JP5648557B2 - Blue coloring composition for color filter, and color filter - Google Patents

Description

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

  The color liquid crystal display device controls the amount of light passing through the second polarizing plate by controlling the degree of polarization of the light that has passed through the first polarizing plate by the liquid crystal layer sandwiched between the two polarizing plates. This is a display device that performs display by using a twisted nematic (TN) type liquid crystal. A liquid crystal display device is capable of color display by providing a color filter between two polarizing plates, and has recently been used in televisions, personal computer monitors, and the like. Along with the advancement, demands for a wide color reproduction area and high reliability are also increasing.

  A color filter is a surface of a transparent substrate such as glass, in which two or more kinds of fine band (striped) filter segments of different hues are arranged in parallel or crossing each other, or fine filter segments are arranged vertically and horizontally. It is made up of those arranged in The filter segments are as fine as several microns to several hundreds of microns, and are regularly arranged in a predetermined arrangement for each hue.

  The color filter production method includes a dyeing method using a dye or a salt-forming dye as a colorant, a dye dispersion method, a pigment dispersion method using a pigment as a colorant, a printing method, and an electrodeposition method. Among these, the dyeing method or the dyeing and dispersing method has a drawback that the heat resistance and light resistance are slightly inferior because the colorant is a dye. Therefore, a pigment having excellent heat resistance and light resistance is used as a colorant for the color filter, and a pigment dispersion method is often used as a manufacturing method because of the accuracy and stability of the forming method.

  In the pigment dispersion method, a color resist is formed by mixing and blending a photosensitive agent or an additive into a resin in which pigment particles as a colorant are dispersed in a resin, and this color resist is applied onto a substrate by a coating device such as a spin coater. In this method, a color filter is produced by forming a coating film by the above, performing selective exposure through a mask with an aligner or a stepper, patterning by alkali development and thermosetting, and repeating this operation.

  Conventionally, as a colorant used for forming a blue filter segment (pixel), in general, a phthalocyanine pigment having excellent resistance and color tone is often used. Phthalocyanine pigments have different crystal types such as α-type, β-type, δ-type, and ε-type, and each has excellent properties such as clearness and high coloring power. It is suitable. As this phthalocyanine pigment, those having various central metals such as copper, zinc, nickel, cobalt, and aluminum are known. Among these, copper phthalocyanine pigments are widely used because they have the clearest color tone. In addition, metal phthalocyanine pigments such as metal-free phthalocyanine pigments, zinc phthalocyanine pigments, aluminum phthalocyanine pigments, and cobalt phthalocyanine pigments have been put into practical use.

  In a display device such as a liquid crystal display device using a conventional cold cathode tube type backlight, a combination of a copper phthalocyanine pigment and a dioxazine pigment is combined with a blue filter segment or a cyan filter segment to achieve high brightness and wide color. The display area could be achieved. However, as described above, the color filter is required to have higher brightness and a wider color reproduction region.

  In order to solve the above problems, a technique has been proposed in which a dye, not a pigment, is dissolved as a colorant in a resin or the like (see Patent Document 1). It has also been proposed to use a triarylmethane dye, particularly a triarylmethane dye, as a colorant for a blue filter segment (see Patent Document 2). However, the dye has a problem that it is inferior in heat resistance, light resistance and solvent resistance as compared with the pigment.

  Therefore, as a method for improving the heat resistance, using a salt of triarylmethane dye and aromatic sulfonic acid or a triarylmethane basic dye as a colorant for a color filter (see Patent Document 3), A method of improving light resistance by adding a metal complex to a dye resist (see Patent Document 4) has been proposed. However, the current situation is that these methods cannot sufficiently satisfy both heat resistance and light resistance.

JP-A-6-75375 JP 2001-81348 A JP 2008-304766 A JP 2004-295116 A

  The object of the present invention is to provide a stable blue coloring composition for a color filter having excellent color characteristics and heat resistance, light resistance, and solvent resistance, and color characteristics using the same, and to provide heat resistance, light resistance, and solvent resistance. It is to provide an excellent color filter.

  As a result of intensive studies to solve the above problems, the present inventor has a blue pigment, a salt-forming compound of a triarylmethane-based basic dye, and an acidic group having a copper phthalocyanine structure or a dioxazine structure as a base skeleton. By including a pigment derivative, it has been found that high brightness and a wide color reproduction region are possible, and that excellent performance is also achieved with respect to heat resistance, light resistance and solvent resistance. It was made.

