JP2010117493A - Colored composition for color filter, color filter, method for producing color filter, liquid crystal display, and solid-state imaging device - Google Patents

Abstract

The present invention provides a coloring composition for a color filter having high pigment dispersibility and stability, providing a color filter having high contrast and little residue upon development, and a method for producing the color filter. Provided are a liquid crystal display device and a solid-state imaging device with favorable characteristics.
SOLUTION: (A) an organic pigment having an average primary particle diameter of 10 nm to 35 nm, (B1) a weight average molecular weight having a main chain portion having a polyallylamine structure or a polyalkyleneimine structure and a side chain portion made of polyester is 3000 to 3000 Graft polymer in the range of 15000, (B2) Graft polymer having a main chain part having a polyallylamine structure or a polyalkyleneimine structure and a side chain part made of polyester and having a weight average molecular weight in the range of 20000 to 60000, (C A coloring composition for a color filter comprising: a) an alkali-soluble resin, (D) a polyfunctional monomer, (E) a photopolymerization initiator, and (F) an organic solvent.
[Selection figure] None

Description

  The present invention relates to a coloring composition for a color filter, a color filter using the coloring composition, a method for producing the color filter, a liquid crystal display device including the obtained color filter, and a solid-state imaging device.

  The color filter contains a pigment dispersion composition in which an organic pigment or an inorganic pigment is dispersed, a polyfunctional monomer, a photopolymerization initiator, an alkali-soluble resin, and other components to form a colored composition. It is manufactured by forming a colored pattern using a photolithography method or the like.

  In recent years, color filters tend to be used not only for monitors but also for televisions (TVs) in liquid crystal display (LCD) applications. With this trend of application expansion, advanced color characteristics in chromaticity, contrast, etc. Has come to be required. In addition, in the image sensor (solid-state imaging device) application, a device having high color characteristics is also demanded.

  It is effective to use a pigment whose primary particle diameter is miniaturized to meet the above requirements. As a method for reducing the primary particle diameter of the pigment, for example, the pigment is combined with a water-soluble inorganic salt such as a synthetic resin that is solid and water-insoluble at room temperature, sodium chloride, and a water-soluble organic solvent that at least partially dissolves the synthetic resin. After kneading mechanically with a kneader or the like (hereinafter, kneading a mixture containing a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent is called salt milling), and then washing with water, the water-soluble inorganic salt and the water-soluble organic There is a method for removing the solvent (see, for example, Patent Document 1). In this method, since the primary particle pulverization and crystal growth occur in parallel with each other, the final particle size distribution is narrow, and a pigment with a small surface area is obtained in spite of a small average particle size. This method is suitable for obtaining a pigment for a use in which a pigment having a diameter needs to be dispersed at a high concentration.

However, the pigments thus produced often cause severe aggregation in the drying process after desalting, and thus the dispersibility and dispersion stability are often not good. When the dispersibility of the pigment is insufficient, fringes (jagged edges) and surface irregularities occur in the colored pattern formed by the coloring composition containing the pigment dispersion, and the chromaticity of the produced color filter There is a problem that the dimensional accuracy is lowered or the contrast is remarkably deteriorated.
Furthermore, when the dispersion stability of the pigment is poor, there is also a problem that the constituent components of the coloring composition are aggregated to increase the viscosity with time and the pot life is extremely shortened. In addition, when producing a color filter using such a colored composition, the uniformity of the film thickness in the coating process is reduced, resulting in variations in sensitivity in the exposure process and alkali solubility in the development process. Problems such as fluctuation and non-uniformity are likely to occur. In particular, when a colored film made of a colored composition is formed on a glass substrate in order to produce a color filter having a large area, defects such as streaks appear on the coated surface when slit coating (or die coating) is performed. There is a problem in that the coating surface property is deteriorated and this causes a pixel defect of the color filter.

  Therefore, as a method for improving the dispersibility and dispersion stability of the pigment, a method of adding rosin or a rosin derivative or a synthetic polymer compound during salt milling has been proposed (for example, see Patent Document 2). Also known is a method of adding a graft polymer obtained by reacting a polyallylamine or polyalkyleneimine with a polyester having a free carboxylic acid group to form an amide or salt as a pigment dispersant (see Patent Documents 3 and 4). ). However, even if these dispersants are used, it has been difficult to achieve the dispersion stability and high contrast of the fine pigment and to achieve good developability without residue.

In addition, it has also been proposed to improve the dispersibility stability of pigments by using two types of dispersants having different molecular weights (see Patent Document 5), but this proposal prevents gelation due to structure formation in aqueous pigment dispersions. This was intended, and it was not possible to improve dispersibility with fine pigments and achieve high contrast. In particular, as shown in Patent Document 5, when a dispersant having a high molecular weight is used before a dispersant having a low molecular weight, high dispersibility cannot be obtained.
Japanese Patent Laid-Open No. 7-13016 JP-A-8-179111 Japanese Patent Laid-Open No. 9-169821 JP 61-174939 A JP-A-6-175362

This invention is made | formed in view of said point, and makes it a subject to achieve the following objectives.
That is, an object of the present invention is to provide a coloring composition for a color filter that can form a colored film having excellent pigment dispersibility and stability and excellent contrast.
Another object of the present invention is to provide a color filter having a good surface shape, a high contrast and a small amount of residue in development, and a method for producing the color filter. It is another object of the present invention to provide a liquid crystal display device and a solid-state imaging device with good color characteristics by using this color filter.

Means for solving the above-mentioned problems are as follows.
<1> (A) Organic pigment having an average primary particle diameter of 10 nm to 35 nm, (B1) A main chain portion having a polyallylamine structure or a polyalkyleneimine structure, and a side chain portion made of polyester, and a weight average molecular weight of 3000 Graft polymer in the range of ˜15000, (B2) Graft polymer having a main chain part having a polyallylamine structure or a polyalkyleneimine structure and a side chain part made of polyester and having a weight average molecular weight in the range of 20,000 to 60,000 (C) An alkali-soluble resin, (D) a polyfunctional monomer, (E) a photopolymerization initiator, and (F) a coloring composition for a color filter containing an organic solvent.

<2> A graft polymer having a main chain part having a polyallylamine structure or a polyalkyleneimine structure and a side chain part made of polyester reacts with a polyester containing a free carboxylic acid group to polyallylamine or polyalkyleneamine. The coloring composition for a color filter according to <1>, which is a graft polymer obtained by making the composition.

<3> For (A) 100 parts by mass of the organic pigment having an average primary particle diameter of 10 nm to 35 nm, (B1) a main chain part having a polyallylamine structure or a polyalkyleneimine structure, and a side chain part made of polyester 5 to 60 parts by mass of a graft polymer having a weight average molecular weight of 3000 to 15000, and (B2) a main chain part having a polyallylamine structure or a polyalkyleneimine structure, and a side chain part made of polyester The coloring composition for color filters according to <1> or <2>, which contains 5 to 30 parts by mass of a graft polymer having a weight average molecular weight of 20,000 to 60,000.

<4> Any one of <1> to <3>, wherein (A) the alkali-soluble resin is contained in an amount of 5 to 100 parts by mass with respect to 100 parts by mass of the organic pigment having an average primary particle diameter of 10 nm to 35 nm. The coloring composition for color filters as described in the item.
<5> Any one of <1> to <4>, further comprising (G) 1 to 40 parts by mass of a pigment derivative with respect to 100 parts by mass of the organic pigment (A) having an average primary particle diameter of 10 nm to 35 nm. The coloring composition for color filters as described in above.
<6> A color filter using the colored composition for color filter according to any one of <1> to <5>.

<7> A photosensitive film forming step of forming a photosensitive film by applying the color filter coloring composition according to any one of <1> to <5> onto a substrate, and the formed photosensitive film And a colored pattern forming step of forming a colored pattern by sequentially performing pattern exposure and development.
<8> A liquid crystal display device comprising the color filter according to <6>.
<9> A solid-state imaging device comprising the color filter according to <6>.

In the present invention, the graft polymer having a specific structure is easily adsorbed to fine pigment particles, and the graft polymer having a specific structure with a low molecular weight having a weight average molecular weight in the range of 3000 to 15000 disperses the pigment particles in the primary particle state. In addition, the polymer particles with a specific structure having a weight average molecular weight in the range of 20000 to 60000 form a protective colloid of the pigment particles to prevent aggregation and stabilize the dispersion. It is estimated that As a result, the fine pigment is covered with the graft polymer having a specific structure, and it is considered that a colored pixel in a primary particle state without aggregation of the fine pigment is obtained. As a result, it is considered that there was no color unevenness and high contrast was exhibited.
Furthermore, in the color filter development process, the pigment particles are covered with a graft polymer having a specific structure, and the alkaline developer is likely to uniformly penetrate the colored layer, and the colored layer is easily dissolved in the alkaline developer. It is presumed that good pattern formability without developing residue is exhibited.

  ADVANTAGE OF THE INVENTION According to this invention, the coloring composition for color filters which can form the colored film excellent in the high pigment dispersibility and its stability, and excellent in contrast can be provided. In addition, it is possible to provide a color filter having a good surface shape, high contrast, and less residue in development, and a method for producing the color filter. Furthermore, by using this color filter, it is possible to provide a liquid crystal display device and a solid-state imaging device with good color characteristics.

  The present invention includes (A) an organic pigment having an average primary particle diameter of 10 nm to 35 nm, (B1) a main chain portion having a polyallylamine structure or a polyalkyleneimine structure, and a side chain portion made of polyester, and having a weight average molecular weight. Graft polymer in the range of 3000 to 15000 (hereinafter referred to as “dispersant B1” as appropriate), (B2) having a main chain portion having a polyallylamine structure or a polyalkyleneimine structure, and a side chain portion made of polyester. A graft polymer having a weight average molecular weight in the range of 20000 to 60000 (hereinafter referred to as “dispersant B2” as appropriate), (C) an alkali-soluble resin, (D) a polyfunctional monomer, and (E) photopolymerization. Coloring composition for color filters characterized by containing an initiator and (F) an organic solvent (hereinafter sometimes referred to as “coloring composition”) ) It is.

