearylamine, dimethyllaurylamine, lauryl ammonium, stearyl ammonium, lauryl trimethyl Alkyl having 12 or more carbon atoms, such as ammonium, dilauryldimethylammonium, stearyltrimethylammonium, distearyldimethylammonium and the like Long chain alkyl quaternary ammonium ions having a group. Among these, when using a salt with a long-chain alkyl quaternary ammonium ion having an alkyl group having 12 or more carbon atoms, such as lauryl ammonium or stearyl ammonium, a coloring composition which is most excellent in the dispersion stability and particularly high in storage stability. Is obtained.

  The number of introduced sulfo groups is preferably 1 to 2 with respect to the dye skeleton. When the number is 3 or more, the affinity to the organic solvent which can be suitably used for the color filter is lost, and the dispersibility is lowered.

  From the viewpoint of interaction with a quinacridone pigment, the pigment skeleton of the pigment derivative is desirably any one of a quinacridone pigment, an isoindoline pigment, a quinophthalone pigment, and an anthraquinone pigment.

  Examples of the structures of dye derivatives suitable for the present invention are shown below.

  The content of the dye derivative is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and most preferably 3 parts by mass or more, with respect to 100 parts by mass of the colorant, from the viewpoint of improving dispersibility. Further, from the viewpoint of heat resistance and light resistance, it is preferably 40 parts by mass or less, and more preferably 35 parts by mass or less.

<Basic Dispersant (C) Containing Acrylic Block Copolymer>
The present invention is essentially characterized in that it contains a basic dispersant having an amino group structure, and is characterized in that it is a basic dispersant containing an acrylic block copolymer. The basic dispersant containing an acrylic block copolymer is a quaternary ammonium base represented by the general formula (1) or a primary, secondary or tertiary represented by the general formulas (2) and (3). It is a block copolymer comprising an A block having a structure of an amino group and a B block having no structure represented by the general formulas (1), (2) and (3). There are no particular limitations on the configuration of A block and B block, but AB block, BAB block, or ABA is preferable, and AB block or BAB block is more preferably used. be able to.

(In the general formula (1), R _{1 to} R ₃ each independently represent a hydrogen atom or a chain or cyclic hydrocarbon group which may have a substituent, and R _{1 to} R ₃ Two or more of them may be bonded to each other to form a cyclic structure, R ₄ represents a hydrogen atom or a methyl group, X represents a divalent linking group, and Y − represents a counter anion.

(In the general formula (2), R ₅ and R ₆ are, independently of each other, hydrogen atom, or a substituted indicates also good chain or cyclic hydrocarbon group, R ₅ and R ₆ R ₄ may be bonded to each other to form a cyclic structure, R ₄ represents a hydrogen atom or a methyl group, and X represents a divalent linking group.

(In the formula (3), R ₇ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an acyl group, an oxy radical group, or OR ₁₀ R ₁₀ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an acyl group, R ₈ · R ₉ · R ₁₀ · R ₁₁ each independently represents a methyl group, an ethyl group or a phenyl group, R ₄ represents a hydrogen atom or a methyl group, and X represents a divalent linking group)

As R _{1 to} R ₃ in the general (1), an alkyl group having 1 to 4 carbon atoms which may have a substituent, and an aralkyl group having 7 to 16 carbon atoms which may have a substituent are more preferable Preferred is a methyl group, an ethyl group, a propyl group, a butyl group or a benzyl group. Further, as R ₅ and R ₆ in the general formula (2), an alkyl group having 1 to 4 carbon atoms which may have a substituent is more preferable, and a methyl group, an ethyl group, a propyl group and a butyl group are particularly preferable preferable.

In R ₇ of the general formula (3), examples of the alkyl group having 1 to 18 carbon atoms include linear, branched and cyclic alkyl groups, and specific examples thereof include methyl group, ethyl group and normal propyl group And isopropyl, n-butyl, t-butyl, n-hexyl, cyclohexyl, n-octyl, hexadecyl and the like.
As a C6-C20 aryl group, a phenyl group, 1-naphthyl group, 2-naphthyl group etc. can be mentioned, for example.
As a C7-C12 aralkyl group, the group which the C1-C8 alkyl group couple | bonded with the C6-C10 aryl group is mentioned, for example, Specifically, A benzyl group, phenethyl group, alpha And -methylbenzyl group, 2-phenylpropan-2-yl group and the like can be mentioned.
Moreover, as an acyl group, a C2-C8 alkanoyl group and aroyl group are mentioned, An acetyl group, a benzoyl group etc. can be mentioned specifically ,.
Among these, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and an oxy radical group are particularly preferable, a hydrogen atom and a methyl group are more preferable, and a methyl group is most preferable.

In the general formula (1), (2) and (3), the divalent linking group X, for example, methylene group, an alkylene group having 2 to 10 carbon atoms, an arylene _{group, -CONH-R 13 -, -} COO -R _{1 14} - (where, R ₁₃ and R ₁₄ is a single bond, a methylene group, an alkylene group having 2 to 10 carbon atoms, or an ether group having 2 to 10 carbon atoms (alkyloxy group)), and include it is preferably -COO-R _{1 4} - a. In the above formula (1), the counter anion of Y ^{- The, Cl -, Br -, I} -, ClO 4 -, BF 4 -, CH 3 COO -, PF 6 - , and the like.

  The A block is not particularly limited as long as it has one of the structures represented by the general formulas (1) (2) (3), but a partial structure derived from an ethylenically unsaturated monomer is preferable .

  Specific examples of the ethylenically unsaturated monomer having a quaternary ammonium base, which is a precursor / partial structure of the general formula (1), include (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyl. Alkyl (meth) acrylate quaternary ammonium salts such as triethyl ammonium chloride, (meth) acryloyloxyethyl dimethyl benzyl ammonium chloride, (meth) acryloyloxy ethyl methyl morpholino ammonium chloride, (meth) acryloyl aminopropyl trimethyl ammonium chloride, ( Alkyl (meth) such as (meth) acryloylaminoethyl triethyl ammonium chloride, (meth) acryloyl aminoethyl dimethyl benzyl ammonium chloride Kuriroiruamido based quaternary ammonium salt, dimethyl diallyl ammonium methyl sulfate, trimethyl vinyl phenyl ammonium chloride.

Specific examples of the ethylenically unsaturated monomer having a tertiary amine group to be a precursor / partial structure of the general formula (2) are
N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (
Meta) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-
(Meth) acrylates having a tertiary amino group such as diethylaminopropyl (meth) acrylate;
Tertiary such as N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, and N, N-diethylaminopropyl (meth) acrylamide Having an amino group (
Meta) acrylamides;
Etc.

  Specific examples of the ethylenically unsaturated monomer to be the precursor / partial structure of the general formula (3) include, for example, compounds represented by the following compounds (3-1) to (3-11) I can do it.

In compounds (3-1) to (3-11), R ₄ represents hydrogen or a methyl group.

Among these, 2,2,6,6-tetramethyl piperidyl methacrylate (a compound in which R ₄ is a methyl group in the above compound (3-1)), 1,2,2,6,6-pentamethyl piperidyl methacrylate (A compound in which R ₄ is a methyl group in the above compound (3-2)) is preferable, and in particular, 1,2,2,6,6-pentamethyl piperidyl methacrylate is preferable.

  The partial structure containing the group represented by General Formula (1) (2) (3) may be contained singly or in combination of two or more in one A block, and in the case of containing two or more, it is random It may be contained in any mode of copolymerization or block copolymerization.

  The content of the group represented by the general formulas (1), (2) and (3) in the A block is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, particularly preferably It is 95-100 mass%.

  On the other hand, a structural unit which does not contain a group represented by the general formulas (1), (2) and (3) in the A block, and a B block have a polymer structure obtained by copolymerizing copolymerizable monomers. If it exists, it will not be specifically limited, According to a use, it can select suitably. The copolymerizable monomers are shown below.

For example,
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth), tertiary butyl (meth) acrylate, isoamyl (meth) Acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cetyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) Linear or branched alkyl (meth) acrylates such as acrylate, isomyristyl (meth) acrylate, stearyl (meth) acrylate, and isostearyl (meth) acrylate;
Cyclic alkyl (meth) acrylates such as cyclohexyl (meth) acrylate, tertiary butyl cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and isobornyl (meth) acrylate;
(Meth) acrylates having a heterocyclic ring such as tetrahydrofurfuryl (meth) acrylate and 3-methyl-3-oxetanyl (meth) acrylate;
Benzyl (meth) acrylate, (meth) acrylates having an aromatic ring of phenoxyethyl (meth) acrylate; 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-methoxypropyl (meth) acrylate , Diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol mono-2-ethylhexyl ether (meth) acrylate, dipropylene glycol monomethyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, Triethylene glycol monoethyl ether (meth) acrylate, tripropylene glycol monomethyl ether (meth) acrylic , Tetraethylene glycol monomethyl ether (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate, polypropylene glycol monomethyl ether (meth) acrylate, polyethylene glycol monolauryl ether (meth) acrylate, polyethylene glycol monostearyl ether (meth) acrylate And (poly) alkylene glycol monoalkyl ether (meth) acrylates such as octoxy polyethylene glycol-polypropylene glycol (meth) acrylate;
Phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, paracumyl phenoxyethyl (meth) acrylate, paraquat Mil phenoxy ethylene glycol (meth) acrylate, paracumyl phenoxy polyethylene glycol (meth) acrylate, nonyl phenoxy polyethylene glycol (meth) acrylate, nonyl phenoxy polypropylene glycol (meth) acrylate, and nonyl phenoxy poly (ethylene glycol-propylene glycol) (meta) ) Having an aromatic ring such as acrylate (poly) Ruki glycol (meth) acrylates;
Alkyloxy such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane (Meth) acrylates having a silyl group;
Fluoroalkyl (meth) acrylates such as trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, and tetrafluoropropyl (meth) acrylate; (meth) acryloxy-modified polydimethyl dimethyl Siloxane (silicone macromer);
N-substituted (meth) acrylamides such as (meth) acrylamide, dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, and acryloyl morpholine; And nitriles such as (meth) acrylonitrile.
Also, styrenes and styrenes such as α-methylstyrene; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether and isobutyl vinyl ether; and fatty acids such as vinyl acetate and vinyl propionate Vinyls etc. are mentioned.

  Furthermore, a carboxyl group-containing ethylenic unsaturated monomer can be used in combination. Examples of the carboxyl group-containing ethylenic unsaturated monomer include (meth) acrylic acid, (meth) acrylic acid dimer, itaconic acid, maleic acid, fumaric acid, crotonic acid, 2- (meth) acryloyloxyethyl phthalate, -(Meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxypropyl hexahydrophthalate, β-carboxyethyl (meth) acrylate, and ω-carboxypoly A caprolactone (meth) acrylate etc. are mentioned.

  Moreover, you may use together the ethylenically unsaturated monomer containing amino groups other than group represented by General formula (1) (2) (3) in the range which does not impair the effect of this invention.

  The B block is preferably a partial structure derived from an ethylenically unsaturated monomer, and further at least from benzyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate and hydroxyethyl (meth) acrylate. Preferably, ethylenically unsaturated monomers selected from the group consisting of

(Production of block copolymer (C))
The block copolymer (C) used in the present invention is prepared, for example, by the living polymerization method described below. Here, the living polymerization is a polymerization method for easily synthesizing a block polymer and a resin having a uniform molecular weight, because side reactions which occur in general radical polymerization are suppressed, and further, polymerization growth occurs uniformly. The molecular weight of the polymer and the ratio of block copolymerized monomers can be freely controlled by the preparation ratio of the polymerization initiator and the vinyl monomer added at the time of polymerization, and block polymer, gradient polymer, star polymer, comb polymer, and further Can be used to produce end-functionalized polymers and the like.