  That is, the present invention is a blue coloring composition for a color filter containing a colorant (A), a pigment derivative (B), a resin (C), and a solvent, wherein the colorant (A) is tria. A pigment derivative (B1) comprising a salt-forming compound (A1) of a reel methane-based basic dye and a blue pigment (A2), wherein the pigment derivative (B) has an acidic group having a copper phthalocyanine structure or a dioxazine structure as a base skeleton. It is related with the blue coloring composition for color filters characterized by including.

Further, the present invention provides the blue colored composition for a color filter, wherein the pigment derivative having an acidic group having a copper phthalocyanine structure or a dioxazine structure as a base skeleton is a pigment derivative represented by the following general formula (2): Related to things.
General formula (2)
P-SO ₃ ^- X ⁺
[In General Formula (2), P represents a copper phthalocyanine structure residue or a dioxazine structure residue, and X is any one of a hydrogen atom, a 1-3 valent metal atom, an organic amine, or ammonia. ]
The present invention also relates to the blue colored composition for a color filter, wherein X in the general formula (2) is an organic amine represented by the general formula (3).
General formula (3)

[Ｒ₁は炭素数１〜２０のアルキル基であり、Ｒ₂、Ｒ₃、及びＲ₄は、それぞれ独立に、水素原子又は炭素数１〜２０のアルキル基を表す。]

[R ₁ is an alkyl group having 1 to 20 carbon atoms, and R ₂ , R ₃ , and R ₄ each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. ]

In the present invention, at least one of R ₁ , R ₂ , R ₃ , or R _{4 in} the general formula (3) is an alkyl group having 10 to 20 carbon atoms. Relates to the composition.
The present invention further relates to the blue coloring composition for a color filter, further comprising a photopolymerizable monomer (D) and a photopolymerization initiator (E).

  The present invention also relates to a color filter comprising a filter segment formed on a substrate with the blue colored composition for a color filter.

  The blue colored composition for a color filter of the present invention is a combination of a triarylmethane salt-forming dye, a blue pigment, and a pigment derivative having an acidic group having a copper phthalocyanine structure or a dioxazine structure as a base skeleton. It is excellent in light resistance and solvent resistance, and can maintain higher brightness. Therefore, a color filter having high brightness can be provided by using the blue coloring composition for a color filter of the present invention.

Hereinafter, the present invention will be described in detail.
The blue coloring composition for a color filter of the present invention is a blue coloring composition for a color filter containing a colorant (A), a pigment derivative (B), a resin (C), and a solvent. (A) includes a salt-forming compound (A1) of a triarylmethane basic dye and a blue pigment (A2), and the pigment derivative (B) has an acidic group having a copper phthalocyanine structure or a dioxazine structure as a base skeleton. It contains the pigment derivative which has.

<< Colorant (A) >>
The colorant (A) of the present invention contains a salt-forming compound (A1) of a triarylmethane basic dye and a blue pigment (A2).

<Salt-forming compound of triarylmethane-based basic dye (A1)>
The salt-forming compound (A1) of the triarylmethane basic dye used in the present invention is blue and purple. That is, the salt-forming compound that can be preferably used in this coloring composition is C.I. I. Basic Blue, C.I. I. It is a salt-forming compound obtained by using a basic dye classified as basic violet and the like and an anionic compound, particularly a colorless anionic compound, as a counter.

  Colorless in the present invention means a so-called transparent state, and is defined as a state in which the transmittance is 80% or more, preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. is there.

  For example, the basic dye and the counter compound can form a salt-forming compound by dissolving both in an aqueous solution or an alcohol solution. Alternatively, it is also possible to obtain a salt-forming compound by melting and kneading them while heating them.

  Although basic dyes have good spectral characteristics, they are extremely poor in light resistance and heat resistance like common dyes. That is, the basic dye has insufficient characteristics for use in a color filter of a color display device or a color imaging device that requires high reliability.

  Therefore, it is preferable to replace the anion of the basic dye with an anion having a higher molecular weight. Preferably, this salt-forming compound is modified with a resin having an acid group.