Below, each component which comprises the coloring composition of this invention is demonstrated in detail.
<(B1) Graft polymer: Dispersant B1 having a main chain portion having a polyallylamine structure or a polyalkylenimine structure and a side chain portion made of polyester and having a weight average molecular weight of 3000 to 15000>
Dispersant B1 and dispersant B2 of the present invention have the same basic structure, and both have a main chain portion having a polyallylamine structure or a polyalkyleneimine structure, and a side chain portion made of polyester. Graft polymer. The dispersant B1 will be described below.

The method for synthesizing the dispersant B1 is characterized by being obtained by reacting polyallylamine or polyalkylenimine with a polyester containing a free carboxylic acid group.
The composition ratio of the dispersant B1 and the dispersant B2 and the structures of the polyallylamine, polyalkyleneimine, and polyester may be the same or different. However, as for the weight average molecular weight, it is essential that the dispersant B1 is in the range of 3000 to 15000 and the dispersant B2 is in the range of 20000 to 60000.

  The polyallylamine constituting the dispersant B1 of the present invention is a compound containing a structural unit represented by the following formula (1), and is preferably composed of the formula (1). As the dispersant B1, the structural unit represented by the following formula is preferably in the range of 5 to 200, and more preferably in the range of 10 to 100. Within this range, the dispersion stability is good.

  In addition, polyallylamine can produce polyallylamine of arbitrary molecular weights using the method of Japanese Patent Publication No.2-14364. In addition, commercially available products of polyallylamine can also be used. Examples of commercially available products include “PA-1L”, “PA-1LV”, “PAA-1.4L”, “PAA-10C”, “PAA-10C”, “ PAA-15 "," PAA-15B "," PAA-L "," PAA-H "," PAA-1L-15C "and the like.

The polyalkyleneimine constituting the dispersant B1 of the present invention is preferably a polymer of alkyleneimine having 2 to 4 carbon atoms, and particularly preferably polyethyleneimine which is a polymer of ethyleneimine having 2 carbon atoms.
The molecular weight of the polyalkyleneimine used for the preparation of the dispersant B1 is preferably 300 to 10,000, more preferably 500 to 5,000.
The polyalkyleneimine can be synthesized and used by a known method, but a commercially available product can also be used. Examples of commercially available products include “Epomin SP-003”, “Epomin SP-006”, “Epomin SP-012”, “Epomin SP-018”, and “Epomin SP-200” manufactured by Nippon Shokubai Co., Ltd.

  Polyesters having free carboxylic acid groups to be reacted with polyallylamine or polyalkyleneimine are: (i) polycondensation of carboxylic acid and lactone, (ii) polycondensation of hydroxy group-containing carboxylic acid, (iii) dihydric alcohol and dialkyl alcohol. Can be obtained by polycondensation of a monovalent carboxylic acid (or cyclic acid anhydride).

  The carboxylic acid used in (i) is preferably an aliphatic carboxylic acid (a linear or branched carboxylic acid having 1 to 30 carbon atoms, such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, n-hexanoic acid, n- Octanoic acid, n-decanoic acid, n-dodecanoic acid, palmitic acid, 2-ethylhexanoic acid, cyclohexane acid, etc.), hydroxy group-containing carboxylic acid (linear or branched hydroxy group-containing carboxylic acid having 1 to 30 carbon atoms) Preferably, for example, glycolic acid, lactic acid, 3-hydroxypropionic acid, 4-hydroxydodecanoic acid, 5-hydroxydodecanoic acid, ricinoleic acid, 12-hydroxydodecanoic acid, 12-hydroxystearic acid, 2,2-bis (hydroxymethyl) Butyric acid etc.), in particular, straight chain aliphatic carboxylic acids having 6 to 20 carbon atoms, hydrides having 1 to 20 carbon atoms. Alkoxy group-containing carboxylic acid is preferred. These carboxylic acids may be used as a mixture.

  A known lactone can be used as the lactone used in (i). For example, β-propiolactone, β-butyrolactone, γ-butyrolactone, γ-hexanolactone, γ-octanolactone, δ-valerolactone, δ-hexalanolactone, δ-octanolactone, ε-caprolactone, δ -Dodecanolactone, α-methyl-γ-butyrolactone and the like can be mentioned, and in particular, ε-caprolactone is preferable from the viewpoint of reactivity and availability. These lactones may be used as a mixture. The charging ratio at the time of the reaction between the carboxylic acid and the lactone cannot be uniquely determined because it depends on the molecular weight of the target polyester chain, but is preferably carboxylic acid: lactone = 1: 1 to 1: 1,000, and 1: 3 to 1: 500 is most preferred.

  The hydroxy group-containing carboxylic acid in (ii) is the same as the hydroxy group-containing carboxylic acid in (i), and the preferred range is also the same.

As the dihydric alcohol in (iii), a linear or branched aliphatic diol (a diol having 2 to 30 carbon atoms is preferable, for example, ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,2-propanediol. 1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, etc., and aliphatic diols having 2 to 20 carbon atoms are particularly preferable.
Further, as the divalent carboxylic acid, a linear or branched divalent aliphatic carboxylic acid (preferably a divalent aliphatic carboxylic acid having 1 to 30 carbon atoms is preferable. For example, succinic acid, maleic acid, adipic acid, sebacin Acid, dodecanedioic acid, glutaric acid, suberic acid, tartaric acid, oxalic acid, malonic acid and the like, and a divalent carboxylic acid having 3 to 20 carbon atoms is particularly preferable. Further, acid anhydrides equivalent to these divalent carboxylic acids (for example, succinic anhydride, glutaric anhydride, etc.) may be used.
The divalent carboxylic acid and the dihydric alcohol are preferably charged at a molar ratio of 1: 1. This makes it possible to introduce a carboxylic acid at the terminal.

The polycondensation during the production of the polyester is preferably performed by adding a catalyst. As the catalyst, a catalyst that functions as a Lewis acid is preferable. For example, a Ti compound (for example, Ti (OBu) ₄ , Ti (Oi-Pr) _4, etc.), a Sn compound (for example, tin octylate, dibutyltin oxide, dibutyltin) Laurate, monobutyltin hydroxybutyl oxide, stannic chloride, etc.), protonic acids (for example, sulfuric acid, paratoluenesulfonic acid, etc.) and the like. The catalyst amount is preferably from 0.01 to 10 mol%, most preferably from 0.1 to 5 mol%, based on the number of moles of all monomers. The reaction temperature is preferably 80 to 250 ° C, and most preferably 100 to 180 ° C. Although reaction time changes with reaction conditions, it is 1 to 24 hours in general.

  The number average molecular weight of the polyester can be measured as a polystyrene converted value by the GPC method. The number average molecular weight of the polyester that can be used in the present invention is preferably 500 to 10,000, and most preferably 1,000 to 8,000 as the dispersant B1.

  Especially as polyester used for preparation of dispersing agent B1 by the present invention, polyester obtained by (i) and (ii) is preferred since manufacture is easy.

  The dispersant B1 of the present invention can be obtained by reacting polyallylamine or polyalkyleneimine with a polyester containing a free carboxyl group. Polyallylamine or polyalkyleneimine and polyester containing a free carboxyl group are reacted at a mass ratio of 1: 100 to 1: 1, but as dispersant B1, it may be reacted at 1:50 to 1: 1. The reaction is preferably performed at 1:50 to 1: 2. By being in this range, the dispersibility becomes good. The reaction temperature is preferably 50 to 250 ° C, and most preferably 70 to 150 ° C. The reaction time is preferably 0.5 to 24 hours.

  The reaction may be performed in the presence of a solvent. Examples of the solvent include a sulfoxide compound (eg, dimethyl sulfoxide), a ketone compound (eg, acetone, methyl ethyl ketone, cyclohexanone, etc.), an ester compound (eg, ethyl acetate, butyl acetate, ethyl propionate, propylene glycol monomethyl ether acetate, etc.), Ether compounds (eg, diethyl ether, dibutyl ether, tetrahydrofuran, etc.), aliphatic hydrocarbon compounds (eg, pentane, hexane, etc.), aromatic hydrocarbon compounds (eg, toluene, xylene, mesitylene, etc.), nitrile compounds (eg, , Acetonitrile, propiononitrile, etc.), amide compounds (eg, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, etc.), carboxylic acid compounds (eg, Acid, propionic acid, etc.), alcohol compounds (eg, methanol, ethanol, isopropanol, n-butanol, 3-methylbutanol, 1-methoxy-2-propanol, etc.), halogenated solvents (eg, chloroform, 1,2-dichloroethane) Etc.). When using a solvent, it is preferable to use 0.1-100 mass times with respect to a substrate, and it is most preferable to use 0.5-10 mass times.

  The weight average molecular weight of the dispersant B1 is in the range of 3,000 to 15,000, preferably in the range of 5,000 to 15,000, and more preferably in the range of 7,000 to 13,000. By being in this range, the dispersibility of the pigment becomes good.

<(B2) Graft polymer having a main chain portion having a polyallylamine structure or a polyalkyleneimine structure and a side chain portion made of polyester and having a weight average molecular weight in the range of 20000 to 60000: Dispersant B2>
The basic structure of the dispersant B2 is the same as that of the dispersant B1, the synthesis method is the same, and the materials used for the synthesis are also the same. The composition ratio of the dispersant B1 and the dispersant B2 and the structures of the polyallylamine, polyalkyleneimine, and polyester may be the same or different. However, as for the weight average molecular weight, it is essential that the dispersant B1 is in the range of 3000 to 15000 and the dispersant B2 is in the range of 20000 to 60000.