  The block copolymer (C) in the present invention can be synthesized by a known radical living polymerization method, and the method described in JP-A-2014-219665 can be used. The atom transfer radical polymerization method (ATRP method) and the nitroxide method (NMP method) can be applied not only to the control of molecular weight and molecular weight distribution of the polymer but also to a wide range of monomers, adaptable to existing equipment The polymerization temperature is preferably adopted, and the nitroxide method (NMP method) is more preferable in that a transition metal or the like which may cause coloring or the like is not used.

[Atom transfer radical polymerization method (ATRP method)]
The atom transfer radical polymerization method is carried out using a transition metal complex such as copper, ruthenium, iron or nickel as a redox polymerization catalyst. Specific examples of transition metal complexes include low valence transition metal halides such as copper (I) chloride copper (I) bromide.

  An organic ligand is used for the transition metal complex. Organic ligands are used to enable solubility in the polymerization solvent and reversible conversion of the redox polymerization catalyst. As a coordination atom of the transition metal, a nitrogen atom, an oxygen atom, a phosphorus atom, a sulfur atom and the like can be mentioned.

  As the initiator used for the atomic radical polymerization method, known ones can be used, but mainly organic halides having high reactivity carbon halogen bond, halogenated sulfonyl compounds and the like are used. Specific examples thereof include ethyl bromoisobutyrate, ethyl bromobutyrate, ethyl chloroisobutyrate, ethyl chlorobutyrate, paratoluenesulfonic acid chloride, 1-bromoethylbenzene, chloroethylbenzene and the like. These are used alone or in combination.

[Nitroxide method (NMP method)]
The nitroxide-mediated living radical polymerization method is carried out using a stable nitroxy free radical (= N-O.) As a radical capping agent. The stable nitroxy free radical is not particularly limited, and examples thereof include 2,2,6,6-tetramethyl-1-piperidinyloxy radical (TEMPO), Peridinyloxy radical, 2,2,6,6-tetramethyl-4-oxo-1-piperidinyloxy radical, 2,2,5,5-tetramethyl-1-pyrrolidinyloxy radical, 1,1 And 3,3,3-tetramethyl-2-isoindolinyloxy radical, N, N-di-t-butylamine oxy radical and the like. Instead of the nitroxy free radical, a stable free radical such as galvinoxyl free radical may be used.

  The radical capping agent is used in combination with a radical polymerization initiator. Although the combined use ratio of both is not specifically limited, 0.1-10 mol of radical initiators are suitable with respect to 1 mol of radical capping agents.

  Although the said radical polymerization initiator is suitably selected according to the weight average molecular weight (Mw) of resin synthesize | combined, (meth) acryloyl group in the monomer used when synthesize | combining a copolymer (B) It is used in a ratio of 0.0001 to 1 mole, preferably 0.001 to 0.1 mole, per 1 mole.

Although a well-known thing can be used as a radical polymerization initiator, If it is a compound which can generate | occur | produce a radical on polymerization temperature conditions, there will be no restriction | limiting in particular. For example, di-t-butyl peroxide, dicumyl peroxide, t-butyl cumyl peroxide, α, α'-bis (t-butylperoxy-m-isopropyl) benzene, 2,5-di (t) -Dialkylperoxides such as butylperoxy) hexin-3;
peroxy esters such as t-butyl peroxybenzoate, t-butyl peroxy acetate, 2,5-dimethyl-2,5-di (benzoyl peroxy) hexane;
Ketone peroxides such as cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide;
2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t- Peroxyketals such as butylperoxy) cyclohexane, n-butyl-4,4-bis (t-butylperoxy) barate, etc .;
Hydroperoxides such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylcyclohexane-2,5-dihydroperoxide;
Diacyl peroxides such as benzoyl peroxide, decanoyl peroxide, lauroyl peroxide, 2,4-dichlorobenzoyl peroxide;
Organic peroxides such as peroxydicarbonates such as bis (t-butylcyclohexyl) peroxydicarbonate, or mixtures thereof.

  Moreover, an azo compound can also be used as a radical polymerization initiator. For example, 2,2′-azobisbutyronitriles such as 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobis (2-methylbutyronitrile), 2, 2, 2,2′-azobisvaleronitriles such as 2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2 ′ 2,2'-azobispropionitriles such as -azobis (2-hydroxymethylpropionitrile), 1,1'-azobis-1- such as 1,1'-azobis (cyclohexane-1-carbonitrile) and the like Alkane nitriles can be used.

Furthermore, as reported in Macromolecules 1995, 28, 2993, instead of using a radical capping agent and the above-mentioned radical polymerization initiator in combination, an alkoxyamine compound represented by the following compounds (N-1 to 4) is started You may use as an agent.

  In the process of producing the block copolymer, no solvent or optionally a solvent can be used. As a solvent, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene Although glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, or diethylene glycol monobutyl ether acetate is used, it is not particularly limited thereto. These polymerization solvents may be used as a mixture of two or more.

  The amount of the solvent to be used is preferably 0 to 300 parts by mass, and more preferably 0 to 100 parts by mass with respect to 100 parts by mass of the monomer consisting of A block and B block. The solvent used may be removed after completion of the reaction by an operation such as distillation, or may be used as it is as part of the product of the composition.

  The content of block A is preferably 1 to 99% by mass, more preferably 20 to 50% by mass, and particularly preferably 20 to 30% by mass, based on the solid content of the block copolymer (C). preferable. When the A block contains 20 to 30% by mass, the remaining 70 to 80% by mass constitutes the B block. Therefore, when the B block is compatible with the solvent which is the dispersion medium, the pigment can be stably present in the dispersion medium.

  The amount of the group represented by the general formula (1) (2) (3) in 1 g of the A-B block copolymer or B-A-B block copolymer used in the present invention is usually 0.1 It is preferable that it is -5 mmol, and it is more compatible with lightness and dispersibility as it is in this range.

  The block copolymer (C) of the present invention more preferably has an amine value of 30 to 350 mg KOH / g, although it depends on the type of the structure represented by the general formulas (1), (2) and (3). The pigment dispersion is excellent in viscosity and viscosity stability when the amine value is 30 mg KOH / g or more, and is excellent in lightness when the amine value is 350 mg KOH / g or less

  In addition, the molecular weight of the block copolymer (C) of the present invention is preferably in the range of usually 1,000 or more and 100,000 or less in terms of weight average in terms of polystyrene. When the molecular weight of the block copolymer is less than 1,000, the dispersion stability tends to decrease, and when it exceeds 100,000, the developability tends to decrease.

  In the colored composition in the present invention, this block copolymer (C) can be used as a dispersant. At that time, various resins may be added. The kind of resin used and the below-mentioned resin type dispersing agent can be used together.

<< Other dispersants >>
The coloring composition for color filters of this invention may use another dispersing agent together.
Specific examples of other dispersants include polyurethanes, polycarboxylic acid esters such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts , Polysiloxane, long chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amide formed by reaction of poly (lower alkyleneimine) with polyester having free carboxyl group, and salts thereof Etc., (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinyl pyrrolidone, etc. Resin, water soluble polymer, polyester, modified polymer Acrylate, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, it can be used alone or in admixture of two or more, not necessarily limited thereto.

  Commercially available resin type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 154, 161, 162, 163, 164, 165, 166, 170 manufactured by Big Chemie Japan. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2070, 2095, 2150, 2155, or Anti-Terra-U, 203, 204, or BYK. -P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykumen et al., SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 160, manufactured by Japan Lubrizol Corporation. 0, 17000, 18000, 20000, 21000, 21000, 24000, 26000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500 etc., BASF Japan made EFKA-46, 47, 48, 452, 4008, 4010, 4015, 4020, 4047, 4050, 4050, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4010 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 554,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

<Binder resin (D)>
The binder resin is one that disperses, dyes, or penetrates a coloring agent, and includes thermoplastic resins and the like. In the case of using in the form of an alkali-developable colored resist material, it is preferable to use an alkali-soluble vinyl resin obtained by copolymerizing an acidic group-containing ethylenic unsaturated monomer. Furthermore, in order to further improve the photosensitivity, an active energy ray curable resin having an ethylenically unsaturated double bond can also be used.

  In particular, when an active energy ray-curable resin having an ethylenically unsaturated double bond in a side chain is used as the alkali-developable colored resist material, the resin is three-dimensionally crosslinked when exposed to active energy rays to form a coating film. As a result, the coloring agent is fixed, the heat resistance is improved, and the color fading (the deterioration of the spectral characteristics) due to the heat of the coloring agent can be suppressed. In addition, it also has the effect of suppressing aggregation and precipitation of the colorant component in the development step.

  The binder resin is preferably a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more, in the entire wavelength range of 400 to 700 nm in the visible light range.

  The weight average molecular weight (Mw) of the binder resin is preferably in the range of 10,000 to 100,000, and more preferably in the range of 10,000 to 80,000 in order to disperse the colorant preferably. 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 binder resin is used as a photosensitive coloring composition for color filters, a colorant-adsorbing group, a carboxyl group acting as an alkali-soluble group during development, an aliphatic group acting as an affinity group for a colorant carrier and a solvent, The balance of the aromatic group is important for the dispersibility, permeability, developability and durability of the colorant, and it is preferable to use a resin having an acid value of 20 to 300 mg KOH / g. If the acid value is less than 20 mg KOH / g, the solubility in a developer is poor, and it is difficult to form a fine pattern. If it exceeds 300 mg KOH / g, no fine pattern will remain.

  The binder resin is preferably used in an amount of 20 parts by mass or more based on 100 parts by mass of the total mass of the colorant because the film forming property and the various resistances are good. It is preferable to use in an amount of 1000 parts by mass or less because it can be expressed.

  As a thermoplastic resin used for binder resin, for example, acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate Polyurethane resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins. . Among them, it is preferable to use an acrylic resin.

As a vinyl type alkali soluble resin which copolymerized the acidic group containing ethylenically unsaturated monomer, resin which has acidic groups, such as a carboxy group and a sulfo group, is mentioned, for example.
Specifically as an alkali-soluble resin, an acrylic resin having an acidic group, an α-olefin / (maleic anhydride) copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or An isobutylene / (anhydride) maleic acid copolymer etc. are mentioned. Among them, at least one resin selected from an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer, in particular an acrylic resin having an acidic group, is preferably used because it is high in heat resistance and transparency.

  Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include resins in which an unsaturated ethylenic double bond is introduced by the method (i) or (ii) shown below.

[Method (i)]
As the method (i), for example, to a side chain epoxy group of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having an epoxy group and one or more other monomers. And the carboxyl group of the unsaturated monobasic acid having an unsaturated ethylenic double bond is added, and the generated hydroxyl group is further reacted with a polybasic acid anhydride to form an unsaturated ethylenic double bond and a carboxyl group There is a way to introduce it.

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

  Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano-substituted, etc. Monocarboxylic acids and the like can be mentioned, and these may be used alone or in combination of two or more.