  The molecular weight of the counter compound is preferably in the range of 200-3500. The molecular weight of the counter compound is more preferably in the range of 250-3500, and more preferably in the range of 300-3500. Or it is preferable that the molecular weight of a counter compound exists in the range of 200-750. When a counter compound having a small molecular weight is used, it is difficult to achieve sufficient heat resistance and light resistance. When a counter compound having a large molecular weight is used, it is difficult for a salt-forming compound to exist in a large mole number in a unit volume, and sufficient color development is difficult.

[Triarylmethane basic dye]
Specific examples of the triarylmethane basic dye that can be used include C.I. I. Basic Violet 1 (Methyl Violet), 3 (Crystal Violet), 14 (Magenta), C.I. I. Basic Blue 1 (Basic Cyanine 6G), 5 (Basic Cyanine EX), 7 (Victoria Pure Blue BO), 26 (Victoria Blue B conc.) And the like. Among them, C.I. I. Basic Blue 7, Violet 1 and Violet 3 are preferably used.

The triarylmethane basic dye develops color when the NH ₂ or OH group located in the para position with respect to the central carbon takes a quinone structure by oxidation. Depending on the number of NH ₂ and OH groups, it can be divided into the following three types. Among them, the triaminotriphenylmethane type basic dye is preferable in terms of good blue color development.
a) Diaminotriphenylmethane basic dye b) Triaminotriphenylmethane basic dye c) Rosolic acid basic dye having OH group Triaminotriphenylmethane basic dye, diaminotriphenylmethane basic dye The dye has a clear color tone and is excellent in sunlight fastness than the other dyes and is preferable. Further, diphenylnaphthylmethane basic dye and / or triphenylmethane basic dye are preferable.
The blue triarylmethane basic dye has spectral characteristics having a high transmittance at 400 to 440 nm.

[Counter compound]
The counter compound used in this coloring composition is an anionic compound, and specifically includes, for example, heteropolyacids, organic sulfonic acids such as aromatic sulfonic acids, and organic carboxylic acids such as aromatic carboxylic acids and fatty acids. Organic acids that are acids, acid dyes, and the like. The counter compound is preferably an organic sulfonic acid or an acid dye. Moreover, since the molecular weight of a counter compound is the range of 250-3500, since it is more excellent in terms of tolerance, it is preferable.

  The molecular weight and average molecular weight specified here are values obtained by rounding off the first decimal place of the theoretical value calculated based on the molecular structure and atomic weight. In addition, when the counter compound is a sodium salt, the molecular weight and the average molecular weight defined here mean a molecular value obtained by replacing sodium with hydrogen.

(Heteropoly acid)
Examples of the heteropolyacid include phosphotungstic acid H3 (PW12O40) .nH2O (n≈30; ≒ represents nearly equal) (molecular weight 3421), silicotungstic acid H4 (SiW12O40) .nH2O (n≈30) (molecular weight 3418) ), Phosphomolybdic acid H3 (PMo12O40) .nH2O (n.apprxeq.30) (molecular weight 2205), silicomolybdic acid H3 (SiMo12O40) .nH2O (n.apprxeq.30) (molecular weight 2202), phosphotungstomolybdate H3 (PW12-XMoXO40) NH2O (n≈30) (6 <X <12) and phosphovanadomolybdic acid H15-X (PV12-XMoXO40) nH2O (n≈30).

  Lintangst molybdic acid, phosphovanadomolybdic acid, and silicotungsto molybdic acid have a molecular weight in the range of 2202 to 3421 by changing the content of components such as phosphotungstic acid, phosphomolybdic acid, silicotungstic acid and silicomolybdic acid Can be adjusted.

  When heteropolyacid is used as the counter compound, the average molecular weight is preferably in the range of 2820-3421. This is because when the counter compound contains molybdenum and tungsten, the proportion of tungsten is preferably more than 50%. In the case of phosphotungstomolybdic acid, a colorant having excellent transparency can be obtained by reducing the Mo content and containing a large amount of W.