Preferred ranges of the dispersant B2 different from the dispersant B1 are shown below.
As polyallylamine which comprises dispersing agent B2, it is preferable that the structural unit represented by above-mentioned Formula (1) is the range of 10-600, and it is more preferable that it is the range of 20-300.
The molecular weight of the polyalkyleneimine used for the preparation of the dispersant B2 is preferably 500 to 30,000, more preferably 1000 to 20,000.
The number average molecular weight of the polyester used for the dispersant B2 is preferably 1,000 to 15,000, and most preferably 2,000 to 12,000.

  The ratio of the polyallylamine or polyalkyleneimine in the dispersant B2 to the polyallylamine or polyalkyleneimine in the reaction of the polyester containing a free carboxyl group and the polyester containing a free carboxyl group is 1: The reaction is preferably carried out at 50 to 1: 1, more preferably carried out at 1:30 to 1: 1. By being in this range, the dispersibility becomes good.

  The weight average molecular weight of the dispersant B2 is in the range of 20,000 to 60,000, preferably in the range of 20,000 to 50,000, and more preferably in the range of 25,000 to 45,000. By being in this range, dispersion stability and developability are improved.

  It is preferable that 5 to 60 parts by mass of the dispersant B1 is added to 100 parts by mass of the organic pigment (A), and 5 to 30 parts by mass of the dispersant B2 is added to 100 parts by mass of the organic pigment (A). . More preferably, the dispersant B1 is added in an amount of 10 to 50 parts by mass with respect to 100 parts by mass of the organic pigment, and the dispersant B2 is added in an amount of 5 to 25 parts by mass with respect to 100 parts by mass of the organic pigment. By setting the addition amount in this range, it is possible to achieve both good dispersibility and good developability for a fine organic pigment having an average primary particle diameter of 10 nm to 35 nm.

  In particular, in the present invention, the ratio of the dispersant B1 and the dispersant B2 is preferably the mass ratio of the dispersant B1: dispersant B2 = 1: 3 to 10: 1, and 1: 2 to 4: 1. More preferred. Within this range, dispersion stability is good and pattern formation with little development residue can be achieved.

<(A) Organic pigment having an average primary particle size of 10 nm to 35 nm>
The colored composition of the present invention contains (A) an organic pigment having an average primary particle diameter in the range of 10 nm to 35 nm.
As the pigment that can be used in the coloring composition of the present invention, various conventionally known organic pigments can be used. Moreover, as a particle size of a pigment, an average primary particle diameter is the range of 10 nm-35 nm, Preferably it is the range of 15 nm-30 nm. Within this range, the contrast is high, the transmittance is high, the color unevenness is small, and the color characteristics are good.
The average primary particle diameter is obtained by observing with an SEM or TEM, measuring 100 particle sizes in a portion where the particles are not aggregated, and calculating an average value.

Examples of the organic pigment include:
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279,

C. 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, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 17 , 175,176,177,179,180,181,182,185,187,188,193,194,199,213,214
C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73,

C. I. Pigment Green 7, 10, 36, 37, 58
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 79 were changed to OH. Stuff, 80,
C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42,
C. I. Pigment Brown 25, 28,
C. I. Pigment Black 1, 7 and the like.

Among these, the pigments that can be preferably used include the following. However, the present invention is not limited to these.
C. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185,
C. I. Pigment Orange 36, 71,
C. I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264,
C. I. Pigment Violet 19, 23, 32,
C. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66, 79, 79 with the Cl substituent changed to OH, 80,
C. I. Pigment Green 7, 36, 37, 58
C. I. Pigment Black 1, 7

-Finer pigments-
In the present invention, the average primary particle diameter is an organic pigment in the range of 10 nm to 35 nm, but an organic pigment obtained by refining a crude pigment can be used as necessary.
The refinement of a pigment is a pigment obtained by preparing a liquid composition with high viscosity together with a pigment, a water-soluble organic solvent, and a water-soluble inorganic salt, and grinding the pigment using this liquid composition (a salt milled pigment). Is preferred.

  Water-soluble organic solvents include methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, ethylene glycol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol, propylene glycol A monomethyl ether acetate etc. can be mentioned. However, if it is adsorbed to the pigment by using a small amount and does not flow away into the wastewater, benzene, toluene, xylene, ethylbenzene, chlorobenzene, nitrobenzene, aniline, pyridine, quinoline, tetrahydrofuran, dioxane, ethyl acetate, isopropyl acetate, butyl acetate, hexane , Heptane, octane, nonane, decane, undecane, dodecane, cyclohexane, methylcyclohesasan, halogenated hydrocarbon, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, etc. Two or more kinds of solvents may be mixed and used as necessary.

  Examples of the water-soluble inorganic salt include sodium chloride, potassium chloride, calcium chloride, barium chloride, sodium sulfate and the like.

The amount of the water-soluble inorganic salt used is 1 to 50 times the mass of the pigment, and a larger amount has a grinding effect, but a more preferred amount is 1 to 10 times the mass in terms of productivity, and further moisture is 1% or less. It is preferable that
The amount of the water-soluble organic solvent used is in the range of 50% by mass to 300% by mass and preferably in the range of 100% by mass to 200% by mass with respect to the pigment.

  After preparing a liquid composition using each of the above components, the pigment is refined by a wet pulverizer. Here, there are no particular restrictions on the operating conditions of the wet pulverizing apparatus, but in order to effectively proceed the grinding with the pulverizing media, the operating conditions when the apparatus is a kneader are: 200 rpm is preferable, and a relatively large biaxial rotation ratio is preferable because the grinding effect is large. The operation time is preferably 1 to 8 hours in combination with the dry pulverization time, and the internal temperature of the apparatus is preferably 50 to 150 ° C. Further, the water-soluble inorganic salt that is a pulverizing medium preferably has a pulverized particle size of 5 to 50 μm, a sharp particle size distribution, and a spherical shape.

-Preparation of pigment (color matching)-
Organic pigments can be used alone, but can be used in various combinations in order to increase color purity. Specific examples of combinations are shown below.
For example, as a red pigment, anthraquinone pigments, perylene pigments, diketopyrrolopyrrole pigments may be used alone, but at least one of them, a disazo yellow pigment, an isoindoline yellow pigment, a quinophthalone pigment A yellow pigment, or a perylene red pigment, an anthraquinone red pigment, or a diketopyrrolopyrrole red pigment may be mixed. For example, as an anthraquinone pigment, C.I. I. Pigment Red 177, and perylene pigments include C.I. I. Pigment red 155, C.I. I. Pigment Red 224, and diketopyrrolopyrrole pigments include C.I. I. Pigment Red 254, and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 139, or C.I. I. Mixing with Pigment Red 177 is preferred.
The mass ratio of the red pigment to the other pigment is preferably 100: 5 to 100: 80. If it is less than 100: 5, it may be difficult to suppress the light transmittance from 400 nm to 500 nm, and the color purity may not be increased. On the other hand, if the ratio exceeds 100: 80, the coloring power may decrease. Particularly, the mass ratio is optimally in the range of 100: 10 to 100: 65. In addition, in the case of the combination of red pigments, it can adjust according to chromaticity.

As the green pigment, a halogenated phthalocyanine pigment may be used alone, but a mixture of this with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment, or an isoindoline yellow pigment. May be performed. For example, C.I. I. Pigment Green 7, 36, 37 and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180, or C.I. I. Mixing with Pigment Yellow 185 is preferred.
The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 200. When the mass ratio is less than 100: 5, it is difficult to suppress the light transmittance of 400 to 450 nm, and the color purity may not be increased. On the other hand, if the ratio exceeds 100: 200, the dominant wavelength tends to be longer and the deviation from the NTSC target hue may become larger. The mass ratio is particularly preferably in the range of 100: 20 to 100: 150.

As the blue pigment, a phthalocyanine pigment may be used alone, but it may be mixed with a dioxazine purple pigment. As a particularly preferred example, C.I. I. Pigment blue 15: 6 and C.I. I. A mixture with pigment violet 23 can be mentioned.
The mass ratio of the blue pigment to the violet pigment is preferably 100: 0 to 100: 100, more preferably 100: 70 or less.

Moreover, as a pigment suitable for black matrix use, carbon black, graphite, titanium black, iron oxide, titanium oxide alone or a mixture thereof can be used, and a combination of carbon black and titanium black is preferable.
The mass ratio of carbon black to titanium black is preferably in the range of 100: 0 to 100: 60. If it is 100: 61 or more, the dispersion stability may decrease.

(dye)
In the present invention, it is also possible to use a dye in combination with the organic pigment.
There is no restriction | limiting in particular as dye which can be used together, The well-known dye currently used as a color filter use can be used. For example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. 1-94301, Japanese Patent Application Laid-Open No. 6-11614, No. 2592207, US Pat. No. 4,808,501. Specification, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 JP-A-6-194828, JP-A-8-21599, JP-A-4-249549, JP-A-10-123316, JP-A-11-302283, JP-A-7-286107, JP 2001-4823, JP-A-8-15522, JP-A-8-29771, JP-A-8-146215, JP-A-11-3434. 7, JP-A-8-62416, JP-A-2002-14220, JP-A-2002-14221, JP-A-2002-14222, JP-A-2002-14223, JP-A-8-302224 JP-A-8-73758, JP-A-8-179120, JP-A-8-151531, and the like.
The chemical structure is pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, A dye such as xanthene, phthalocyanine, benzopyran, or indigo can be used.

(Pigment dispersion)
In the present invention, the coloring composition of the present invention is prepared using a pigment dispersion prepared in advance from (A) an organic pigment, (B1) dispersant B1 and (B2) dispersant B2, and (F) an organic solvent. Is preferably prepared.
As content of the organic pigment in a pigment dispersion liquid, 10-60 mass% is preferable with respect to the total solid (mass) of this composition, and 15-50 mass% is more preferable. When the content of the organic pigment is within the above range, the color density is sufficient to ensure excellent color characteristics.