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride and the like, which may be used alone or in combination of two or more. I do not mind. The remaining anhydride is obtained by using tricarboxylic acid anhydride such as trimellitic acid anhydride or using tetracarboxylic acid dianhydride such as pyromellitic acid dianhydride, if necessary, such as increasing the number of carboxyl groups. It is also possible to hydrolyze the group. In addition, unsaturated ethylenic double bonds can be further increased by using, as the polybasic acid anhydride, ethahydrophthalic anhydride having maleic unsaturated double bonds, or maleic anhydride.

  As a similar method of method (i), for example, a side chain of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having a carboxyl group and one or more other monomers. There is a method in which an unsaturated ethylenic monomer having an epoxy group is added to a part of the carboxyl group to introduce an unsaturated ethylenic double bond and a carboxyl group.

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

  As the unsaturated ethylenic monomer having a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, glycerol (Meth) acrylates or hydroxyalkyl (meth) acrylates such as cyclohexanedimethanol mono (meth) acrylate may be mentioned, and these may be used alone or in combination of two or more. Further, polyether mono (meth) acrylate obtained by addition polymerizing ethylene oxide, propylene oxide, and / or butylene oxide etc. to the above hydroxyalkyl (meth) acrylate, (poly) γ-valerolactone, (poly) ε-caprolactone And / or (poly) ester mono (meth) acrylates to which (poly) 12-hydroxystearic acid or the like is added can also be used. From the viewpoint of coating foreign matter suppression, 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferred.

  Examples of the unsaturated ethylenic monomer having an isocyanate group include 2- (meth) acryloyloxyethylisocyanate or 1,1-bis [(meth) acryloyloxy] ethylisocyanate, but are not limited thereto. Alternatively, two or more types can be used in combination.

<Thermosetting compound>
The coloring composition of the present invention can contain a thermosetting compound. If it is a thermosetting compound, there is no particular limitation, but it is preferable to use an epoxy compound from the viewpoint of chemical resistance and solvent resistance.

<< Epoxy Compound >>
The epoxy compound is not particularly limited as long as it has an epoxy group, and may be a low molecular weight compound or a high molecular weight compound such as a resin.
In particular, a polyfunctional epoxy resin is preferable, and the number of functional groups is preferably bifunctional or more, and more preferably trifunctional or more. The epoxy group of the epoxy resin can be thermally crosslinked with the binder resin or the carboxyl group of the dispersing agent at the time of firing which is a color filter production step, whereby a colored film having a high crosslinking density can be obtained.

  When it is an epoxy resin, as a preferable weight average molecular weight, 1500 or more and 100,000 or less are preferable. A more preferable molecular weight is 1750 or more and 10,000 or less, and more preferably 2,000 or more and 7,000 or less.

  As for content of the epoxy compound in the coloring composition for color filters, 5-20 mass% is preferable. If it is 5 mass% or more, the improvement effect of solvent resistance will be excellent, and if it is 20 mass% or less, the quality of the color filter due to yellowing after baking can be prevented, and the coloring composition is stabilized with time. The quality also becomes good.

  As an epoxy resin which can be used in the present invention, any of bisphenol A epoxy resin, bisphenol F epoxy resin, cresol novolac epoxy resin, biphenyl epoxy resin, alicyclic epoxy resin and the like can be used.

  As a bifunctional epoxy resin, EPICLON 830, 840, 850, 860, 1050, 2050, 3050, 4050, 7050, HM-091, 101 manufactured by DIC, and Nagase ChemteX Denacol EX-211, 212, 252, 711 , 721 and the like.

  Examples of trifunctional or higher polyfunctional epoxy resins include novolak epoxy resins and alicyclic epoxy resins.

  The novolac epoxy resin is a compound represented by the following general formula (4), and is classified into a phenol novolac epoxy resin and a cresol novolac epoxy resin.

  R 1 is each independently a methyl group or a hydrogen atom, and q is an integer of 2 to 100.

  Specifically as the novolac type epoxy resin, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, EOCN-4500, EOCN-4600, XD-1000, XD-1000, XD-1000-L, XD-1000- 2 L, NC-3000, NC-3000-H (above, Nippon Kayaku Co., Ltd.), YDPN-638, YDCN-700-2, YDCN-700-3, YDCN-700-5, YDCN-700-7, YDCN -700-10, YDCN-704, YDCN-704A (above, manufactured by Nippon Steel Chemical Co., Ltd.), N-660, N-665, N-670, N-673, N-680, N-690, N-695 , N-665-EXP, N-672-EXP, N-655-EXP-S, N-662-EXP-S (all by DIC) And the like.

The alicyclic epoxy resin is, for example, a compound represented by the following general formula (5). As an alicyclic epoxy resin, EHPE3150 (made by Daicel Chemical Industries, Ltd.) etc. are mentioned.

  j, k and l are integers of 1 to 30, respectively.

As other trifunctional or higher polyfunctional epoxy resins, Techmore VG3101 (made by Printech Co., Ltd.) which is a trifunctional epoxy resin, TETRAD-C which is a tetrafunctional epoxy resin, TETRAD-X (all, Mitsubishi Gas Chemical Co., Ltd.) Company company).
In addition, Denacol EX-313, 314, 321, 411, 421, 512, 521, 611, 612, 614, 614B, 622 and the like manufactured by Nagase ChemteX can be mentioned.
Moreover, Mitsubishi Chemical Corporation JER1031S, 1302 H60, 604, 630, 630LSD etc. are mentioned.

<< Other thermosetting compounds >>
As other thermosetting compounds, for example, thermosetting compounds such as benzoguanamine compound / resin, rosin modified maleic resin, rosin modified fumaric resin, melamine compound / resin, urea resin, and phenol resin, and these thermosetting resins It is also possible to use monomers and oligomers prior to heat polymerization of the base resin.

<Solvent>
In the coloring composition of the present invention, the coloring agent is sufficiently dispersed and infiltrated into the coloring agent carrier, and the filter segment is coated by applying a dry film thickness of 0.2 to 5 μm on a substrate such as a glass substrate. An organic solvent is included to facilitate formation. The organic solvent is selected in consideration of the solubility of each component of the coloring composition as well as the safety, as well as the application property of the coloring composition is good.

As the solvent, for example, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl 1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol , 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene , N, N-dimethylacetamide, N, N-dimethylformamide, n-butylal , N-butylbenzene, n-propylacetate, 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 Ether, ethylene glycol monohexyl ether, ethylene glycol 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 Recall monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin alcohol, tripropylene, 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 Tons, methylcyclohexanol, acetate n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.
These solvents may be used alone or in combination of two or more at an arbitrary ratio as needed.

  The solvent can be used in an amount of 100 to 10000 parts by mass, preferably 500 to 5000 parts by mass, with respect to 100 parts by mass of the colorant in the coloring composition.

<Photopolymerizable monomer>
The photopolymerizable monomer which may be added to the coloring composition of the present invention includes a monomer or an oligomer which is cured by ultraviolet light, heat or the like to form a transparent resin.

Examples of monomers and oligomers that cure by ultraviolet light and heat to form a transparent resin include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di ( Meta) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglyci Ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodeca Various acrylic and methacrylic esters such as (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate, epoxy (meth) acrylate, urethane acrylate, (meth) acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxy ester Examples include, but not limited to, chill (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.
These photopolymerizable compounds can be used alone or in combination of two or more at an arbitrary ratio as needed.

  The content of the photopolymerizable monomer is preferably 5 to 500 parts by mass with respect to 100 parts by mass of the colorant, and more preferably 10 to 400 parts by mass from the viewpoint of photocurability and developability. .

<Photoinitiator>
A photopolymerization initiator is added to the coloring composition of the present invention to cure the composition by ultraviolet irradiation and to form a filter segment by photolithography, and a solvent development type or alkali development type photosensitive coloring composition It can be prepared in the form of

As the photopolymerization initiator, 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] -1 Acetophenone compounds such as-[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 benzyl dimethyl 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-methyl thioxanthone, isopropyl thioxanthone, 2,4-diisopropyl thioxanthone, or 2,4-diethyl thioxanthone Etc .; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p- Toxiphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis ( Trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (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; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoylo] Shim)], or oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4'-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6 Phosphine compounds such as -trimethyl benzoyl) phenyl phosphine oxide or 2,4, 6 -trimethyl benzoyl diphenyl phosphine oxide; quinone compounds such as 9, 10- phenanthrene quinone, camphor quinone, ethyl anthraquinone; borate compounds; Carbazole compounds; imidazole compounds; or titanocene compounds are used.
These photopolymerization initiators can be used alone or in combination of two or more at an arbitrary ratio as needed.

  It is preferable that it is 1-500 mass parts with respect to 100 mass parts of coloring agents, and, as for photoinitiator content, it is more preferable that it is 5-400 mass parts from a photocurable and developable viewpoint.

<Sensitizer>
Furthermore, the coloring composition for color filters of the present invention can contain a sensitizer.
As sensitizers, unsaturated ketones represented by chalcone derivatives and dibenzalacetone etc., 1,2-diketone derivatives represented by benzyl and camphorquinone etc., benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, polymethine dyes such as oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapyrazino porphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalylo porphyrazine derivative, naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrilium derivative, tetraphyrin derivative, anurene derivative, spiropyran derivative, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, Michler's ketone derivatives and the like can be mentioned.
These sensitizers can be used alone or in combination of two or more at an arbitrary ratio as required.

Further, specific examples include Shin Ogawara et al., "Dye Handbook" (1986, Kodansha), Okawara Shin et al., "Chemicals of functional dyes" (1981 CMC), Tadazori Ikemori et al., Special The sensitizers described in "Functional materials" (1986, CMC) are included, but not limited thereto. In addition, a sensitizer that absorbs light in the ultraviolet to near-infrared region can also be contained.
Among the above-mentioned sensitizers, particularly preferred sensitizers include thioxanthone derivatives, Michler ketone derivatives and carbazole derivatives. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 1-chloro-4-propoxy thioxanthone, 4,4'-bis (Dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (ethylmethylamino) benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl- N-ethylcarbazole or the like is used.

  The content of the sensitizer is preferably 3 to 60 parts by mass with respect to 100 parts by mass of the photopolymerization initiator contained in the coloring composition, and 5 to 50 parts by mass from the viewpoint of photocurability and developability. It is more preferable that

<Multifunctional thiol>
The coloring composition for color filters of the present invention can contain a multifunctional thiol. The multifunctional thiol is a compound having two or more thiol (SH) groups.
The multifunctional thiol functions as a chain transfer agent in the radical polymerization process after light irradiation by using it together with the above-mentioned photopolymerization initiator, and generates a thiyl radical which is less susceptible to inhibition of polymerization by oxygen, so the coloration of the color filter obtained The composition is sensitive. In particular, polyfunctional aliphatic thiols in which an SH group is bonded to an aliphatic group such as a methylene or ethylene group are preferable.

As polyfunctional thiol, for example, hexane dithiol, decane dithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bis thioglycolate, ethylene glycol bis thiopropio , Trimethylolpropane tristhioglycollate, trimethylolpropane tristhiopropionate, trimethylolethane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), trimethylolpropane tris (3- Mercaptopropionate), Pentaerythritol tetrakisthioglycolate, Pentaerythritol tetrakisthiopropionate, Pentaerythritol tetrakis (3-mercaptopropione D) Dipentaerythritol hexakis (3-mercaptopropionate), tris (2-hydroxyethyl) isocyanurate trimercaptopropionate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s- Triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s-triazine and the like can be mentioned.
These polyfunctional thiols can be used alone or in combination of two or more at any ratio as required.