(Organic acid)
As the organic sulfonic acid, for example, aromatic sulfonic acid can be used. Preferred compounds as the aromatic sulfonic acid include, for example, 1-naphthylamine-4,8-disulfonic acid (molecular weight 303), 1-naphthylamine-3,8-disulfonic acid (molecular weight 303), 1-naphthylamine-5,7-disulfone. Acid (molecular weight 303), 1-naphthylamine-3,6-disulfonic acid (molecular weight 303), 1-naphthylamine-3,6,8-trisulfonic acid (kofoic acid) (molecular weight 383), 2-naphthylamine-6,8 -Disulfonic acid (molecular weight 303), 2-naphthylamine-1,6-disulfonic acid (molecular weight 303), 2-naphthylamine-4,8-disulfonic acid (molecular weight 303), 2-naphthylamine-3,6-disulfonic acid (amino) -R acid) (molecular weight 303), 2-naphthylamine-5,7-disulfonic acid (amino J acid) (molecular weight) 03), 1-naphthol-4,8-disulfonic acid (molecular weight 304), 1-naphthol-3,8-disulfonic acid (ε acid) (molecular weight 304), 1-naphthol-3,6-disulfonic acid (molecular weight 304) ), 1-naphthol-3,6,8-trisulfonic acid (molecular weight 384), 2-naphthol-6,8-disulfonic acid (molecular weight 304), 2-naphthol-3,6-disulfonic acid (R acid) ( Molecular weight 304), 2-naphthol-3,6,8-trisulfonic acid (molecular weight 384), N-phenyl-1-naphthylamine-8-sulfonic acid (molecular weight 299), Np-tolyl-1-naphthylamine-8 -Sulfonic acid (molecular weight 313), N-phenyl-1-naphthylamine-5-sulfonic acid (molecular weight 299), N-phenyl-2-naphthylamine-6-sulfonic acid (min 299), N-acetyl-7-amino-1-naphthol-3-sulfonic acid (molecular weight 281), N-phenyl-7-amino-1-naphthol-3-sulfonic acid (molecular weight 315), N-acetyl -6-amino-1-naphthol-3-sulfonic acid (molecular weight 281), N-phenyl-6-amino-1-naphthol-3-sulfonic acid (molecular weight 315), 1,8-dihydro-3,6-disulfone Acid (chromotropic acid) (molecular weight 320), 8-amino-1-naphthol-3,6-disulfonic acid (molecular weight 319), 8-amino-1-naphthol-5,7-disulfonic acid (molecular weight 319), 1 , 6-Diamino-2-naphthol-4-sulfonic acid (molecular weight 254), 1-amino-2-naphthol-6,8-disulfonic acid (molecular weight 319), 1-amino-2 Naphthol-3,6-disulfonic acid (molecular weight 319), 2,8-diamino-1-naphthol-5,7-disulfonic acid (molecular weight 334), 2,7-diamino-1-naphthol-3-sulfonic acid (molecular weight) 254), 2,6-diamino-1-naphthol-3-sulfonic acid (molecular weight 254), 2,8-diamino-1-naphthol-3,6-disulfonic acid (molecular weight 334), and 2-amino-7- And phenylamino-1-naphthol-3-sulfonic acid (molecular weight 330).

  It is also preferable to use anthracene sulfonic acid (molecular weight 258), anthraquinone-2-sulfonic acid, or anthraquinone-1-sulfonic acid (molecular weight 288).

  When naphthylamine sulfonic acid having one amino group and one sulfonic acid group is used, excellent heat resistance and light resistance can be achieved. Examples of naphthylamine sulfonic acid include 2-amino-1-naphthalene sulfonic acid (tobias acid, molecular weight 223), 4-amino-1-naphthalene sulfonic acid (naphthoic acid, molecular weight 223), and 8-amino-1-naphthalene sulfone. Acid (peric acid, molecular weight 223), 2-amino-6-naphthalenesulfonic acid (brennic acid, molecular weight 223), 1-amino-5-naphthalenesulfonic acid (Lorentzic acid, molecular weight 223), 5-amino-2-naphthalene Sulfonic acid (molecular weight 223), 1-amino-6-naphthalenesulfonic acid (molecular weight 223), 6-amino-1-naphthalenesulfonic acid (molecular weight 223), and 3-amino-1-naphthalenesulfonic acid (molecular weight 223) Can be mentioned. Among these, 2-amino-1-naphthalenesulfonic acid (tobias acid, molecular weight 223) is particularly preferable in terms of color characteristics and resistance.