The pigment dispersion preferably contains a dispersant B1 and a dispersant B2. As for the addition of the dispersant B1 and the dispersant B2 in the preparation of the pigment dispersion liquid, it is preferable to add the total amount of the additive in the aforementioned colored composition. Further, a part of the dispersant B1 and / or the dispersant B2 may be added at the time of preparing the pigment dispersion, and the remainder may be added at the stage of preparing the coloring composition. It is also possible to add the entire amount of the dispersant B1 and / or the dispersant B2 at the stage of preparing the coloring composition.
Further, the order of addition of the dispersant B1 and the dispersant B2 may be the same, or the dispersant B1 may be added at the time of preparing the pigment dispersion, and the dispersant B2 may be added at the stage of preparing the coloring composition. Alternatively, it is also possible to add the dispersant B1 at the initial stage of the preparation of the pigment dispersion and add the dispersant B2 during the dispersion step.

<(F) Organic solvent>
The pigment dispersion can contain an organic solvent as necessary.
Examples of the organic solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, Such as ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate 3-oxypropionic acid alkyl esters; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, 2-oxypropionate Ethyl acetate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-oxy- Methyl 2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, pyruvate Propyl, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like; ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl Ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc .; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc .; aromatic hydrocarbons such as toluene, xylene and the like.

Of these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl Carbitol acetate, propylene glycol methyl ether acetate and the like are suitable.
Two or more organic solvents may be used in combination, in addition to being used alone.

<Other dispersants>
About this invention, it is also possible to use together other dispersing agents other than the dispersing agent B1 and the dispersing agent B2 in the range which does not worsen the effect of this invention. When other dispersants other than the dispersant B1 and the dispersant B2 are used in combination, the content is preferably 30% by mass or less, more preferably 20% by mass or less with respect to the organic pigment.
As other dispersants other than the dispersant B1 and the dispersant B2, for example, known pigment dispersants and surfactants can be appropriately selected and used.

  Specifically, many types of compounds can be used. For example, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, no. 90, no. Cationic surfactants such as 95 (manufactured by Kyoeisha Chemical Industry Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), etc .; Nonionic surfactants such as octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester; anionic systems such as W004, W005, and W017 (manufactured by Yusho Co., Ltd.) Surfactant: EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (all manufactured by Ciba Specialty Chemicals) Polymer dispersants such as Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (all manufactured by San Nopco); Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, Various Solsperse dispersants such as 26000, 28000 (manufactured by Nippon Lubrizol Corp.); Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (Asahi Denka Co., Ltd.) and Isonet S-20 (Sanyo Kasei Co., Ltd.), Disperbyk 101, 103, 106, 108, 109, 111, 112, 116, 130, 140, 142, 162, 163, 164, 166, 167, 170, 171, 174, 176, 180, 182, 2000, 2001, 2050, 2150 (by Big Chemie). In addition, an oligomer or polymer having a polar group at the molecular end or side chain, such as an acrylic copolymer, may be mentioned.

<(G) Pigment derivative>
It is preferable to add the pigment derivative (G) to the pigment dispersion as necessary. By adsorbing a pigment derivative having a part having affinity for the dispersant or a polar group to the pigment surface and using this as the adsorption point of the dispersant, the pigment is made into fine particles in the pigment dispersion or colored. It can be more effectively dispersed in the composition to prevent re-aggregation. As a result, this colored composition can be preferably used when forming a color filter having higher contrast, higher transparency, and excellent color characteristics.

  (G) The pigment derivative is specifically a compound in which an organic pigment is used as a base skeleton, and an acidic group, a basic group, or an aromatic group is introduced as a substituent in the side chain. Specific examples of organic pigments include quinacridone pigments, phthalocyanine pigments, azo pigments, quinophthalone pigments, isoindoline pigments, isoindolinone pigments, quinoline pigments, diketopyrrolopyrrole pigments, and benzoimidazolone pigments. Is mentioned. In general, light yellow aromatic polycyclic compounds such as naphthalene series, anthraquinone series, triazine series and quinoline series which are not called pigments are also included.

  Examples of pigment derivatives include JP-A-11-49974, JP-A-11-189732, JP-A-10-245501, JP-A-2006-265528, JP-A-8-295810, and JP-A-11-199796. For example, JP-A-2005-234478, JP-A-2003-240938, and JP-A-2001-356210 can be used.

  As content in the pigment dispersion liquid of a pigment derivative, 1-50 mass% is preferable with respect to the mass of an organic pigment, and 10-40 mass% is more preferable. When the content is within the above range, while maintaining the viscosity low, it is possible to achieve good dispersion and further improve the dispersion stability after dispersion, high transmittance and excellent color characteristics are obtained, When producing a color filter, it can be configured to have high contrast with good color characteristics.

-Distribution method-
As a method for dispersing the pigment, for example, (A) an organic pigment, (B) a specific graft polymer, (F) an organic solvent, etc., previously mixed and dispersed with a homogenizer or the like, particles of 0.01 to 1 mm are used. Using a bead made of glass having a diameter, zirconia or the like, a vertical or horizontal sand grinder mill, pin mill, slit mill, ultrasonic disperser or the like is used to obtain a pigment dispersion.
In addition, before dispersing, while applying a strong shearing force using a kneader such as a two-roll, three-roll, ball mill, tron mill, disper, kneader, kneader, homogenizer, blender, single or twin screw extruder, etc. It is also preferable to knead.
For details on kneading and dispersing, see T.W. C. “Paint Flow and Pigment Dispersion” by Patton (published by John Wiley and Sons, 1964) and the like.

<(C) Alkali-soluble resin>
To the pigment dispersion obtained as described above, (C) an alkali-soluble resin, (D) a polyfunctional monomer, (E) a photopolymerization initiator, (F) an organic solvent, and the like are added and mixed. It adjusts and obtains the coloring composition of this invention.
(C) The alkali-soluble resin is a linear organic high molecular polymer, and at least one alkali-soluble polymer in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be suitably selected from alkali-soluble resins having a group that promotes (for example, carboxyl group, phosphoric acid group, sulfonic acid group, etc.). (C) The alkali-soluble resin is soluble in an organic solvent and developable with a weak alkaline aqueous solution.

  For production of the alkali-soluble resin, for example, a known radical polymerization method can be applied. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and the conditions are determined experimentally. It can also be done.

  As said linear organic high molecular polymer, the polymer which has carboxylic acid in a side chain is preferable. For example, it is described in JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-59-53836, and JP-A-59-71048. Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., as well as in the side chain Preferred examples include acidic cellulose derivatives having a carboxylic acid, those obtained by adding an acid anhydride to a polymer having a hydroxyl group, and a polymer having a (meth) acryloyl group in the side chain. Here, (meth) acrylic acid is a general term that combines acrylic acid and methacrylic acid, and (meth) acrylate is also a general term for acrylate and methacrylate.

As a specific structural unit of the alkali-soluble resin, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is particularly suitable.
Of these, benzyl (meth) acrylate / (meth) acrylic acid copolymers and multi-component copolymers composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are particularly suitable.
In addition, those obtained by copolymerizing 2-hydroxyethyl methacrylate are also useful. The polymer can be used by mixing in an arbitrary amount.

  In addition to the above, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate described in JP-A-7-140654 Macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer Etc.

Examples of other monomers copolymerizable with the (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. Here, the hydrogen atom of the alkyl group and the aryl group may be substituted with a substituent.
Specific examples of the alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl ( Examples include meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like. it can.

Examples of the vinyl compound include styrene, α-methylstyrene, vinyl toluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, CH _2. = CR ³¹ R ³² , CH ₂ = C (R ³¹ ) (COOR ³³ ) [wherein R ³¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ³² is an aromatic group having 6 to 10 carbon atoms. Represents a hydrocarbon ring, and R ³³ represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group having 6 to 12 carbon atoms. ], Etc. can be mentioned.

These other copolymerizable monomers can be used singly or in combination of two or more. Other preferred copolymerizable monomers are selected from CH ₂ ═CR ³¹ R ³² , CH ₂ ═C (R ³¹ ) (COOR ³³ ), phenyl (meth) acrylate, benzyl (meth) acrylate and styrene. is at least one, particularly _preferably CH ^{2 = CR} 31 ^{R 32} and / or ^{_{CH 2 = C (R 31)}} (COOR 33).

  (C) As content in the coloring composition of alkali-soluble resin, 1-60 mass% is preferable with respect to the total solid of this composition, More preferably, it is 2-50 mass%, Most preferably Is 3-40 mass%.

<(D) Multifunctional monomer>
The coloring composition of the present invention contains (D) a polyfunctional monomer.
As this polyfunctional monomer, a compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C. or higher at normal pressure is preferable. Among them, a tetrafunctional or higher acrylate compound is preferable. More preferred.

Examples of the compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C. or higher at normal pressure include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxy Monofunctional acrylates and methacrylates such as ethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, penta Erythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ester Ter, tri (acryloyloxyethyl) isocyanurate, polyfunctional alcohols such as glycerin and trimethylol ethane, added with ethylene oxide and propylene oxide and then (meth) acrylated, poly (pentaerythritol or dipentaerythritol) (Meth) acrylate, urethane acrylates described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, JP-A-48-64183, JP-B-49-43191 Polyfunctional acrylates and methacrylates such as polyester acrylates described in Japanese Patent Publication No. 52-30490 and epoxy acrylates which are reaction products of epoxy resins and (meth) acrylic acid can be mentioned.
Furthermore, the Japan Adhesion Association Vol. 20, no. 7, what is introduced as a photocurable monomer and oligomer on pages 300 to 308 can also be used.

  In addition, a compound which has been (meth) acrylated after adding ethylene oxide or propylene oxide to the polyfunctional alcohol described in JP-A-10-62986 as general formulas (1) and (2) together with specific examples thereof. Can be used.