The content of the polyfunctional thiol is preferably 0.05 to 100 parts by mass, and more preferably 1.0 to 50.0 parts by mass with respect to 100 parts by mass of the colorant.
By using a multifunctional thiol in an amount of 0.05 parts by mass or more, better development resistance can be obtained. In the case where a monofunctional thiol having one thiol (SH) group is used, such improvement in development resistance can not be obtained.

<Leveling agent>
It is preferable to add a leveling agent to the colored composition of the present invention in order to improve the leveling properties of the composition on a transparent substrate. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in its main chain is preferred. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by BYK Chemie, and the like. As a specific example of dimethylsiloxane which has a polyester structure in a principal chain, BYK-310 by BYK-Chemie company, BYK-370, etc. are mentioned. The dimethylsiloxane having a polyether structure in the main chain and the dimethylsiloxane having a polyester structure in the main chain can also be used in combination. In general, the content of the leveling agent is preferably 0.003 to 1.0 parts by mass with respect to 100 parts by mass of the total weight of the coloring composition.

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, which has a low solubility in water while having a hydrophilic group, and when it is added to a coloring composition, It is characterized by low surface tension reduction ability, and in addition to low surface tension reduction ability, it is useful that the wettability to the glass plate is good, and the addition amount at which defects of the coating film due to foaming do not appear. Those which can sufficiently suppress the chargeability can be preferably used. As a leveling agent which has such a preferable characteristic, dimethylpolysiloxane which has a polyalkylene oxide unit can use it preferably. The polyalkylene oxide unit may be a polyethylene oxide unit or a polypropylene oxide unit, and the dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding form of the polyalkylene oxide unit to dimethylpolysiloxane is a pendent type in which the polyalkylene oxide unit is bonded to a repeating unit of dimethylpolysiloxane, a terminal-modified type bonded to the terminal of dimethylpolysiloxane, and dimethylpolysiloxane It may be any of linear block copolymer types alternately and repeatedly bonded. Dimethylpolysiloxanes having polyalkylene oxide units are commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ-2203. -2-207, but not limited thereto.

The leveling agent may be supplemented with an anionic, cationic, nonionic or amphoteric surfactant. The surfactant may be used as a mixture of two or more.
Examples of anionic surfactants to be added to leveling agents include polyoxyethylene alkyl ether sulfate, sodium dodecyl benzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearic acid, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphoric acid Ester etc. are mentioned.

  Examples of the cationic surfactant added to the leveling agent include alkyl quaternary ammonium salts and ethylene oxide adducts thereof. As a nonionic surfactant which is added to the leveling agent as auxiliaries, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate And ether surfactants such as polyethylene glycol monolaurate; alkyl betaines such as alkyl dimethylamino acetic acid betaine; amphoteric surfactants such as alkyl imidazoline; and fluorine-based and silicone-based surfactants.

<UV absorber, polymerization inhibitor>
The coloring composition for color filters of the present invention can contain an ultraviolet absorber or a polymerization inhibitor. By containing a UV absorber or a polymerization inhibitor, the shape and resolution of the pattern can be controlled.

As a UV absorber, for example, 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. Hydroxyphenyl triazine series, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, Benzotriazole-based compounds such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2,4- Benzophenone such as hydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, salicylate such as phenyl salicylate, p-tert-butylphenyl salicylate, etc. Cyanoacrylates such as ethyl 2-cyano-3,3'-diphenylacrylate, 2,2,6,6-tetramethylpiperidin-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] Hindered amines such as [(2,2,6,6-tetramethyl-4-piperidinyl) imino] and the like can be mentioned.
These ultraviolet absorbers can be used alone or in combination of two or more at an arbitrary ratio as needed.

Examples of polymerization inhibitors include hydroquinones such as methyl hydroquinone, t-butyl hydroquinone, 2,5-di-t-butyl hydroquinone, 4-benzoquinone, 4-methoxyphenol, 4-methoxy-1-naphthol, t-butyl catechol and the like Derivatives and amine compounds such as phenolic compounds, phenothiazine, bis- (1-dimethylbenzyl) phenothiazine, 3,7-dioctylphenothiazine, copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate, manganese diphenyldithiocarbamate and the like 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 alone or in combination of two or more at an arbitrary ratio as needed.

The ultraviolet absorber and the polymerization inhibitor can be used in an amount of 0.01 to 20 parts by mass, preferably 0.05 to 10 parts by mass, with respect to 100 parts by mass of the colorant in the coloring composition.
Better resolution can be obtained by using 0.01 part by mass or more of the ultraviolet absorber or the polymerization inhibitor.

<Antioxidant>
The coloring composition for color filters of the present invention can contain an antioxidant to increase the transmittance of the coating film. In order to prevent the photopolymerization initiator contained in the coloring composition for color filters from being oxidized and yellowed due to a thermal process at the time of heat curing or ITO annealing, the antioxidant may increase the transmittance of the coating film. it can. Therefore, by including an antioxidant, it is possible to prevent yellowing due to oxidation in the heating step and to obtain a high transmittance of the coating film.

Preferred examples of the antioxidant include hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants and sulfide-based antioxidants. Also, more preferably, hindered phenol antioxidants, hindered amine antioxidants, or phosphorus antioxidants are used.
These antioxidants can be used alone or in combination of two or more at an arbitrary ratio as required.

  Examples of hindered phenolic antioxidants include 2,4-bis [(laurylthio) methyl] -o-cresol, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), and 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-) Examples include di-t-butylanilino) -1,3,5-triazine, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, and the like.

  Among the hindered amine antioxidants, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, N N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine, 2-methyl-2- (2,2,6,6-tetramethyl-4-) Piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) (1,2,3,4 -Butane tetracarboxylate, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl} {(2,2,6,6- Tetramethyl-4-piperidyl) Mino} hexamethyl {(2,2,6,6-tetramethyl-4-piperidyl) imino}], poly [(6-morpholino-1,3,5-triazine-2,4-diyl) {(2,2 , 6,6-Tetramethyl-4-piperidyl) imino} hexamethine {(2,2,6,6-tetramethyl-4-piperidyl) imino}], dimethyl succinate and 1- (2-hydroxyethyl) -4 N, N'-4,7-tetrakis [4,6-bis {N-butyl-N- (1,2,2,6, polycondensate with 4-hydroxy-2,2,6,6-tetramethylpiperidine; 6,6-pentamethyl-4-piperidyl) amino} -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine and the like.

  As the phosphorus-based antioxidant, tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphepine- 6-yl] oxy] ethyl] amine, tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphepin-2-one Yl) oxy] ethyl] amine and ethyl phosphite bis (2,4-di-tert-butyl-6-methylphenyl).

  As a sulfide-based antioxidant, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis [(octylthio) methyl]- o-cresol, 2,4-bis [(laurylthio) methyl] -o-cresol, etc. may be mentioned.

The content of the antioxidant is preferably 0.1 to 5% by mass in the total 100% by mass of the solid content of the color composition for a color filter.
When the amount of the antioxidant is less than 0.1% by mass, the effect of increasing the transmittance is small, and when the amount is more than 5% by mass, the hardness is largely reduced and the sensitivity of the color composition for color filter is largely reduced.

<Other ingredients>
The coloring composition for a color filter of the present invention contains an adhesion improver such as a silane coupling agent or the like, or an amine compound having a function of reducing dissolved oxygen in order to enhance the adhesion to a transparent substrate. It can be done.

  As the silane coupling agent, for example, vinylsilanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, 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-epoxy Epoxysilanes such as cyclohexyl) methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (Aminoethyl) γ-ami Propyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, Aminosilanes such as N-phenyl-γ-aminopropyltriethoxysilane; and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane.

  The silane coupling agent can be used in an amount of 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, with respect to 100 parts by mass of the colorant in the coloring composition.

  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.

<Method of Producing Colored Composition for Color Filter>
The coloring composition of the present invention for a color filter comprises a colorant, a dispersant, a colorant carrier such as a resin and / or a solvent, optionally together with a dispersion aid, a kneader, and a two-roll mill. It can be finely dispersed and manufactured using various dispersing means such as 3-roll mill, ball mill, horizontal sand mill, vertical sand mill, annular type bead mill or attritor (colorant dispersion). At this time, two or more kinds of colorants and the like may be simultaneously dispersed in the colorant carrier, or those separately dispersed in the colorant carrier may be mixed.

Moreover, when using as a photosensitive coloring composition for color filters (resist material), it can prepare as a solvent development type or an alkali development type coloring composition. A solvent-developable or alkali-developable coloring composition comprises the colorant dispersion, a photopolymerizable monomer and / or a photopolymerization initiator, and, if necessary, a solvent, another pigment dispersant, and an additive. Etc. can be mixed and adjusted. The photopolymerization initiator may be added at the stage of preparing the coloring composition, or may be added later to the prepared coloring composition.
(Dispersion aid)
When the coloring agent is dispersed in the coloring agent carrier, not only the dispersing agent but also, optionally, a dispersing aid such as a pigment derivative or a surfactant may be contained. Since the dispersion aid has a great effect of preventing re-aggregation of the colorant after dispersion, the coloring composition formed by dispersing the colorant in the colorant carrier using the dispersion aid has brightness and viscosity stability. It becomes good.

  As the surfactant, sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecyl benzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate Anionic surfactants such as lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearic acid, monoethanolamine styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate ester, etc. Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; cationic surfactants such as alkyl quaternary ammonium salts and ethylene oxide adducts thereof; alkyl dimethylamino There may be mentioned amphoteric surfactants such as alkyl betaines such as betaine acetate and alkyl imidazolines, which may be used alone or in combination of two or more, but it is not necessarily limited thereto.

  When a surfactant is added, it is preferably 0.1 to 55 parts by mass, more preferably 0.1 to 45 parts by mass with respect to 100 parts by mass of the colorant. When the content of the surfactant is less than 0.1 parts by mass, the added effect is difficult to be obtained, and when the content is more than 55 parts by mass, the dispersing agent may affect the dispersion due to an excess of the dispersing agent. .

<Removal of coarse particles>
The coloring composition of the present invention may be coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more, by means of centrifugation, filtration with a sintered filter or membrane filter, and the like. It is preferable to carry out the removal of the mixed dust. Thus, the coloring composition preferably contains substantially no particles of 0.5 μm or more. More preferably, it is 0.3 μm or less.

<Color filter>
Next, the color filter of the present invention will be described.
The color filter of the present invention comprises a red filter segment, a green filter segment and a blue filter segment on a substrate, and further comprises a magenta filter segment, a cyan filter segment or a yellow filter segment The at least one filter segment may be formed of the coloring composition of the present invention.

  Examples of base materials such as transparent substrates constituting color filters include glass plates such as soda lime glass, low alkali borosilicate glass, non-alkali aluminoborosilicate glass, and resin plates such as polycarbonate, polymethyl methacrylate and polyethylene terephthalate. Used. In addition, on the surface of a glass plate or a resin plate, a transparent electrode made of indium oxide, tin oxide or the like may be formed for driving liquid crystal after panelization.

<Method of manufacturing color filter>
The color filter of the present invention can be produced by a printing method or a photolithography method using the above-mentioned coloring composition. Since formation of the filter segment by the printing method can be patterned only by repeating printing and drying of the coloring composition prepared as printing ink, it is low-cost as a manufacturing method of a color filter, and excellent in mass productivity. There is. Furthermore, with the development of printing technology, printing of fine patterns having high dimensional accuracy and smoothness can be performed. In order to print, it is preferable to set it as a composition which an ink does not dry and solidify on the printing plate or on a blanket. In addition, control of the flowability of the ink on the printing press is also important, and the preparation of the ink viscosity can also be performed by the dispersant and the extender pigment.