  It is also preferable to use hydroxynaphthalenesulfonic acid having one hydroxyl group and one sulfonic acid group. Examples of the hydroxy naphthalene sulfonic acid include 2-hydroxy-6-naphthalene sulfonic acid (shephatic acid, molecular weight 224), 1-hydroxy-4-naphthalene sulfonic acid (nevir-winter acid: NW acid, molecular weight 224), 1- Examples include hydroxy-5-naphthalenesulfonic acid (L acid, molecular weight 224), and 2-hydroxy-8-naphthalenesulfonic acid (croseinic acid, molecular weight 224).

  Among them, an organic sulfonic acid having 2 to 3 sulfonic acid groups is preferable in terms of good color developability and high brightness. When there are 4 or more sulfonic acids, environmental stability deteriorates and changes with time are likely to occur. With one sulfonic acid, the basic dye and the counter compound react in a 1: 1 ratio, and color is generated when the main color is used. May be worse.

  However, in the case of an organic sulfonic acid having a molecular weight in the range of 200 to 250, the molecular weight of the counter compound is small, so even if there is one sulfonic acid group per molecule, the color developability is not impaired. .

As the organic carboxylic acid, for example, an aromatic carboxylic acid or a fatty acid can be used. Specific examples of the organic carboxylic acid include tetrachlorophthalic acid (molecular weight 304), palmitic acid (molecular weight 257), stearic acid (molecular weight 285), arachidic acid (molecular weight 313), behenic acid (molecular weight 341), and lignoceric acid. (Molecular weight 369), oleic acid (molecular weight 282), elaidic acid (molecular weight 282), erucic acid (molecular weight 339), nervonic acid (molecular weight 367), linoleic acid (molecular weight 280), gamolenic acid (molecular weight 278), arachidonic acid ( Molecular weight 305), α-linolenic acid (molecular weight 278), stearidonic acid (molecular weight 276), eicosapentaenoic acid (molecular weight 302), and docosahexaenoic acid (molecular weight 328).
(Acid dyes)
The hue can also be controlled by using a counter compound as an acid dye.

  Preferred acid dyes are C.I. I. Acid Red 52 (Acid Rhodamine B) (molecular weight 580), C.I. I. Acid Red 87 (Eosin G) (molecular weight 691.6), C.I. And I. Acid Red 289 (molecular weight 676.7).

  In the case of an acid dye, a more preferable molecular weight range is 300 to 750. More preferably, it is the range of 350-700. By setting the molecular weight within this range, a colorant having a good balance between weather resistance and coloring power can be obtained, which is preferable.

[Additives to salt-forming compounds]
The salt-forming compound is a resin having an acid group, for example, a resin having an acid group such as rosin-modified maleic acid resin and rosin-modified fumaric acid resin, rosin ester, polyester resin, or acid value. When the styrene-acrylic copolymer and the like are added, the compatibility and dispersibility in the binder resin and the dispersibility in the solvent are greatly improved. As a result, further excellent color developability, heat resistance and light resistance can be realized. Here, the acid group is preferably a carboxyl group (—COOH) or a sulfonic acid group (for example, —SO 3 H or —SO 3 Na).

  The weight average molecular weight of the resin having an acid group is preferably in the range of 400 to 12000, more preferably in the range of 400 to 6000, and in the range of 400 to 2000. Is more preferable. Such a resin is excellent in compatibility with the salt-forming compound. Therefore, when this resin is used, the dispersion of the salt-forming compound in the binder resin is improved.

The weight average molecular weight of the resin having an acid group is measured as follows.
Tetrahydrofuran (THF) is added to the specimen and left for 12 hours. Thereafter, the THF solution of the specimen is filtered, and the molecular weight of the specimen dissolved in the filtrate is measured. For measurement, gel permeation chromatography (GPC) method is used, and molecular weight is calculated from a calibration curve prepared using standard polystyrene. Below, an example of measurement conditions is described.