Among these, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and a structure in which these acryloyl groups are via ethylene glycol and propylene glycol residues are preferable. These oligomer types can also be used.
Also, urethane acrylates as described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, and JP-B-58-49860 are disclosed. Urethane compounds having an ethylene oxide skeleton described in JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable. Furthermore, by using addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, JP-A-1-105238 Can obtain a colored composition having a very high photosensitive speed. Commercially available products include urethane oligomer UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 "(manufactured by Shin-Nakamura Chemical Co., Ltd., DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA- 306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) and the like.
In addition, ethylenically unsaturated compounds having an acid group are also suitable. Examples of commercially available products include TO-756, which is a carboxyl group-containing trifunctional acrylate manufactured by Toagosei Co., Ltd., and a carboxyl group-containing pentafunctional acrylate. Some TO-1382 and the like can be mentioned.

The polyfunctional monomer can be used in combination of two or more, in addition to being used alone.
As content in the coloring composition of a polyfunctional monomer, it is preferable that it is 5-50 mass% in a total solid, It is more preferable that it is 7-40 mass%, 10-35 mass% More preferably.

<(E) Photopolymerization initiator>
The coloring composition of the present invention contains (E) a photopolymerization initiator.
Examples of the photopolymerization initiator include halomethyl oxadiazole described in JP-A-57-6096, halomethyl-s-triazine described in JP-B-59-1281, JP-A-53-133428, and the like. Isoactive halogen compounds, aromatic carbonyl compounds such as ketals, acetals, or benzoin alkyl ethers described in US Pat. No. 4,318,791 and European Patent Application No. 88050, described in US Pat. No. 4,199,420 Aromatic ketone compounds such as benzophenones, (thio) xanthones or acridine compounds described in French Patent No. 2456741, coumarins or lophine dimers described in JP-A-10-62986, etc. Compound, sulfonium organoboron such as JP-A-8-015521 Body, etc., etc. can be mentioned.

  Examples of the photopolymerization initiator include acetophenone, ketal, benzophenone, benzoin, benzoyl, xanthone, triazine, halomethyloxadiazole, acridine, coumarins, lophine dimers, biphenyl Imidazole type, oxime ester type and the like are preferable.

  Examples of the acetophenone photopolymerization initiator include 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, p-dimethylaminoacetophenone, Preferable examples include 4′-isopropyl-2-hydroxy-2-methyl-propiophenone.

  Preferable examples of the ketal photopolymerization initiator include benzyl dimethyl ketal and benzyl-β-methoxyethyl acetal.

  Examples of the benzophenone photopolymerization initiator include benzophenone, 4,4 ′-(bisdimethylamino) benzophenone, 4,4 ′-(bisdiethylamino) benzophenone, 4,4′-dichlorobenzophenone, and 1-hydroxy-cyclohexyl. -Phenyl-ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-tolyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1 and the like can be preferably exemplified.

  Preferred examples of the benzoin-based or benzoyl-based photopolymerization initiator include benzoin isopropyl ether, zenzoin isobutyl ether, benzoin methyl ether, methyl o-benzoyl bezoate, and the like.

  Preferable examples of the xanthone photopolymerization initiator include diethylthioxanthone, diisopropylthioxanthone, monoisopropylthioxanthone, chlorothioxanthone, and the like.

  Examples of the triazine photopolymerization initiator include 2,4-bis (trichloromethyl) -6-p-methoxyphenyl-s-triazine, 2,4-bis (trichloromethyl) -6-p-methoxystyryl- s-triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl) -1,3-butadienyl-s-triazine, 2,4-bis (trichloromethyl) -6-biphenyl- s-triazine, 2,4-bis (trichloromethyl) -6- (p-methylbiphenyl) -s-triazine, p-hydroxyethoxystyryl-2,6-di (trichloromethyl) -s-triazine, methoxystyryl- 2,6-di (trichloromethyl-s-triazine, 3,4-dimethoxystyryl-2,6-di (trichloromethyl) -s-to Azine, 4-benzoxolane-2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN, N- (diethoxycarbonylamino) -phenyl) -2,6-di (Chloromethyl) -s-triazine, 4- (pN, N- (diethoxycarbonylamino) -phenyl) -2,6-di (chloromethyl) -s-triazine and the like can be preferably exemplified.

  Examples of the halomethyloxadiazole-based photopolymerization initiator include 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3. , 4-oxodiazole, 2-trichloromethyl-5- (naphth-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl-1,3 A preferred example is 4-oxodiazole.

  Preferred examples of the acridine-based photopolymerization initiator include 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, and the like.

  Examples of the coumarin-based photopolymerization initiator include 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-chloro-5-diethylamino-((s Preferred examples include -triazin-2-yl) amino) -3-phenylcoumarin, 3-butyl-5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, and the like.

  Examples of the lophine dimer-based photopolymerization initiator include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer and 2- (o-methoxyphenyl) -4,5-diphenylimidazolyl dimer. And 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer and the like can be preferably exemplified.

  Preferable examples of the biimidazole photopolymerization initiator include 2-mercaptobenzimidazole, 2,2′-benzothiazolyl disulfide and the like.

  In addition to the above, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, O-benzoyl-4 ′-(benzmercapto) benzoyl-hexyl-ketoxime, 2,4,6-trimethylphenyl Examples thereof include carbonyl-diphenyl phosphonyl oxide and hexafluorophospho-trialkylphenyl phosphonium salt.

In this invention, it is not limited to the above photoinitiator, Other well-known things can also be used. For example, a vicinal polykettle aldonyl compound described in US Pat. No. 2,367,660 and an α-carbonyl compound described in US Pat. Nos. 2,367,661 and 2,367,670. An acyloin ether described in US Pat. No. 2,448,828, an α-hydrocarbon-substituted aromatic acyloin compound described in US Pat. No. 2,722,512, US Pat. , 046,127 and 2,951,758, a triarylimidazole dimer / p-aminophenyl ketone combination described in US Pat. No. 3,549,367, Benzothiazole compounds / trihalomethyl-s-triazine compounds described in JP-A-51-48516; C. S. Perkin II (1979) 1653-1660, J. MoI. C. S. Examples include Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, and oxime ester compounds described in JP-A No. 2000-66385.
Moreover, these photoinitiators can also be used together.

  As content in the coloring composition of a photoinitiator, 0.1-10.0 mass% is preferable with respect to the total solid of this composition, More preferably, it is 0.5-5.0 mass%. It is. When the content of the photopolymerization initiator is within the above range, the polymerization reaction can proceed well to form a film with good strength.

<(F) Organic solvent>
As the organic solvent (F), the organic solvent described in the section of the pigment dispersion can be used for the coloring composition. Although it may be the same as the organic solvent used in the preparation of the pigment dispersion, it may be different and two or more kinds may be used in combination.
The amount of the organic solvent contained in the coloring composition is appropriately adjusted so that the coloring composition can be easily applied and so that unevenness or the like does not occur in the drying step, but is 70 to 95 with respect to the total amount of the coloring composition. % By mass is preferable, and more preferably 75 to 90% by mass.

<Other optional ingredients>
In the coloring composition of the present invention, if necessary, a thermal polymerization initiator, a thermal polymerization component, a thermal polymerization inhibitor, other fillers, a polymer compound other than the above alkali-soluble resin, an adhesion promoter, an antioxidant Various additives such as an agent, an ultraviolet absorber, a chain transfer agent, a fluorine-based organic compound, a surfactant, and an anti-aggregation agent can be contained.

-Thermal polymerization initiator-
It is also effective to contain a thermal polymerization initiator in the colored composition of the present invention.
Examples of the thermal polymerization initiator include various azo compounds and peroxide compounds. Examples of the azo compounds include azobis compounds. Examples of the peroxide compounds include ketones. Examples thereof include peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, peroxydicarbonates, and the like.

-Thermal polymerization component-
In order to improve the film strength, it is also effective to contain a thermal polymerization component in the colored composition of the present invention.
An epoxy compound is used as the thermal polymerization component. The epoxy compound is a compound having two or more epoxy rings in the molecule such as bisphenol A type, cresol novolac type, biphenyl type, and alicyclic epoxy compound.
Specifically, for example, as bisphenol A type, Epototo YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF-170 and the like (manufactured by Tohto Kasei), Denacol EX-1101, EX-1102, EX-1103 and the like (manufactured by Nagase Kasei), Plaxel GL-61, GL-62, G101 and G102 (manufactured by Daicel Chemical) In addition, these similar bisphenol F type and bisphenol S type can also be mentioned. Epoxy acrylates such as Ebecryl 3700, 3701, 600 (manufactured by Daicel UC) may also be used.

Examples of the cresol novolak type include Epototo YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704, etc. (manufactured by Toto Kasei), Denacol EM-125, etc. (manufactured by Nagase Kasei),
As the biphenyl type, 3,5,3 ′, 5′-tetramethyl-4,4′diglycidylbiphenyl, etc.
Examples of the alicyclic epoxy compounds include Celoxide 2021, 2081, 2083, 2085, Epolide GT-301, GT-302, GT-401, GT-403, EHPE-3150 (manufactured by Daicel Chemical), Santo Tote ST-3000, ST. -4000, ST-5080, ST-5100 (manufactured by Tohto Kasei) and the like.
1,1,2,2-tetrakis (p-glycidyloxyphenyl) ethane, tris (p-glycidyloxyphenyl) methane, triglycidyltris (hydroxyethyl) isocyanurate, o-phthalic acid diglycidyl ester, terephthalic acid Diglycidyl ester, amine type epoxy resins such as Epototo YH-434 and YH-434L, and glycidyl ester obtained by modifying dimer acid in the skeleton of bisphenol A type epoxy resin can also be used.

-Thermal polymerization inhibitor-
A thermal polymerization inhibitor may be added to the colored composition of the present invention.
Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t- Butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole, and the like are useful.

-Adhesion promoter-
If necessary, an adhesion promoter such as an organosilicon compound for imparting adhesion, a silane coupling agent, and a leveling agent may be added to the colored composition in the present invention.
Examples of these are, for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryl. Trimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, ureapropyltriethoxysilane, tris ( Acetylacetonate) aluminum, acetylacetate aluminum diisopropylate and the like. When using an adhesion promoter for the coloring composition, 0.001 to 1 part by mass is preferable and 0.01 to 0.5 part by mass is more preferable with respect to the total amount of the coloring composition.