  When a filter segment is formed by photolithography, the coloring composition prepared as the above-mentioned solvent development type or alkali development type coloring resist material is coated on a transparent substrate by spray coating, spin coating, slit coating, roll coating, etc. The dry film is applied to a thickness of 0.2 to 5 μm by a method. The film dried if necessary is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Thereafter, it is immersed in a solvent or an alkaline developer, or the developer is sprayed by a spray or the like to remove the uncured portion to form a desired pattern. A color filter can be manufactured by repeating the same operation as this for other colors. Furthermore, in order to accelerate | stimulate superposition | polymerization of a coloring resist material, heating can also be given as needed. According to the photolithography method, it is possible to manufacture a color filter with higher accuracy than the above-mentioned printing method.

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

  The color filter of the present invention can be produced by an electrodeposition method, a transfer method, an inkjet method, etc. in addition to the above method, but the coloring composition of the present invention can be used in any method. The electrodeposition method is a method of manufacturing a color filter by electrodepositing each color filter segment on the transparent conductive film by electrophoresis of colloidal particles using the transparent conductive film formed on the substrate. . In the transfer method, filter segments are formed in advance on the surface of a peelable transfer base sheet, and the filter segments are transferred to a desired substrate.

  Before forming the color filter segments on a transparent substrate or a reflective substrate, a black matrix can be formed in advance. As the black matrix, although a multilayer film of chromium or chromium / chromium oxide, an inorganic film such as titanium nitride, or a resin film in which a light shielding agent is dispersed is used, it is not limited thereto. Alternatively, thin film transistors (TFTs) may be formed in advance on the transparent substrate or the reflective substrate and then the color filter segments may be formed. Moreover, an overcoat film, a transparent conductive film, etc. are formed on the color filter of this invention as needed.

  The color filter is bonded to the opposing substrate using a sealing agent, and liquid crystal is injected from the injection port provided in the seal portion, and then the injection port is sealed, and a polarizing film or retardation film is formed on the outside of the substrate as necessary. By bonding, a liquid crystal display panel which is a liquid crystal display device is manufactured.

<Solid-state imaging device>
The solid-state imaging device of the present invention comprises the color filter of the present invention. The configuration of the solid-state imaging device of the present invention is a configuration provided with the color filter for the solid-state imaging device of the present invention, and is not particularly limited as long as it functions as a solid-state imaging device. Configuration is mentioned.
A transfer electrode comprising a plurality of photodiodes and polysilicon forming a light receiving area of a solid-state imaging device (CCD sensor, CMOS sensor, organic CMOS sensor, etc.) is provided on a substrate, and the photodiode and the transfer electrode are formed on the substrate. It has a light shielding film made of tungsten or the like in which only the light receiving portion of the photodiode is opened, and has a device protective film made of silicon nitride or the like formed on the light shielding film so as to cover the entire light shielding film and the photodiode light receiving portion. It is a structure which has a color filter for solid-state image sensors of this invention on a device protective film.
Furthermore, a configuration having a condensing means (for example, a micro lens etc. hereinafter the same) on the device protective layer and under the color filter (closer to the substrate), a configuration having a condensing means on the color filter, etc. It may be
The organic CMOS sensor includes a thin film panchromatic photosensitive organic photoelectric conversion film and a CMOS signal readout substrate as a photoelectric conversion layer, and an organic material plays a role of capturing light and converting it into an electric signal. This is a two-layer hybrid structure in which the inorganic material plays the role of extracting the signal to the outside, and in principle, the aperture ratio can be 100% with respect to incident light. The organic photoelectric conversion film is a structure-free continuous film and can be laid on a CMOS signal reading substrate, so it does not require an expensive microfabrication process and is suitable for filter segment miniaturization.
The arrangement of the color filter segments is not particularly limited, and known methods can be used.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereby. In the examples, “parts” and “%” represent “parts by mass” and “% by mass”, respectively. Also, "PGMAC" means propylene glycol monomethyl ether acetate.

(Polymerization average molecular weight (Mw) of resin)
The polymerization average molecular weight (Mw) of the resin was measured using a TSK gel column (manufactured by Tosoh Corporation) and a GPC equipped with a RI detector (HLC-8120GPC manufactured by Tosoh Corporation), using polystyrene as the developing solvent and polystyrene conversion It is a weight average molecular weight (Mw).

(Acid number of resin)
80 ml of acetone and 10 ml of water are added to 0.5 to 1.0 parts of the resin solution, and the mixture is stirred and uniformly dissolved, and a 0.1 mol / L KOH aqueous solution is used as a titration solution to make an automatic titrator ("COM-555") The acid value of the resin solution was measured by titration using Hiranuma Sangyo Co., Ltd.). And the acid value per solid content of resin was computed from the acid value of resin solution, and solid content concentration of resin solution.

(Average molecular weight of block copolymer)
The number average molecular weight (Mn) and weight average molecular weight (Mw) of the block copolymer were measured using HLC-8320GPC (manufactured by Tosoh Corporation) as an apparatus, using SUPER-AW 3000 as a column, and 30 mM triethylamine and 10 mM as an eluent. It is the number average molecular weight (Mn) and weight average molecular weight (Mw) of polystyrene conversion measured using the N, N- dimethylformamide solution of LiBr.

(Amine value of block copolymer)
The amine value of the block copolymer is a value obtained by converting the total amine number (mg KOH / g) measured in solid content in accordance with the method of ASTM D 2074.

<Method of producing binder resin>
(Preparation of Acrylic Resin Solution 1)
70.0 parts of cyclohexanone is charged into a reaction vessel in which a thermometer, a cooling pipe, a nitrogen gas introduction pipe, and a stirring device are attached to a separable four-necked flask, the temperature is raised to 80 ° C., the inside of the reaction vessel is purged with nitrogen, and then a dropping pipe 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate ("Alonix M110" manufactured by Toagosei Co., Ltd.), A mixture of 0.4 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a solution of an acrylic resin having a weight average molecular weight (Mw) of 26000. After cooling to room temperature, about 2 g of the resin solution is sampled, dried by heating at 180 ° C. for 20 minutes, non-volatile content is measured, and propylene glycol monoethyl so that non-volatile content is 20% by mass in the resin solution synthesized above. Ether acetate was added to prepare an acrylic resin solution 1.

Preparation Example 1 Synthesis of quinacridone dye derivative CG-1 I. 6 parts of C.I. pigment red 209 (Klariant "hosta palm" red EGtransp) was introduced into 60 parts of fuming sulfuric acid (25% SO ₃ ) at 15 ° C. with stirring. C. I. Pigment Red 209 was dissolved in fuming sulfuric acid, heated to 30 ° C. and stirred for 3 hours, and then added to 150 parts of ice. After standing for 30 minutes, the resulting suspension is filtered and the product obtained is washed with 30 parts of water. The product was poured into 200 parts of water and neutralized (added with an aqueous ammonia solution until the pH reached 7) with an aqueous ammonia solution. 117 parts of lauryl ammonium were added and the mixture was stirred at 80 ° C. for 30 minutes, and the deposited precipitate was filtered at 60 ° C. The filtered wet crystals are washed with a 2% aqueous solution of ammonium chloride and then with methanol, and then dried at 80 ° C. to obtain a 9 parts C.I. I. Pigment red 209 sulfonated derivative to obtain an amine salt.

Preparation Example 2 Synthesis of quinacridone pigment derivative CG-2 I. 6 parts of CI Pigment Red 122 (Clariant's Hostaperm Pink E) was introduced into 60 parts of fuming sulfuric acid (25% SO ₃ ) at 15 ° C. while stirring. C. I. Pigment Red 122 was dissolved in fuming sulfuric acid, heated to 30 ° C. and stirred for 3 hours, and then added to 150 parts of ice. After standing for 30 minutes, the resulting suspension is filtered and the product obtained is washed with 30 parts of water. The product was poured into 200 parts of water and neutralized (added with an aqueous ammonia solution until the pH reached 7) with an aqueous ammonia solution. 125 parts of lauryl ammonium was added and stirred at 80 ° C. for 30 minutes, and the deposited precipitate was filtered at 60 ° C. The filtered wet crystals are washed with methanol and then dried at 80 ° C. to give 9 parts of formula (B-9) C.I. I. Pigment Red 122 sulfonated derivative to obtain an amine salt.

Production Example 3 Synthesis of Isoindoline-Based Dye Derivative · CG-3 C. I. 5 parts of pigment pigment yellow 139 (BASF Pariotello yellow D 1819) were added at room temperature while stirring in 65 parts of 28 mass% fuming sulfuric acid. After stirring at 90 ° C. for 19 hours, the mixture was poured into a mixture of 80 parts of ice, 15 parts of water, and 30 parts of isopropyl alcohol. The suspension was stirred in an ice bath for 30 minutes and then suction filtered to obtain a wet cake. The obtained wet cake is stirred and washed in 40 parts of isopropyl alcohol at room temperature, and suction filtration is performed four times, and then the wet cake is vacuum dried at 80 ° C. and pulverized to obtain Formula (B-11). C. indicated by I. Pigment pigment yellow 139 sulfonated derivative was obtained.

Preparation Example 4 Synthesis of Quinophthalone Dye Derivative · CG-4 C. I. In 300 parts of 101% sulfuric acid, 30 parts of pigment pigment yellow 138 ("Palitol yellow K0960-HD" manufactured by BASF Corporation) was dissolved, and the mixture was stirred at 70 ° C for 8 hours to conduct a sulfonation reaction. The end point of the reaction was determined by measuring the spectrum of the sulfuric acid solution and finding no change in the spectrum. Then, the reaction solution was poured into 3000 parts of ice water, and the precipitated sulfonated dye derivative was separated by filtration and washed with water to obtain a paste of the sulfonated dye derivative. With respect to the obtained sulfonated dye derivative, as a result of mass analysis by TOF-MS and elemental analysis, C.I. I. It matched with the molecular weight of the sulfonated derivative of pigment pigment yellow 138. The paste of the obtained sulfonated dye derivative was redispersed in 10000 parts of water (pH 2.5). Then, the solution was adjusted to pH 11 with an aqueous solution of sodium hydroxide and dissolved to give a red solution. To this solution, 278 parts of an aqueous solution of aluminum sulfate (liquid sulfuric acid band) was gradually added. The precipitate appeared one after another from the dripping point, and the pH decreased with the addition, and the pH was 3.6 at the end of the addition, and no bleeding was observed. The slurry containing this precipitate is separated by filtration, washed with water, and C.I. I. An aluminum salt of a sulfonated derivative of pigment pigment yellow 138 was obtained.