GPC device: HLC-8120GPC manufactured by Tosoh Corporation
Column: TOS Guard Co., Ltd. TSK Guardcolumn Super H-HT / SK-GEL / Super HM-M 3 flow rate: 1.0 ml / min (THF)

  As the resin having an acid group, a rosin-modified maleic acid resin is preferably used. The rosin-modified maleic resin has an acid-containing polar group and a nonpolar rosin skeleton. The polar group having this acid is a carboxyl group derived from unreacted abietic acid and a carboxyl group of maleic acid, and reacts and is compatible with the polar group of the binder resin. On the other hand, the nonpolar rosin skeleton is compatible with the nonpolar part of the binder resin. Furthermore, the polar group having an acid of the rosin-modified maleic resin reacts with the amino group of the basic dye (unreacted basic dye in the salt-forming compound).

  The acid value of the resin having an acid group is preferably in the range of 100 to 300 mgKOH / g. If the acid value is small, the compatibility between the resin and the salt-forming compound may be insufficient. Moreover, when an acid value is large, when this coloring composition is used as an alkali development type coloring resist mentioned later, it will be easy to produce image development defect. Here, the acid value is a value measured by a method defined in JIS K-0070.

Mixing of the salt-forming compound and the resin having an acid group is performed, for example, by the following method.
(1) Method of mixing resin dissolved in solvent and salt-forming compound (2) Method of mixing molten resin and salt-forming compound In addition, the salt-forming compound and the resin having an acid group Mixing may be performed by other methods.

Specific examples of the mixing methods (1) and (2) are described below. Here, an example using a triarylmethane basic dye and a rosin-modified maleic resin is shown.
(1) Method of mixing resin dissolved in solvent and salt-forming compound (1-1)
A triarylmethane-based basic dye is dissolved in water, and a counter compound such as an organic sulfonic acid is added to the solution while stirring the solution. As a result, the amino group (-NHC2H5) of the triarylmethane basic dye and the acid group of the counter compound are bonded to obtain a salt-forming compound. Prior to the salt formation reaction, the counter compound may be dissolved in an alkali solution such as sodium hydroxide and used, for example, in the form of sodium sulfonate (-SO3Na).

(1-2)
Next, the rosin-modified maleic resin is added to the previous liquid containing the salt-forming compound. Specifically, first, an alkaline aqueous solution such as an aqueous sodium hydroxide solution is added to the liquid containing the salt-forming compound to adjust the liquid to neutrality. Next, rosin-modified maleic resin dissolved in an alkaline aqueous solution is added to this solution, and this is stirred. Thereafter, mineral acid such as hydrochloric acid and sulfuric acid is added to the solution to adjust the solution to be acidic. This insolubilizes the rosin-modified maleic resin. Further, filtration, washing and drying are performed to obtain a colored composition. If necessary, the colored composition may then be pulverized to a desired particle size.

(2) Method of mixing molten resin and salt-forming compound A salt-forming compound and a resin having an acid group, here a rosin-modified maleic acid resin, are heated kneader, Banbury mixer, three roll mill, It puts into kneading machines, such as a two roll mill, a vibration mill, a ball mill, an attritor, and an extruder, and performs melt kneading at a temperature higher than the softening point of the resin having an acid group. Thereby, the salt-forming compound is uniformly dispersed in the resin having an acid group. In addition, the coloring composition obtained here exists in the form with which the resin which has an acid group was coat | covered with the salt-forming compound. Further, the coloring composition is crushed and pulverized to adjust to a desired particle size.

  The weight ratio between the salt-forming compound and the resin having an acid group (salt-forming compound: resin having an acid group) is preferably in the range of 70:30 to 95: 5. As the ratio of the resin having an acid group in the coloring composition increases, the color developability decreases. Specifically, the color derived from the resin having an acid group greatly affects the hue of the colored composition. Moreover, the dispersibility improvement effect of the salt-forming compound in binder resin becomes small, so that the ratio of resin which has an acid group in a coloring composition is small. The weight ratio between the salt-forming compound and the resin having an acid group (salt-forming compound: resin having an acid group) is more preferably in the range of 75:25 to 90:10.

<Blue pigment (A2)>
The blue coloring composition for a color filter of the present invention contains a blue pigment (A2) for further improving heat resistance, and may contain other pigments as long as the effects of the present invention are not impaired. Hereinafter, specific examples of usable pigments are indicated by pigment numbers. The following “CI” means a color index (CI).

  Examples of the blue pigment (A1) used in the present invention include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79. Of these, C.I. I. Pigment Blue 1, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, and more preferably C.I. I. Pigment Blue 15: 6.