-Chain transfer agent-
Examples of the chain transfer agent that can be added to the coloring composition of the present invention include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester, 2-mercaptobenzothiazole, and 2-mercapto. Examples include mercapto compounds having a heterocyclic ring such as benzoxazole and 2-mercaptobenzimidazole, and aliphatic polyfunctional mercapto compounds.
A chain transfer agent may be used individually by 1 type, and may use 2 or more types together.

-Fluorine organic compounds-
The coloring composition of the present invention can improve liquid properties (particularly fluidity) when used as a coating liquid by containing a fluorine-based organic compound, and can improve uniformity of coating thickness and liquid-saving properties. . That is, the interfacial tension between the substrate and the coating liquid is reduced to improve the wettability to the substrate and the coating property to the substrate is improved, so that a thin film of about several μm is formed with a small amount of liquid. This is also effective in that a film having a uniform thickness with small thickness unevenness can be formed.

  3-40 mass% is suitable for the fluorine content rate of a fluorine-type organic compound, More preferably, it is 5-30 mass%, Most preferably, it is 7-25 mass%. When the fluorine content is within the above range, it is effective in terms of coating thickness uniformity and liquid-saving properties, and the solubility in the composition is also good.

  As the fluorosurfactant, a compound having a fluoroalkyl or fluoroalkylene group in at least one of the terminal, main chain and side chain can be suitably used. Specific commercial products include, for example, MegaFuck F142D, F172, F173, F176, F176, F177, F183, 780, 781, R30, R08, F-472SF, BL20, R- 61, R-90 (manufactured by DIC Corporation), Florard FC-135, FC-170C, FC-430, FC-431, Novec FC-4430 (manufactured by Sumitomo 3M), Asahi Guard AG7105 7000, 950, 7600, Surflon S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC- 103, SC-104, SC-105, SC-106 (Asahi Glass Co., Ltd.), Ftop EF351, 352, 801, 802 ( Manufactured by EMCO (Ltd.)), and the like.

The fluorine-based organic compound is particularly effective in preventing coating unevenness and thickness unevenness when the coating film is thinned. Further, it is also effective in slit coating that is liable to cause liquid breakage.
0.001-2.0 mass% is preferable with respect to the total mass of a coloring composition, and, as for the addition amount of a fluorine type organic compound, More preferably, it is 0.005-1.0 mass%.

-Surfactant-
The colored composition of the present invention is preferably composed of various surfactants from the viewpoint of improving coatability. In addition to the above-mentioned fluorosurfactants, nonionic, cationic and anionic Various surfactants can be used. Among these, the above-mentioned fluorine-based surfactants and nonionic surfactants are preferable.

  Examples of nonionic surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and the like. Particularly preferred. Specifically, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene octylphenyl ether, polyoxyethylene polystyrylated ether, polyoxyethylene triethyl ether Polyoxyethylene aryl ethers such as benzyl phenyl ether, polyoxyethylene-propylene polystyryl ether, polyoxyethylene nonyl phenyl ether; polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate, sorbitan fatty acid esters , Polyoxyethylene sorbitan fatty acid esters, ethylenediamine polyoxyethylene-polyoxypropylene Nonionic surfactants such as thione condensates, which are commercially available from Kao Corporation, Nippon Oil & Fats Co., Ltd., Takemoto Oil & Fat Co., Ltd., ADEKA Co., Ltd., Sanyo Kasei Co., Ltd. It can be used as appropriate. In addition to the above, the aforementioned dispersants can also be used.

  In addition to the above, various additives can be added to the coloring composition. Specific examples of additives include ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenone, and anti-aggregation agents such as sodium polyacrylate. Fillers such as glass and alumina; itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, acidic cellulose derivatives, and acid anhydrides added to hydroxyl group-containing polymers And alcohol-soluble nylon, alkali-soluble resins such as phenoxy resin formed from bisphenol A and epichlorohydrin.

  In addition, in order to promote alkali solubility of the uncured part and further improve the developability of the colored composition, an organic carboxylic acid, preferably a low molecular weight organic carboxylic acid having a molecular weight of 1000 or less is added to the colored composition. Can be performed. Specifically, for example, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, and camphoronic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, and mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid , Aromatic polycarboxylic acids such as trimesic acid, merophanic acid, pyromellitic acid; phenyl And other carboxylic acids such as acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylideneacetic acid, coumaric acid, and umberic acid .

<Color filter and manufacturing method thereof>
The color filter of the present invention is characterized by having a colored pattern formed of the colored composition of the present invention on a substrate.
In addition, the method for producing a color filter of the present invention includes a photosensitive film forming step of forming a photosensitive film by applying the coloring composition for a color filter of the present invention onto a substrate, and pattern exposure on the formed photosensitive film. And a colored pattern forming step of forming a colored pattern by sequentially performing development.
Hereinafter, the color filter of the present invention will be described in detail through its manufacturing method (color filter manufacturing method of the present invention).

As a method for producing the color filter of the present invention, first, the colored composition of the present invention is applied to the substrate directly or via another layer by a spin coating method, a slit-and-spin method, or a die coating method. Perform the process. In this step, after a photocurable coating film is formed on the substrate, the coating film is exposed through a predetermined mask pattern. After exposure, the uncured portion is developed and removed with a developer to form a colored pattern. By repeating such steps, pixel portions (colored patterns) of each color (three colors or four colors) are formed on the substrate, and a color filter can be obtained.
By the above method, a color filter used for a liquid crystal display device or a solid-state imaging device can be manufactured with high quality and low cost with little difficulty in process.
Hereinafter, each process of application | coating, exposure, and image development is demonstrated.

[Coating process]
In the coating step, the colored composition of the present invention is coated on the substrate using a spin coating method, a slit-and-spin method, or a die coating method.
In the case of the slit-and-spin method or the die coating method, the conditions vary depending on the size of the coated substrate. For example, when a fifth generation glass substrate (1100 mm × 1250 mm) is coated by the die coating method, coloring from the slit nozzle The discharge rate of the composition is usually 500 to 2000 microliters / second, preferably 800 to 1500 microliters / second, and the coating speed is usually 50 to 300 mm / second, preferably 100 to 200 mm / second. Seconds. As solid content of a coloring composition, it is 10-20 mass% normally, Preferably it is 13-18 mass%.
When a 3.5th generation glass substrate 720 mm × 600 mm is applied by a spin coating method, the discharge amount of the coloring composition from the nozzle is usually 40 to 50 mL, and the coating rotation speed is 500 to 1000 rpm. The solid content of the coloring composition is usually 15 to 25%, preferably 18 to 22%.

  When forming the coating film by the coloring composition of this invention on a board | substrate, as thickness (after a prebaking process) of this coating film, it is 0.3-5.0 micrometers generally, Preferably it is 0.5-4.0 micrometers. Most preferably, the thickness is 0.8 to 3.0 μm.

Next, the board | substrate with which the coloring composition of this invention is apply | coated is demonstrated.
As the substrate in the present invention, for example, non-alkali glass, soda glass, Pyrex (registered trademark) glass, quartz glass, and those obtained by attaching a transparent conductive film to these, a solid-state imaging device, etc. Examples of the photoelectric conversion element substrate used in the present invention include a silicon substrate and a plastic substrate. On these substrates, usually, a black matrix for isolating each pixel may be formed, or a transparent resin layer may be provided for promoting adhesion.
The plastic substrate preferably has a gas barrier layer and / or a solvent resistant layer on its surface.

In addition, the coloring composition of the present invention is also applied to a driving substrate (hereinafter referred to as “TFT type liquid crystal driving substrate”) on which a thin film transistor (TFT) of a thin film transistor (TFT) type color liquid crystal display device is disposed. By forming a colored pattern, a color filter can be produced. Examples of the substrate in the TFT type liquid crystal driving substrate include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide. These substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired. For example, a substrate on which a passivation film such as a silicon nitride film is formed on the surface of the TFT liquid crystal driving substrate or on the surface of the driving substrate can be used.
In addition, when forming a coloring pattern with the coloring composition of the present invention on such a TFT type liquid crystal driving substrate, in addition to the pattern for forming pixels, the photomask used in the exposure, It is preferable that a pattern for forming a through hole or a U-shaped depression is also provided.

After the colored composition (photo-curable) coating film is formed as described above, a pre-bake treatment is usually performed. If necessary, vacuum treatment can be performed before pre-baking. The vacuum drying condition is that the degree of vacuum is usually about 0.1 to 1.0 torr, preferably about 0.2 to 0.5 torr.
The pre-bake treatment can be performed in a temperature range of 50 to 140 ° C. (preferably 70 to 110 ° C.) for 10 to 300 seconds using a hot plate, an oven or the like. Here, a high-frequency treatment or the like may be used in combination with the pre-bake treatment. The high frequency treatment can be used alone.

[Exposure process]
In the exposure step, after the coating film of the colored composition is formed on the substrate, the coating film is exposed through a predetermined mask pattern.
In this case, ultraviolet rays such as g-line, h-line, i-line and j-line are particularly preferable as the radiation to be used. When manufacturing a color filter for a liquid crystal display device, it is preferable that exposure using mainly h-line and i-line is performed by a proximity exposure machine and a mirror projection exposure machine.

[Development process]
In the development step, the uncured portion after exposure is eluted in the developer, leaving only the cured portion.
The development temperature is usually 20 to 30 ° C., and the development time is 20 to 90 seconds.
Moreover, as a developing solution, what melt | dissolves the coating film of the photocurable coloring composition in an uncured part can be used as long as it does not melt | dissolve a hardening part. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used.