Preparation Example 5 Synthesis of Quinophthalone Dye Derivative CG-5 To 100 parts of methyl benzoate, 40 parts of 8-aminoquinaldine, 115 parts of 2,3-naphthalenedicarboxylic acid anhydride and 154 parts of benzoic acid are added, and 180 is added. The mixture was heated to ° C and stirred for 6 hours while distilling off water. After cooling to room temperature, the reaction mixture was poured into 1200 parts of methanol and stirred at room temperature for 1 hour. The precipitated crystals were separated by filtration, further washed with methanol, and dried under reduced pressure. Subsequently, 900 parts of water and 150 parts of potassium hydroxide were added to the above product, and the mixture was heated to 90 ° C. and stirred for 16 hours. After cooling to room temperature, 200 parts of 36% hydrochloric acid was added dropwise. The precipitated crystals were separated by filtration, further washed with methanol, and dried under reduced pressure. Subsequently, the above product was added to 300 parts of methyl benzoate, 87 parts of tetrachlorophthalic anhydride and 123 parts of benzoic acid were further added, and the mixture was heated to 180 ° C. and stirred for 5 hours while distilling off water. After cooling to room temperature, the reaction mixture was poured into 1200 parts of methanol and stirred at room temperature for 1 hour. The precipitated crystals were separated by filtration, further washed with methanol, and dried under reduced pressure to obtain 141 parts (yield: 92%) of a quinophthalone compound (a) represented by the following formula. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a quinophthalone compound (a).
A solution of 26 parts of the quinophthalone compound (a) obtained above was dissolved in 214 parts of 98% sulfuric acid and 236 parts of 25% fuming sulfuric acid, and the mixture was stirred at 85 ° C. for 2 hours to conduct a sulfonation reaction. Next, this reaction solution was dropped into 3,000 parts of ice water, and the deposited quinophthalone compound was filtered off and washed with water to obtain a paste. The obtained paste was re-dispersed in 8000 parts of water and stirred at room temperature for 1 hour. The precipitate was separated by filtration, washed with water and then dried overnight at 80 ° C. to obtain 26 parts (yield: 89%) of a quinophthalone compound represented by the formula (B-16).

Production Example 6 Synthesis of dianthraquinone pigment derivative · CG-6 In 240 parts of chlorosulfonic acid, C.I. I. The pigment pigment red 177. 30 parts were added, and it heated at 90 degreeC for 3 hours, and poured into 2000 parts ice water. The resulting suspension is filtered, washed with water, C.I. I. 180 parts of a water paste of chlorosulfonated pigment pigment red 177 were obtained. Obtained C.I. I. An aqueous paste of a chlorosulfonate of pigment pigment red 177 was reslurried in 10000 parts of water, adjusted to pH 11 with an aqueous sodium hydroxide solution, and stirred at 90 ° C. for 6 hours while appropriately adding so as to maintain pH 11. The pH is adjusted to 10 with hydrochloric acid, 50 g of aluminum sulfate aqueous solution (liquid sulfuric acid band) is added, and after stirring at 90 ° C. for 2 hours, the deposited precipitate is filtered, washed with water and dried to give formula (B-18) C. I. 25 parts of an aluminum salt of a sulfonated derivative of pigment pigment red 177 was obtained.

<Production Method of Basic Dispersant (C) Containing Acrylic Block Copolymer>
(Production example of block copolymer (EB-1): AB type block polymer)
60 parts of methyl methacrylate, 20 parts of n-butyl methacrylate, 13.2 parts of tetramethylethylenediamine as a catalyst are charged into a reaction apparatus equipped with a gas introduction pipe, a condenser, a stirring blade and a thermometer, and a nitrogen flow is carried out at 50 ° C. The mixture was stirred for 1 hour, and the system was purged with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate as an initiator, 5.6 parts of cuprous chloride as a catalyst, and 133 parts of methoxypropyl acetate are charged, the temperature is raised to 110 ° C. under a nitrogen stream, and the first block (B Polymerization of block) was started. After polymerization for 4 hours, the polymerization solution was sampled and the solid content was measured, and it was confirmed from conversion of non-volatile matter that the polymerization conversion rate was 98% or more. Next, 61 parts of methoxypropyl acetate and 20 parts of dimethylaminoethyl methacrylate as the second block (A block) monomer were charged into this reactor, and the reaction was continued while maintaining the nitrogen atmosphere at 110 ° C. . After 2 hours from the addition of dimethylaminoethyl methacrylate, the polymerization solution is sampled and the solid content is measured, and it is confirmed that the conversion conversion of the second block (A block) is 98% or more by converting it from the nonvolatile content. The solution was cooled to room temperature to stop the polymerization. As a result of GPC measurement, the polymer had a Mw of 9900, a molecular weight distribution Mw / Mn of 1.2, and a reaction conversion of 98.5%. Thus, an acrylic block copolymer (EB-1) having an amine value of 71.4 mg KOH / g per solid content was obtained. After cooling to room temperature, about 2 g of the resin solution is sampled, dried by heating at 180 ° C. for 20 minutes, non-volatile content is measured, and propylene is synthesized so that the non-volatile content is 50% by mass in the block copolymer solution previously synthesized. Glycol monomethyl ether acetate was added to prepare an acrylic block copolymer (EB-1) solution.

(Production of block copolymer (EB-2 to EB-8, EB-10))
The synthesis is carried out in the same manner as (EB-1) except that the raw materials and charge amounts described in Table 1 are used, and solutions of block copolymers (EB-2) to (EB-8) and (EB-10) I got
(Production example of block copolymer (EB-9): BAB type block polymer)
Charge 20 parts of methyl methacrylate, 15 parts of n-butyl methacrylate, 13.2 parts of tetramethylethylenediamine into a reactor equipped with a gas introduction pipe, a condenser, a stirring blade, and a thermometer, and flow for 1 hour at 50 ° C while flowing nitrogen Stir and replace the inside of the system with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride and 133 parts of methoxypropyl acetate are charged, and the temperature is raised to 110 ° C. under nitrogen stream to polymerize the first block (B block). It started. After polymerization for 3 hours, the polymerization solution was sampled to conduct solid content measurement, and conversion from non-volatile matter confirmed that the polymerization conversion ratio was 98% or more.
Next, 30 parts of methoxypropyl acetate and 25 parts of dimethylaminoethyl methacrylate as a second block (A block) monomer are charged into this reactor, and stirring is carried out while maintaining the nitrogen atmosphere at 110 ° C. to continue the reaction did. After 2 hours from the addition of dimethylaminoethyl methacrylate, the polymerization solution was sampled and the solid content was measured, and it was confirmed that the polymerization conversion ratio of the second block (A block) was 98% or more by converting from non-volatile content.
Next, 31 parts of methoxypropyl acetate, third block (B block), 25 parts of methyl methacrylate and 15 parts of n-butyl methacrylate are charged into this reactor, and the temperature is raised to 110 ° C. under a nitrogen stream to Polymerization of the block (B block) was continued. 4 hours after the third block (B block) monomer was charged, the polymerization solution was sampled to measure the solid content, and the reaction solution was confirmed to have a polymerization conversion ratio of 98% or more converted from non-volatile matter and cooled to room temperature The polymerization was stopped.
After cooling to room temperature, about 2 g of the resin solution is sampled, dried by heating at 180 ° C. for 20 minutes, non-volatile content is measured, and propylene is synthesized so that the non-volatile content is 50% by mass in the block copolymer solution previously synthesized. Glycol monomethyl ether acetate was added to prepare a block copolymer (EB-9) solution.

The amine value and weight average molecular weight of each block copolymer were as described in Table 1.
MMA; methyl methacrylate nBA; n-butyl acrylate HEMA; hydroxyethyl methacrylate DM; dimethylaminoethyl methacrylate DE; diethylaminoethyl methacrylate LA-82; 1,2,2,6,6-pentamethyl piperidyl methacrylate DMC Benzyldimethylammonium chloride DMAPMA; N, N-dimethylaminoethyl (meth) acrylamide

<Method of producing finely divided pigment>

(Quinacridone micronized pigment (R-1))
C. I. 100 parts of C.I. Pigment Red 122 (Klariant "Hosta Palm Pink E" (quinacridone magenta red pigment), 1200 parts of sodium chloride, and 120 parts of diethylene glycol are charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.), 60 ° C The mixture was kneaded for 6 hours and subjected to salt milling. The resulting kneaded product is poured into 3 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, repeated filtration and washing with water to remove sodium chloride and diethylene glycol, and then dried overnight at 80 ° C. , 98 parts of quinacridone finely divided pigment (R-1) were obtained.

(Quinacridone micronized pigment (R-2))
C. I. Pigment red 122, C.I. I. Pigment red 202 ("QUIND MAGENTA 202 228-6843" (quinacridone red pigment) manufactured by DIC), the same procedure as in the preparation of quinacridone micronized pigment (R-1) was carried out, and quinacridone micronized pigment (R -2) I got 97 copies.

(Quinacridone micronized pigment (R-3))
C. I. Pigment red 122, C.I. I. Pigment red 207 ("FASTOGEN SUPER SCARLET GK" (quinacridone red pigment) manufactured by DIC), except that it is carried out in the same manner as in the production of quinacridone micronized pigment (R-1), and quinacridone micronized pigment (R-3) ) Obtained 97 copies.

(Quinacridone micronized pigment (R-4))
C. I. Pigment red 122, C.I. I. Pigment red 209 ("Hosta palm red EGtransp" (quinacridone red pigment) manufactured by Clariant Co., Ltd.) in the same manner as in the preparation of quinacridone micronized pigment (R-1), and quinacridone micronized pigment (R-4) ) Obtained 97 copies.

<Method of producing finely divided pigment of other colors>
(Production of red finely divided pigment: PR254-1)
Diketopyrrolopyrrole red pigment C.I. I. 200 parts of CI pigment red 254 ("B-CF" manufactured by BASF Corporation), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 80C for 6 hours. Next, this kneaded material is added to 8000 parts of hot water, stirred for 2 hours while heating to 80 ° C. to form a slurry, repeated filtration, washing with water to remove sodium chloride and diethylene glycol, and then dried overnight at 85 ° C. , 190 parts of a finely divided red pigment PR254-1. The specific surface area of the red finely divided pigment PR254-1 was 67 m ² / g.

(Production of green finely divided pigment: PG 58-1)
Phthalocyanine-based green pigment C.I. I. Pigment Green 58 ("FASTOGEN GREEN A 110" manufactured by DIC Corporation), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 80 ° C for 6 hours. The kneaded material is poured into 8000 parts of hot water, stirred for 2 hours while heating to 80 ° C. to form a slurry, repeated filtration and washing with water to remove sodium chloride and diethylene glycol, and dried at 85 ° C. overnight. The green refined pigment PG58-1 was obtained, The specific surface area of the green refined pigment PG58-1 was 75 m ² / g.

(Production of yellow finely divided pigment: PY 138-1)
Quinophthalone yellow pigment C.I. I. Pigment Yellow 138 (BASF "Parior Yellow K 0960-HD") 500 parts, sodium chloride 500 parts, and diethylene glycol 250 parts were charged in a stainless steel 1 gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded at 120 ° C for 8 hours . Next, the kneaded product is poured into 5 liters of warm water and stirred for 1 hour while heating to 70 ° C. to form a slurry, repeated filtration, washing with water to remove sodium chloride and diethylene glycol, and drying overnight at 80 ° C. 490 parts of yellow finely divided pigment PY 138-1 were obtained. The specific surface area of the yellow finely divided pigment PY138-1 was 85 m ² / g.

(Production of yellow finely divided pigment: PY139-1)
Isoindoline yellow pigment C.I. I. Pigment Yellow 139 ("PARIOTOL Yellow D1819" manufactured by BASF Corp.) 500 parts, 500 parts of sodium chloride and 250 parts of diethylene glycol were charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 120 ° C for 8 hours. Next, the kneaded product is poured into 5 liters of warm water and stirred for 1 hour while heating to 70 ° C. to form a slurry, repeated filtration, washing with water to remove sodium chloride and diethylene glycol, and drying overnight at 80 ° C. 490 parts of a finely divided yellow pigment PY139-1 were obtained. The specific surface area of the yellow finely divided pigment PY139-1 was 93 m ² / g.