  The blue pigment (A2) is preferably in the range of 500 parts by weight or less with respect to 100 parts by weight of the salt-forming compound (A1) of the present invention in order to maintain sufficient brightness as a coloring component for the color filter. Even when the ratio of the blue pigment (A2) is increased as a whole of the coloring component, the effect of adding the salt-forming compound of the present invention is obtained for the purpose of increasing the brightness.

<Other pigments>
Other pigments other than the blue pigment (A2) can be used in combination with the blue coloring composition for a color filter of the present invention. Examples of the chemical structure include organic pigments such as phthalocyanine, quinacridone, benzimidazolone, dioxazine, indanthrene, perylene, and rhodamine lakes. In addition, various inorganic pigments can be used. Among these, a purple pigment is preferable.

  Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50. Of these, C.I. I. Pigment violet 19 and 23, and more preferably C.I. I. Pigment Violet 23.

[Miniaturization of pigment]
The pigment used in the colored composition of the present invention is preferably a finely sized pigment obtained by a salt milling process. The primary particle diameter of the pigment is preferably 20 nm or more because of good dispersion in the colorant carrier. Moreover, since it can form a filter segment with high contrast ratio, it is preferable that it is 100 nm or less. A particularly preferable range is a range of 25 to 85 nm. In addition, the primary particle diameter of a pigment includes the method performed by the method of measuring directly the magnitude | size of a primary particle from the electron micrograph by TEM (transmission electron microscope) of a pigment, for example. Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment are measured, the average is the particle diameter of the pigment particles, and then the volume of each of the 100 or more pigment particles is determined. There is a method in which the volume average particle diameter is obtained as an average primary particle diameter by approximating the cube of the obtained particle diameter.

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

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

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

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

  It is also preferable to add the triarylmethane dye of the present invention at the same time when the salt is milled (miniaturized). When the pigment is refined, a good colorant can be obtained by adding it together.

<< Pigment derivative (B) >>
The blue coloring composition for a color filter of the present invention includes a pigment derivative (B1) having an acidic group having a copper phthalocyanine structure or a dioxazine structure as a base skeleton.

<Pigment derivative (B1)>
The acidic derivative (B1) is a compound represented by the following general formula (1), and is a pigment derivative having a base skeleton of a copper phthalocyanine structure or a dioxazine structure having an acidic group such as a phosphoric acid group, a sulfonic acid group, or a carboxyl group. is there.
General formula (1):
P-Lm
[However, in general formula (1),
P is an m-valent copper phthalocyanine structure residue or dioxazine structure residue;
m is an integer of 1 to 4,
L is an acidic substituent. ]

Especially, since the acidic pigment derivative represented by General formula (2) is excellent from a viewpoint of a dispersibility and tolerance, it is preferable.
General formula (2)
P-SO ₃ ^- · X ⁺
[In General Formula (2), P represents a copper phthalocyanine structure residue or a dioxazine structure residue, and X is any one of a hydrogen atom, a 1-3 valent metal atom, an organic amine, or ammonia. ]
Examples of 1 to 3 metal atoms include lithium, potassium, sodium, calcium, magnesium, strontium, and aluminum. Examples of organic amines include monoalkylamines such as ethylamine and butylamine, dialkylamines such as dimethylamine and diethylamine, and trimethylamine. And alkanolamines such as trialkylamine monoethanolamine such as triethylamine, diethanolamine and triethanolamine.

Furthermore, X in the general formula (2) is more preferably an organic amine represented by the general formula (3) because the heat resistance is improved and the brightness is excellent.
General formula (3)

[Ｒ₁は炭素数１〜２０のアルキル基であり、Ｒ₂、Ｒ₃、及びＲ₄は、それぞれ独立に、水素原子又は炭素数１〜２０のアルキル基を表す。]
なかでも、一般式（３）におけるＲ₁、Ｒ₂、Ｒ₃、またはＲ₄の少なくとも一つが、炭素数１０〜２０のアルキル基である顔料誘導体においては、より優れた明度を得ることができる。

[R ₁ is an alkyl group having 1 to 20 carbon atoms, and R ₂ , R ₃ , and R ₄ each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. ]
Among these, in the pigment derivative in which at least one of R ₁ , R ₂ , R ₃ , or R _{4 in} the general formula (3) is an alkyl group having 10 to 20 carbon atoms, more excellent brightness can be obtained. .