Examples of the organic solvent include those described above that can be used when preparing the pigment dispersion or the colored composition in the present invention.
Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, Concentration of an alkaline compound such as tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene, in a concentration of 0.001 to 10% by mass, preferably 0.01 to An alkaline aqueous solution dissolved so as to be 1% by mass can be mentioned. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline aqueous solution.

The development method may be any of a dip method, a shower method, a spray method, and the like, and may be combined with a swing method, a spin method, an ultrasonic method, or the like. Before the developer is touched, the surface to be developed can be previously moistened with water or the like to prevent uneven development.
In addition, development can be performed with the substrate inclined.

After the development processing, after a rinsing step for washing and removing excess developer, drying is performed, and then heat treatment (post-baking) is performed to complete the curing.
The rinsing process is usually performed with pure water, but in order to save liquid, pure water is used in the final cleaning, and at the beginning of cleaning, used pure water is used. Sound wave irradiation can be used together.

  After the rinsing step, after draining and drying, a heat treatment is usually performed at about 200 ° C. to 250 ° C. In this heat treatment (post-bake), the coating film after development is continuously or batch-treated using a heating means such as a hot plate, a convection oven (hot air circulation dryer) or a high-frequency heater so as to satisfy the above conditions. It can be done with an expression.

  By sequentially repeating the above operation for each color in accordance with the desired number of hues, a color filter in which a plurality of colored patterns (pixels) are formed can be produced.

Although the application of the colored composition of the present invention has been described mainly focusing on the application to a color filter, it can also be applied to the formation of a black matrix that isolates each colored pixel constituting the color filter.
The black matrix exposes and develops the pigment dispersion in the present invention using a black pigment such as carbon black or titanium black as a pigment, and then further post-bake as necessary to promote film hardening. Can be formed.

<Liquid crystal display device>
The liquid crystal display device of the present invention comprises the color filter of the present invention.
More specifically, an alignment film is formed on the inner surface side of the color filter of the present invention, is opposed to the electrode substrate, and is filled with a liquid crystal in the gap portion and sealed to obtain a panel which is the liquid crystal display device of the present invention. It is done.

The present invention will be described more specifically with reference to the following examples. The materials, reagents, amounts and ratios of substances, operations, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples. In the following, all parts and% are based on mass unless otherwise specified.
The molecular weight of the resin is a weight average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography).

(Synthesis Example 1)
10 parts of polyethyleneimine having a molecular weight of about 1200 (SP-012 manufactured by Nippon Shokubai Co., Ltd.) and 45 parts of polycaprolactone (acid value 16 mg KOH / g) with n = 30 (ie, degree of polymerization 30) and 200 parts of propylene glycol monomethyl ether acetate The mixture was stirred at 150 ° C. for 3 hours under a nitrogen atmosphere. The weight average molecular weight Mw measured by GPC of the dispersant 1 thus synthesized was about 11,000. The obtained dispersant 1 is a dispersant B1 in which a polyester side chain is grafted to a polyethyleneimine main chain.

(Synthesis Example 2)
21 parts of polyethyleneimine having a molecular weight of about 10,000 (SP-200 manufactured by Nippon Shokubai Co., Ltd.) and 34 parts of polycaprolactone (acid value 8 mgKOH / g) with n = 60 (ie, degree of polymerization 60) and 200 parts of propylene glycol monomethyl ether acetate The mixture was stirred at 150 ° C. for 3 hours under a nitrogen atmosphere. The weight average molecular weight Mw measured by GPC of the dispersant 2 thus synthesized was about 45,000. The obtained dispersant 2 is a dispersant B2 in which a polyester side chain is grafted to the main chain of polyethyleneimine.

(Synthesis Example 3)
In a reactor equipped with a Dean-Stark tube, 50 parts of a polyallylamine (Nittobo PAA-03, weight average molecular weight 3,000) aqueous solution and 500 parts of toluene were refluxed at an external temperature of 130 ° C. until distillation of water stopped. Then, it was concentrated to remove toluene. Next, 45 parts of polycaprolactone (acid value 16 mgKOH / g) with n = 30 (that is, polymerization degree 30) was mixed with 200 parts of propylene glycol monomethyl ether acetate and stirred at 150 ° C. for 3 hours in a nitrogen atmosphere. The weight average molecular weight Mw measured by GPC of the dispersant 3 thus synthesized was about 10,000. The obtained dispersant 3 is a dispersant B1 in which a polyester side chain is grafted to the main chain of polyallylamine.

(Synthesis Example 4)
In a reactor equipped with a Dean-Stark tube, 140 parts of polyallylamine (Nittobo PAA-08, weight average molecular weight 8,000) aqueous solution and 500 parts of toluene were refluxed at an external temperature of 130 ° C. until distillation of water stopped. Then, it was concentrated to remove toluene. Next, 34 parts of polycaprolactone (acid value 8 mgKOH / g) with n = 60 (ie, degree of polymerization 60) was mixed with 200 parts of propylene glycol monomethyl ether acetate and stirred at 150 ° C. for 3 hours in a nitrogen atmosphere. The weight average molecular weight Mw measured by GPC of the dispersant 4 thus synthesized was about 39000. The obtained dispersant 4 is a dispersant B2 in which a polyester side chain is grafted to the main chain of polyallylamine.

(Synthesis Example 5 for Comparative Example)
15 parts of polyethyleneimine having a molecular weight of about 10,000 (SP-200 manufactured by Nippon Shokubai Co., Ltd.) and 40 parts of polycaprolactone (acid value 5 mg KOH / g) with n = 90 (ie, degree of polymerization 90) are mixed with 200 parts of propylene glycol monomethyl ether acetate. The mixture was stirred at 150 ° C. for 3 hours under a nitrogen atmosphere. The weight average molecular weight Mw measured by GPC of the dispersant 5 thus synthesized was about 70000. The obtained dispersant 5 is a dispersant having a weight average molecular weight of about 70000 in which a polyester side chain is grafted to a polyethyleneimine main chain.

(Synthesis Example 6 for Comparative Example)
11 parts of polyethyleneimine having a molecular weight of about 300 (SP-003 manufactured by Nippon Shokubai Co., Ltd.) and 44 parts of polycaprolactone (acid value 49 mgKOH / g) with n = 10 (ie, degree of polymerization 10) and 200 parts of propylene glycol monomethyl ether acetate The mixture was stirred at 150 ° C. for 3 hours under a nitrogen atmosphere. The weight average molecular weight Mw measured by GPC of the dispersant 6 thus synthesized was about 2500. The obtained dispersant 6 is a dispersant having a weight average molecular weight of about 2500, in which a polyester side chain is grafted to a polyethyleneimine main chain.

(Synthesis Example 7 for Comparative Example)
10 parts of polyethyleneimine having a molecular weight of about 1800 (SP-018 manufactured by Nippon Shokubai Co., Ltd.) and 45 parts of polycaprolactone (acid value 16 mgKOH / g) with n = 30 (ie, degree of polymerization 30) and 200 parts of propylene glycol monomethyl ether acetate The mixture was stirred at 150 ° C. for 3 hours under a nitrogen atmosphere. The weight average molecular weight Mw measured by GPC of the dispersant 7 thus synthesized was about 18000. The obtained dispersant 7 is a dispersant having a weight average molecular weight of about 18,000 in which a polyester side chain is grafted to a polyethyleneimine main chain.

(Synthesis of sulfonated dye derivative aluminum salt)
Quinophthalone yellow pigment C.I. I. 30 parts of Pigment Yellow 138 (“Pariotol Yellow K0960-HD” manufactured by BASF) was dissolved in 300 parts of 101% sulfuric acid and stirred at 70 ° C. for 8 hours to carry out sulfonation reaction. The end point of the reaction was defined as the point at which no change in the spectrum was observed by measuring the spectrum of the sulfuric acid solution. Next, this 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 sulfonated dye derivative paste.
The obtained sulfonated dye derivative was subjected to LC-MASS analysis. In HPLC (column: “ODS-100S” manufactured by Tosoh Corporation), the molecular weight of the main peak occupying an area ratio of 80% is Mw = 774 (electron spray method, minus mode). I. Consistent with the molecular weight of the monosulfonated derivative of Pigment Yellow 138. Moreover, it was identified by ¹ H-NMR to be a sulfonated dye derivative having the following structure.

The obtained paste of the sulfonated dye derivative was redispersed in 10,000 parts of water (pH 2.5). Next, the solution was adjusted to pH 11 with an aqueous sodium hydroxide solution and dissolved to give a red solution. To this solution, 278 parts of an aqueous aluminum sulfate solution (liquid sulfuric acid band) was gradually added. Precipitates appeared one after another from the dropped portion, and the pH decreased with the addition. At the end of the addition, pH 3.6 and bleed were not observed. The slurry containing this precipitate was filtered off and washed with water. I. An aluminum salt of a sulfonated derivative of Pigment Yellow 138 was obtained.
The yield after drying was 334 parts, and the yield was 99%. The resulting aluminum salt of the sulfonated dye derivative is presumed to have the following structure.

(Synthesis of copolymer resin 1)
70.0 parts of cyclohexanone was charged into a separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirring device, heated to 80 ° C., and the atmosphere in the flask was replaced with nitrogen. , 10.2 parts of n-butyl methacrylate, 4.0 parts of 2-hydroxyethyl methacrylate, 7.4 parts of methacrylic acid, 8.0 parts of benzyl methacrylate and 0.4 part of 2,2′-azobisisobutyronitrile. The mixture was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain a solution of copolymer resin 1 having a solid content of 30%. The weight average molecular weight of this copolymer resin 1 was 21000.