(Preparation of blue finely divided pigment: PB 15: 6-1)
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 ("LIONOL BLUE ES" manufactured by Toyo Color Co., Ltd., specific surface area 60 m ² / g) 200 parts, sodium chloride 1400 parts, and diethylene glycol 360 parts in a stainless steel 1 gallon kneader And kneading at 80 ° C. for 6 hours. Next, this kneaded material is added to 8000 parts of hot water, stirred for 2 hours while heating to 80 ° C. to form a slurry, repeated filtration and washing with water to remove sodium chloride and diethylene glycol, and then dried overnight at 85 ° C. , 190 parts of a blue finely divided pigment PB15: 6-1 are obtained. The specific surface area of the blue finely divided pigment · PB 15: 6-1 was 80 m ² / g.

(Preparation of purple finely divided pigment: PV 23-1)
Dioxazine purple pigment C.I. I. Pigment Violet 23 ("LIONOGEN VIOLET RL" manufactured by Toyo Color Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 80 ° C for 6 hours. Next, this kneaded material is added to 8000 parts of hot water, stirred for 2 hours while heating to 80 ° C. to form a slurry, repeated filtration, washing with water to remove sodium chloride and diethylene glycol, and then dried overnight at 85 ° C. , 190 parts of a violet finely divided pigment PV23-1 were obtained. The specific surface area of the purple finely divided pigment PV23-1 was 95 m ² / g.

<Method of producing pigment dispersion>
Subsequently, a pigment dispersion was produced and evaluated as a colored composition.
Example 1
(Pigment dispersion (RP-1))
The following mixture is stirred and mixed so as to be uniform, and then dispersed for 3 hours with an Eiger mill ("Mini model M-250 MKII" manufactured by Eiger Japan) using zirconia beads of 0.5 mm in diameter, and then the pore diameter is 5. The mixture was filtered through a 0 μm filter to prepare a pigment dispersion (RP-1) having a non-volatile component of 20% by mass.
Quinacridone micronized pigment · (R-1): 10.8 parts pigment derivative (CG-1): 1.2 parts acrylic resin solution 1: 25.0 parts propylene glycol monomethyl ether acetate (PGMAc): 57.0 parts acrylic Block copolymer (EB-1): 6.0 parts

[Examples 2 to 18, Comparative Examples 1 to 8]
(Pigment dispersion (RP-2 to 26))
The pigment dispersion (RP-2 to 26) is the same as the pigment dispersion (RP-1) except that the quinacridone finely divided pigment, the pigment derivative and the acrylic block copolymer are changed to the compositions shown in Table 2 below. Was produced.

<Method of Producing Other Pigment Dispersions>
(Preparation of PR254 pigment dispersion (RP-27))
The following mixture is stirred and mixed so as to be uniform, and after being dispersed for 3 hours with an Eiger mill ("Mini model M-250 MKII" manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, a pore diameter of 5. The mixture was filtered through a 0 μm filter to prepare a pigment dispersion (RP-27) having a non-volatile component of 20% by mass.

Refined pigment PR254-1: 12.0 parts Acrylic resin solution: 40.0 parts Propylene glycol monomethyl ether acetate (PGMAc): 48.0 parts

  Pigment dispersions (GP-1) to (VP-1) were produced in the same manner as (RP-27) except that PR254-1 was changed to the finely divided pigment shown in Table 3.

<Evaluation of pigment dispersion>
The following evaluation was performed about pigment dispersions (RP-1)-(RP-26). The results are shown in Table 4.

(Contrast ratio (CR) evaluation of coating film)
The light emitted from the liquid crystal display backlight unit is polarized through the polarizing plate, passes through the coating of the coloring composition applied on the glass substrate, and reaches the other polarizing plate. At this time, light passes through the polarizing plate if the polarizing planes of the polarizing plate and the polarizing plate are parallel, but light is blocked by the polarizing plate if the polarization planes are orthogonal to each other. However, when light polarized by the polarizing plate passes through the coating film of the coloring composition, the colorant particles cause scattering or the like, and when a part of the polarization plane is deviated, transmission occurs when the polarizing plates are parallel. The amount of light to be reduced decreases, and when the polarizing plates are orthogonal, some light is transmitted. The transmitted light was measured as the brightness on the polarizing plate, and the ratio of the brightness when the polarizing plate was parallel to the brightness when orthogonal was calculated as the contrast ratio.
(Contrast ratio) = (brightness in parallel) / (brightness in orthogonal)
Therefore, when scattering occurs due to the coloring agent in the coating film, the brightness in parallel decreases and the brightness in orthogonal increases, so the contrast ratio decreases.

  A color luminance meter ("BM-5A" manufactured by Topcon Corporation) was used as a luminance meter, and a polarizing plate ("NPF-G1220DUN" manufactured by Nitto Denko Corporation) was used as a polarizing plate. In the measurement, it measured through the black mask which opened the 1-cm square hole in the measurement part.

The pigment dispersions are respectively coated on a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater, then dried at 70 ° C. for 20 minutes, then heated at 230 ° C. for 60 minutes, and allowed to cool The coated substrate was produced by The contrast ratio (CR) of the obtained coated substrate was measured. The prepared coated substrate was adjusted to have a film thickness of 1.5 μm after heat treatment at 230 ° C. The contrast ratio was determined according to the following criteria.

:: 3000 or more: extremely good ○: 2000 to less than 3000: good 良好: more than 1000 to less than 2000: practicable x: less than 1000: defective

(Viscosity evaluation (dispersion stability))
The initial viscosity at 25 ° C. was measured for the viscosity of the pigment dispersion using an E-type viscometer (“ELD-type viscometer” manufactured by Toki Sangyo Co., Ltd.). Separately, 25 g of the pigment dispersion was allowed to stand at 40 ° C. for 24 hours in a sealed state in a glass container, and then the viscosity was measured by the same method as described above to obtain the viscosity over time. Dispersion stability was evaluated on the basis of the following by viscosity change rate = (initial viscosity-viscosity over time) / initial viscosity x 100 (%). Evaluation criteria are shown below.

○ (Good for practical use): When the viscosity change rate is within ± 10% and no sediment is generated.
Δ (practical possibility): When the viscosity change rate is ± 10% to 20% and the sediment is not generated.
X (not practical): When the rate of viscosity change exceeds ± 20%, or when the rate of viscosity change is within ± 20%, a precipitate is produced.

(Foreign body evaluation)
The evaluation of the generation of foreign matter is carried out by applying the pigment dispersion to a transparent substrate so that the dried coating film is about 1.5 μm, heating in an oven at 250 ° C. for 60 minutes, and leaving it to cool. The number of foreign objects in it was counted. The surface was observed using a metallurgical microscope "BX60" manufactured by Olympus Systems Corporation. The magnification was set to 500 times, and the number of foreign substances observable in any five fields of view was measured in transmission.

:: number of foreign matter less than 3: extremely good ○: number of foreign matter is 3 or more and less than 20: good Δ: number of foreign matter is 21 or more and less than 100: practicable ×: number of foreign matter is 100 Pieces or more: Defective

  As shown in Table 4, by using the quinacridone pigment and the dye derivative / block copolymer in combination, excellent results in contrast ratio, viscosity characteristics and foreign matter were obtained. Among them, as the dye derivative, CG-1 and CG-2, which are sulfonic acid forms of quinacridone pigments, showed good results. The block copolymer was relatively good in the system using dimethylaminoethyl methacrylate.

<Production of Photosensitive Colored Composition for Color Filter>
[Example 19]
(Red photosensitive coloring composition (RR-1))
The mixture of the following composition was stirred and mixed so as to be uniform, and then filtered through a filter with a pore size of 1 μm to prepare a red photosensitive coloring composition (RR-1).

Pigment dispersion (RP-1): 14.0 parts Pigment dispersion (RP-27): 36.0 parts Acrylic resin solution 1: 7.5 parts Photopolymerizable monomer (manufactured by Toagosei Co., Ltd. "ALONIX M-" 402 "): 2.0 parts Photopolymerization initiator (" IRGACURE OXE-02 "manufactured by BASF Corporation): 1.2 parts Sensitizer (" EAB-F "manufactured by Hodogaya Chemical Industry Co., Ltd.): 0.3 parts Cyclohexanone: 39.0 parts

[Examples 20 to 36, Comparative Examples 9 to 16] (Red photosensitive coloring composition (RR-2 to 26))
A red photosensitive coloring composition (RR-2) was prepared in the same manner as in Example 19, except that the breakdown of 50 parts of the total of the pigment dispersion which is the coloring liquid was changed to the components and parts by mass shown in Table 5, respectively. ) To (RR-26) were produced.

<Evaluation of photosensitive coloring composition for color filter>
The following evaluation was performed about the obtained red photosensitive coloring composition. The results are shown in Table 5.

(Evaluation of heat resistance)
The obtained red photosensitive coloring composition was applied to a glass substrate on which a black matrix is formed in advance by a spin coating method, and then dried in a clean oven at 70 ° C. for 20 minutes. Then, the substrate was cooled to room temperature and then exposed to ultraviolet light through a photomask using an extra-high pressure mercury lamp. Thereafter, the substrate was spray developed for 30 seconds in a 0.2% by mass aqueous solution of sodium carbonate at 23 ° C., washed with ion exchanged water, and dried. Further, heat treatment was performed at 230 ° C. for 30 minutes in a clean oven to form a stripe-like colored pixel layer on the substrate. The prepared colored pixel layer was adjusted to have a film thickness of 2.0 μm after heat treatment at 230 ° C. [L ^* (1), a ^* (1), b ^* (1)] was measured using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.) of the obtained coating film. Further, the chromaticity [L ^* (2), a ^* (2), b ^* (2)] after heat treatment at 250 ° C. for 60 minutes was measured, and the color difference ΔE ^* ab was determined by the following equation. The heat resistance was determined according to the following criteria.
ΔE ^* ab = [[L ^* (2) -L ^* (1)] ² + [a ^* (2) -a ^* (1)] ² + [b ^* (2) -b ^* (1)] ² ] ^1/2

:: ΔE ^* ab = 1 less: extremely good ○: ΔE ^* ab = 1 or more and less than 3: good Δ: ΔE ^* ab = 3 or more and less than 5: practicable x: ΔE ^* ab = 5 or more: defective

(Foreign body evaluation)
In the evaluation of the generation of foreign matter, the number of foreign matter in colored pixels was measured using the substrate after the heat treatment at 250 ° C. manufactured in the heat resistance evaluation. The surface was observed using a metallurgical microscope "BX60" manufactured by Olympus Systems Corporation. The magnification was set to 500 times, and the number of foreign substances observable in any five fields of view was measured in transmission.

:: number of foreign matter less than 3: extremely good ○: number of foreign matter is 3 or more and less than 20: good Δ: number of foreign matter is 21 or more and less than 100: practicable ×: number of foreign matter is 100 Pieces or more: Defective

(Evaluation of solvent resistance)
The obtained photosensitive coloring composition was applied to a glass substrate on which a black matrix is formed in advance by a spin coating method, and then dried in a clean oven at 70 ° C. for 20 minutes. Then, the substrate was cooled to room temperature and then exposed to ultraviolet light through a photomask using an extra-high pressure mercury lamp. Thereafter, the substrate was spray developed for 30 seconds in a 0.2% by mass aqueous solution of sodium carbonate at 23 ° C., washed with ion exchanged water, and dried. Further, heat treatment was performed at 230 ° C. for 30 minutes in a clean oven to form a stripe-like colored pixel layer on the substrate. The prepared colored pixel layer was adjusted to have a film thickness of 2.0 μm after heat treatment at 230 ° C. [L ^* (1), a ^* (1), b ^* (1)] was measured using the microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.) for the obtained striped colored pixels. . After that, soak in N-methyl-2-pyrrolidone (NMP) or methanol (MeOH) for 15 minutes, and measure the chromaticity [L ^* (2), a ^* (2), b ^* (2)] after immersion. The color difference ΔE ^* ab was determined. The calculation method of the color difference ΔE ^* ab and the evaluation standard of the solvent resistance are the same as those of the heat resistance evaluation of the coloring composition for color filter.