[Example 1]
(Chip manufacturing)
A mixture having the following composition was mixed in advance, and then kneaded with a two-roll mill to obtain a sheet. The sheet was folded into several sheets and passed through a two-roll mill again. After repeating this process 30 times, the green chip | tip was produced by grind | pulverizing with a grinder.
-Composition-
C. I. Pigment Green 36 (average primary particle size 20 nm) 7.0 parts C.I. I. Pigment Yellow 150 (average primary particle size 25 nm) 4.0 parts Aluminum salt of sulfonated dye derivative 1.0 part Solution of copolymer resin 1 12.0 parts

(Manufacture of pigment dispersion)
After uniformly stirring and mixing a mixture having the following composition, it was dispersed for 3 hours with an Eiger mill ("Mini Model M-250 MKII" manufactured by Eiger Japan) using zirconia beads having a diameter of 0.3 mm, and a filter having a pore size of 5 μm. To prepare a pigment dispersion.
Green chip prepared in Example 1 15.6 parts Dispersant solution of Synthesis Example 1 11.1 parts Dispersant solution of Synthesis Example 2 5.6 parts Propylene glycol monomethyl ether acetate 67.7 parts

(Method for producing green coloring composition)
Next, a mixture having the following composition was stirred and mixed, and then filtered through a filter having a pore size of 1 μm to obtain a green colored composition having photosensitivity.
Pigment dispersion prepared in Example 1 67.0 parts Solution of copolymer resin 1 5.0 parts Dipentaerythritol hexaacrylate 4.0 parts Photopolymerization initiator (“Irgacure 907” manufactured by Ciba Specialty Chemicals) 4 parts sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.2 parts propylene glycol monomethyl ether acetate 22.4 parts

  The obtained green coloring composition was used on a 100 mm × 100 mm glass substrate (1737, manufactured by Corning) using a spin coater so that the y value of the CIE color system used as an index of color density was 0.595. After coating two sheets, prebaking was performed in a clean oven at 90 ° C. for 2 minutes to form a substrate with a coating film of a green coloring composition.

Next, after this substrate is cooled to room temperature, one of the two coated substrates is irradiated with radiation having a wavelength of 365 nm, 405 nm, and 436 nm through a photomask using a high-pressure mercury lamp. Was exposed at an exposure amount of 1,000 J / m ² . Thereafter, the substrate is immersed in a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, developed, washed with ultrapure water, air-dried, and further post-baked at 230 ° C. for 30 minutes. To form a green stripe pixel pattern on the substrate. This substrate is used as a development evaluation substrate.

Furthermore, another substrate with a coating film was exposed to radiation containing each wavelength of 365 nm, 405 nm, and 436 nm at an exposure amount of 1,000 J / m ² without using a photomask and using a high-pressure mercury lamp. Exposed. Thereafter, post baking was performed at 230 ° C. for 30 minutes to form a solid green coating film on the substrate. This substrate is used as a contrast ratio evaluation substrate.

-Evaluation of stability over time (dispersion stability)-
When the viscosity η1 (25 ° C.) immediately after preparation of the obtained green coloring composition and the viscosity η2 (25 ° C.) after one week had passed after preparation were measured using an E-type viscometer, η1 and η2 Were 5.0 mPa · s and 5.1 mPa · s, respectively. The stability over time is good when the amount of change (η2−η1) is 0.5 mPa · s or less.

-Evaluation of developability-
In the exposure process, the presence or absence of a residue in a region not irradiated with light (unexposed portion) was observed with an optical microscope, and the developability was evaluated. As a result, no residue was found in the unexposed portion.

-Evaluation of contrast ratio-
The obtained substrate is sandwiched between two polarizing plates, the front side polarizing plate is rotated while irradiating with a fluorescent lamp (wavelength range of 380 to 780 nm) from the back side, and the transmitted light intensity is measured with a luminance meter LS-100 (MINOLTA). When the maximum value and the minimum value were measured by the company, and the contrast ratio was evaluated as a value obtained by dividing the maximum value by the minimum value, it was 11,100. The contrast value is good if it exceeds 10,000.

[Example 2]
In Example 1, “the dispersant solution of Synthesis Example 1” is changed to “the dispersant solution of Synthesis Example 3”.
A green colored composition was obtained in the same manner as in Example 1 except that the “dispersant solution of Synthesis Example 2” was changed to “the dispersant solution of Synthesis Example 4”.
η1 and η2 were 5.0 mPa · s and 4.9 mPa · s, respectively. Further, no residue was observed in the unexposed area. The contrast ratio was 11,000.

[Example 3]
A green colored composition was obtained in the same manner as in Example 1 except that the “dispersant solution of Synthesis Example 2” was changed to “the dispersant solution of Synthesis Example 4” in Example 1.
η1 and η2 were 4.9 mPa · s and 4.9 mPa · s, respectively. No residue was observed in the unexposed area. The contrast ratio was 11,500.

[Comparative Example 1]
In Example 1, a green colored composition was obtained in the same manner as in Example 1 except that “the dispersant solution of Synthesis Example 2” was changed to “the dispersant solution of Synthesis Example 1”.
η1 and η2 were 4.5 mPa · s and 5.2 mPa · s, respectively. No residue was observed in the unexposed area. The contrast ratio was 9,500.

[Comparative Example 2]
In Example 1, a green colored composition was obtained in the same manner as in Example 1 except that “the dispersant solution of Synthesis Example 1” was changed to “the dispersant solution of Synthesis Example 2”.
η1 and η2 were 5.1 mPa · s and 5.1 mPa · s, respectively. Residues of a level causing practical problems were found in the unexposed areas. The contrast ratio was 9,600.

[Comparative Example 3]
A green colored composition was obtained in the same manner as in Example 1 except that the “dispersant solution of Synthesis Example 2” was changed to “the dispersant solution of Synthesis Example 5” in Example 1.
η1 and η2 were 5.5 mPa · s and 5.6 mPa · s, respectively. Residues of a level causing practical problems were found in the unexposed areas. The contrast ratio was 9,500.

[Comparative Example 4]
In Example 1, a green colored composition was obtained in the same manner as in Example 1 except that “the dispersant solution of Synthesis Example 1” was changed to “the dispersant solution of Synthesis Example 6”.
η1 and η2 were 6.0 mPa · s and 7.2 mPa · s, respectively. Further, no residue was observed in the unexposed area. The contrast ratio was 8,900.

[Comparative Example 5]
A green colored composition was obtained in the same manner as in Example 1 except that “the dispersant solution of Synthesis Example 2” was changed to “the dispersant solution of Synthesis Example 7” in Example 1.
η1 and η2 were 4.8 mPa · s and 5.4 mPa · s, respectively. Further, no residue was observed in the unexposed area. The contrast ratio was 9,900.

The following can be seen from Examples 1 to 3 and Comparative Examples 1 to 5 described above.
Examples 1 to 3 in which a dispersant B1 having a weight average molecular weight of 3,000 to 15,000 and a dispersant B2 having a weight average molecular weight of 20,000 to 60,000 are used in combination. The color composition has good stability over time, and there is no residue after development. It can also be seen that a good color filter was obtained with a contrast exceeding 10,000, and a colored composition having both dispersibility and developability was obtained. On the other hand, Comparative Example 1 produced using only the dispersant B1 without using the dispersant B2 was poor in the temporal stability of the coloring composition and poor in contrast at less than 10,000. Moreover, the comparative example 2 produced only by the dispersing agent B2 without using the dispersing agent B1 had a poor residue in development. Further, Comparative Examples 3 to 5 using a dispersant having a weight average molecular weight outside the range of the present invention are all poor because the contrast is less than 10,000, and the weight average molecular weight of the dispersant B1 is outside the range of the present invention. In Comparative Example 4 using the dispersant and Comparative Example 5 using the dispersant in which the weight average molecular weight of the dispersant B2 is outside the range of the present invention, the temporal stability of the coloring composition was also poor. Thus, it can be seen that Comparative Examples 1 to 5 not using the present invention cannot achieve both dispersibility and developability.

Claims (9)

  (A) An organic pigment having an average primary particle diameter of 10 nm to 35 nm, (B1) a main chain portion having a polyallylamine structure or a polyalkyleneimine structure, and a side chain portion made of polyester, and having a weight average molecular weight of 3000 to 15000. (B2) Graft polymer having a main chain part having a polyallylamine structure or a polyalkyleneimine structure and a side chain part made of polyester and having a weight average molecular weight in the range of 20000 to 60000, (C A coloring composition for a color filter comprising: a) an alkali-soluble resin, (D) a polyfunctional monomer, (E) a photopolymerization initiator, and (F) an organic solvent.   A graft polymer having a main chain part having a polyallylamine structure or a polyalkyleneimine structure and a side chain part made of polyester reacts polyallylamine or polyalkyleneamine with a polyester containing a free carboxylic acid group. The coloring composition for a color filter according to claim 1, which is the obtained graft polymer.   (B) the main chain part having a polyallylamine structure or a polyalkyleneimine structure and a side chain part made of polyester with respect to 100 parts by weight of the organic pigment (A) having an average primary particle diameter of 10 nm to 35 nm. 5-60 parts by mass of a graft polymer having a weight average molecular weight of 3000-15000, and (B2) a main chain part having a polyallylamine structure or a polyalkyleneimine structure, and a side chain part made of polyester The coloring composition for color filters according to claim 1 or 2, comprising 5 to 30 parts by mass of a graft polymer having a weight average molecular weight in the range of 20000 to 60000.   The said (A) 5-100 mass parts of (C) alkali-soluble resin are contained with respect to 100 mass parts of organic pigments with an average primary particle diameter of 10 nm-35 nm, The said any one of Claims 1-3. Coloring compositions for color filters.   5. The composition according to claim 1, further comprising (G) 1 to 40 parts by mass of a pigment derivative with respect to 100 parts by mass of the organic pigment having an average primary particle diameter of 10 nm to 35 nm. Coloring composition for color filter.   The color filter which uses the coloring composition for color filters of any one of Claims 1-5.   A photosensitive film forming step of forming a photosensitive film by applying the color filter coloring composition according to any one of claims 1 to 5 on a substrate, and pattern exposure on the formed photosensitive film And a colored pattern forming step of forming a colored pattern by sequentially performing development.   A liquid crystal display device comprising the color filter according to claim 6.   A solid-state imaging device comprising the color filter according to claim 6.