  From Table 5, similar to the result of the pigment dispersion, the combination of quinacridone pigment and the pigment derivative / block copolymer is also used in the photosensitive coloring composition, and the result excellent in solvent resistance, heat resistance and foreign matter is obtained. The Among them, as the dye derivative, CG-1 and CG-2, which are sulfonic acid forms of quinacridone pigments, showed good results. The block copolymer was relatively good in the system using dimethylaminoethyl methacrylate.

<Preparation of color filter>
A red photosensitive coloring composition containing the quinacridone pigment of the present invention was used to prepare a color filter. The green photosensitive coloring composition and the blue photosensitive coloring composition used were prepared as follows.

(Green photosensitive coloring composition (GR-1))
The mixture of the following composition was stirred and mixed so as to be uniform, and then filtered through a filter with a pore size of 1 μm to prepare a green photosensitive coloring composition (GR-1).
PG 58. Pigment dispersion (GP-1): 35.0 parts PY 138. Pigment dispersion (YP-1): 15.0 parts Methacrylic resin solution 1: 7.5 parts Photopolymerizable monomer (manufactured by Toagosei Co., Ltd.) "Alonics M-402": 2.0 parts Photopolymerization initiator ("IRGACURE 907" manufactured by BASF Corporation): 1.2 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Industry Co., Ltd.): 0. 3 parts cyclohexanone: 39.0 parts

(Blue photosensitive coloring composition (BR-1))
The mixture of the following composition was stirred and mixed so as to be uniform, and then filtered through a filter with a pore diameter of 1 μm to prepare a blue photosensitive colored composition (BR-1).
PB 15: 6 pigment dispersion (BP-1): 45.0 parts PV 23 pigment dispersion (VP-1): 5.0 parts methacrylic resin solution 1: 7.5 parts photopolymerizable monomer (Toago synthesis "Alonics M-402" manufactured by Co., Ltd .: 2.0 parts Photopolymerization initiator ("IRGACURE 907" manufactured by BASF Corporation): 1.2 parts sensitizer ("EAB-F" manufactured by Hodogaya Chemical Industry Co., Ltd.): 0.3 parts cyclohexanone: 39.0 parts

[Example 37]
The red photosensitive coloring composition (RR-1) was applied to a glass substrate on which a black matrix is formed in advance by a spin coating method, and then dried in a clean oven at 70 ° C. for 20 minutes. The substrate was then cooled to room temperature, and then exposed to ultraviolet light through a photomask using an extra-high pressure mercury lamp.
Thereafter, the substrate was spray developed for 30 seconds in a 0.2% by mass aqueous solution of sodium carbonate at 23 ° C., washed with ion exchanged water, and dried. Further, heat treatment was performed at 230 ° C. for 30 minutes in a clean oven to form a stripe-like colored pixel layer on the substrate.
Next, using a green photosensitive coloring composition (GR-1), a green colored pixel layer was formed in the same manner as the red colored pixel layer. Furthermore, the blue photosensitive pixel composition was similarly formed using blue photosensitive coloring composition (BR-1), and the color filter (CF-1) was obtained. The formed film thickness of each colored pixel layer was 2.0 μm.

  About the obtained color filter, it confirmed about the presence or absence of the foreign material on the pixel. The measuring method is the same as in the case of evaluation of the pigment dispersion. It was confirmed that the color filter using the coloring composition by the quinacridone pigment of the present invention has no foreign matter. From the above, the effect of the quinacridone pigment of the present invention was proved.

<Production of Photosensitive Colored Composition for Solid-State Imaging Device>
[Example 38]
(Red photosensitive coloring composition (RR-27))
The mixture of the following composition was stirred and mixed so as to be uniform, and then filtered through a filter with a pore size of 1 μm to prepare a red photosensitive coloring composition (RR-27).

Pigment dispersion (RP-1): 39.0 parts Pigment dispersion (YP-2): 11.0 parts Acrylic resin solution 1: 7.5 parts Photopolymerizable monomer (manufactured by Toagosei Co., Ltd. "ALONIX M-" 402 "): 2.0 parts Photopolymerization initiator (" IRGACURE OXE-02 "manufactured by BASF Corporation): 1.2 parts Sensitizer (" EAB-F "manufactured by Hodogaya Chemical Industry Co., Ltd.): 0.3 parts Cyclohexanone: 39.0 parts

[Examples 39 to 52, Comparative Examples 17 to 19] (Red photosensitive coloring composition (RR-28 to 44))
A red photosensitive coloring composition (RR-28) was prepared in the same manner as in Example 38, except that the breakdown of 50 parts of the total of the pigment dispersion which is the coloring liquid was changed to the components and parts by mass shown in Table 6, respectively. ) To (RR-44) were produced.

<Evaluation of photosensitive coloring composition for solid-state imaging device>
Then, evaluation as a photosensitive coloring composition (spectral characteristic) for solid-state imaging devices was performed using the obtained red photosensitive coloring composition (RR-27-44). The results are shown in Table 6.
(Spectroscopic characterization)
The obtained red photosensitive coloring composition is coated on a 1.1 mm thick glass substrate using a spin coater so that the wavelength at which the spectral transmittance is 50% is in the wavelength range of 580 nm to 590 nm. After drying at 70 ° C. for 20 minutes, the coated substrate was further heated at 230 ° C. for 60 minutes. The spectrum of the obtained substrate was measured with a microspectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.). Evaluation criteria are as follows.

"Transmission of 400 nm"
・ ・ ・ ··· 400 nm transmittance is less than 15.0% ○ · · · 400 nm transmittance is 15.0% or more and less than 20.0% × · · · 400 nm transmittance is 20.0% or more “530 nm Transmittance
・ ・ ・ ··· 530 nm transmittance is less than 1.0% ○ · · · 530 nm transmittance is 1.0% or more and less than 3.0% × · · · 530 nm transmittance is 3.0% or more "600 nm Transmittance
・ ・ ・ · · · 600 nm transmittance is 90.0% or more ○ · · · 600 nm transmittance is 80.0% to less than 90.0% × · · · 600 nm transmittance is less than 80.0%

  As shown in Table 6, by using the quinacridone pigment of the present invention in combination with the dye derivative / block copolymer, it was possible to achieve both of the spectral characteristics at 400 nm, 530 nm, and 600 nm.

(Production of color filter for solid-state imaging device)
A resist solution for flattening film (HL-18s: manufactured by Nippon Steel Chemical Co., Ltd.) was applied by spin coating on a 6-inch silicon wafer, and heat treated on a hot plate at 100 ° C. for 6 minutes as pre-baking. Furthermore, the coated film was cured by treatment in an oven at 230 ° C. for 1 hour to form a 1.0 μm planarized film, and a wafer with a planarized film was obtained.

  The green photosensitive coloring composition (GR-1) was applied on a silicon wafer with a planarizing film by a spin coater, and heat treated on a hot plate at 100 ° C. for 1 minute as pre-baking. The film thickness after prebaking was adjusted to be 0.9 μm.

Then, using an i-line stepper exposure apparatus FPA-3000i5 + (Canon Co., Ltd.), pass a photomask for forming a 1.0 μm square red pixel at a wavelength of 365 nm and pattern at an exposure dose of 150 mJ / cm ² Exposure was done.

  The coated film after exposure was subjected to paddle development for 1 minute with an organic alkaline developer. After the paddle development, rinsing was performed with pure water in a spin shower for 20 seconds, and washing with water was performed for 20 seconds more pure. Thereafter, water droplets remaining on the wafer were blown away with high pressure air, the substrate was naturally dried, and heat treatment was further performed on a hot plate having a surface temperature of 230 ° C. for 5 minutes to form a square pixel pattern. The film thickness of the green pattern after the heat treatment was 0.80 μm.

  Next, a red photosensitive colored composition (RR-27) is used to form a red colored pixel layer in the same manner as the green colored pixel layer, and a blue photosensitive colored composition (BR-1) is used. A blue colored pixel layer was formed to obtain a color filter (CF-2).

The color filter for solid-state imaging device manufactured in this manner was very excellent in spectral characteristics.
In particular, in the red filter, the bumps around 530 nm are suppressed and the spectral characteristics are excellent and the heat resistance is excellent. Therefore, the solid-state imaging device using the color filter for the solid-state imaging device is particularly skin-colored It was excellent in reproducibility.

Claims (9)

  A color filter comprising a quinacridone pigment (A), a pigment derivative (B), a basic dispersant (C) containing an acrylic block copolymer, and a binder resin (D) Coloring composition.   The quinacridone pigment (A) is C.I. I. Pigment red 122, C.I. I. Pigment red 202, C.I. I. Pigment red 207 and C.I. I. The coloring composition for color filters according to claim 1, which is at least one selected from the group consisting of C.I.   The coloring composition for color filters according to claim 1 or 2, wherein the dye derivative (B) is a sulfonated dye derivative, or a metal salt or amine salt of a sulfonated dye derivative.   4. The color filter according to any one of claims 1 to 3, wherein the dye skeleton of the dye derivative (B) is at least one selected from the group consisting of quinacridone dyes, isoindoline dyes, quinophthalone dyes, and anthraquinone dyes. Composition. The basic dispersant (C) containing an acrylic block copolymer is a repeating unit represented by the following general formula (1), a repeating unit represented by the following general formula (2), and the following general formula (3) The coloring composition for color filters according to any one of claims 1 to 4, which has a block having at least one selected from the group consisting of repeating units represented by
(In the general formula (1), R _{1 to} R ₃ each independently represent a hydrogen atom or a chain or cyclic hydrocarbon group which may have a substituent, and R _{1 to} R ₃ Two or more of them may be bonded to each other to form a cyclic structure, R ₄ represents a hydrogen atom or a methyl group, X represents a divalent linking group, and Y − represents a counter anion.
(In the general formula (2), R ₅ and R ₆ are, independently of each other, hydrogen atom, or a substituted indicates also good chain or cyclic hydrocarbon group, R ₅ and R ₆ R ₄ may be bonded to each other to form a cyclic structure, R ₄ represents a hydrogen atom or a methyl group, and X represents a divalent linking group.
(In the general formula (3), R ₇ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an acyl group, an oxy radical group, or OR represents _12, R ₁₂ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group or an acyl group, having 7 to 12 carbon atoms, R _8, R _9, R ₁₀ and R ₁₁ each independently represent a methyl group, an ethyl group, or a phenyl group, R ₄ represents a hydrogen atom or a methyl group, and X represents a divalent linking group.   Furthermore, the photopolymerizable monomer (D) and the photoinitiator (E) are included, The coloring composition for color filters of any one of the Claims 1-5 characterized by the above-mentioned.   A color filter comprising a red filter segment formed using the coloring composition for a color filter according to any one of claims 1 to 6.   A liquid crystal display device comprising the color filter according to claim 7.   A solid-state image pickup device comprising the color filter according to claim 7.