  The blue coloring composition of the present invention may contain other dye derivatives in addition to the pigment derivative (B1), and the dye derivative is a compound in which a substituent is introduced into an organic dye, Also included are pale yellow aromatic polycyclic compounds such as naphthalene and anthraquinone which are not generally called dyes. Examples of the dye derivative are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, and the like. These can be used alone or in combination of two or more.

<< Resin (C) >>
The resin (C) is a colorant (A), particularly one that disperses a pigment, or one that dyes and permeates a salt-forming compound, and examples thereof include a thermoplastic resin and a thermosetting resin.
The resin (C) is preferably a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Moreover, when using with the form of an alkali image development type colored resist material, it is preferable to use the alkali-soluble vinyl resin which copolymerized the acidic group containing ethylenically unsaturated monomer. In order to further improve the photosensitivity, an energy ray curable resin having an ethylenically unsaturated active double bond can also be used.

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

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

  Energy ray curable resins having ethylenically unsaturated active double bonds include reactive substitution of isocyanate groups, aldehyde groups, epoxy groups, etc. on polymers having reactive substituents such as hydroxyl groups, carboxyl groups, amino groups, etc. A resin in which a photo-crosslinkable group such as a (meth) acryloyl group or a styryl group is introduced into the polymer by reacting a (meth) acrylic compound having a group or cinnamic acid is used. In addition, polymers containing acid anhydrides such as styrene-maleic anhydride copolymer and α-olefin-maleic anhydride copolymer are half-esterified with a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. A modified version is also used.

  A thermoplastic resin having both alkali-soluble performance and energy ray curing performance is also preferable as a blue coloring composition for a color filter.

  Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.

  The resin (C) is preferably used in an amount of 30 parts by weight or more with respect to 100 parts by weight of the colorant (A) because the film formability and various resistances are good. Since the characteristics can be expressed, it is preferably used in an amount of 500 parts by weight or less.

"solvent"
In the blue coloring composition for a color filter of the present invention, the colorant (A) is sufficiently dispersed in the resin (C) or solvent, and the dry film thickness becomes 0.2 to 5 μm on a substrate such as a glass substrate. In order to make it easy to apply and form a filter segment, a solvent can be included.

  Examples of the solvent include 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, benzyl alcohol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3 -Butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m -Dichlorobenzene, N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-alkyl Silene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene Glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol mono Hexyl ether, ethylene glycol monomethyl ether , Ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone , Dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipro Lenglycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether , Propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, vinegar Isobutyl, propyl acetate, dibasic esters, and the like.

  Among them, since the dispersibility and solubility of the salt-forming compound (A2) of the triarylmethane basic dye of the present invention are good, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, It is preferable to use glycol acetates such as ethylene glycol monoethyl ether acetate, ketones such as cyclohexanone, and aromatic alcohols such as benzyl alcohol.

  A solvent can be used individually by 1 type or in mixture of 2 or more types. Moreover, since the solvent can adjust the coloring composition for color filters to an appropriate viscosity and can form the filter segment of the target uniform film thickness, it is 800-8000 weight part with respect to 100 weight part of colorants (A). It is preferable to use it in the quantity.

<< Method for Producing Blue Coloring Composition for Color Filter >>
The blue coloring composition for a color filter of the present invention includes, for example, a blue roll (A1), a pigment derivative (B1), and a resin (C) with a solvent added as necessary to a three roll mill, a two roll mill, A pigment dispersion finely dispersed using various dispersing means such as a sand mill, a kneader, or an attritor, and a salt-forming compound-containing resin solution that is a resin solution of a salt-forming compound (A2) of a triarylmethane-based basic dye; Can be mixed and manufactured. The salt-forming compound (A2) of the triarylmethane basic dye may be dissolved or dispersed in the resin solution.

(Dispersing aid)
When dispersing the blue pigment (A1), in addition to the pigment derivative (B), a dispersion aid such as a resin-type dispersant and a surfactant can be used. Since the dispersion aid is excellent in dispersion of the blue pigment (A1) and has a great effect of preventing reaggregation of the blue pigment (A1) after dispersion, the dispersion aid is used to bring the blue pigment (A1) into the resin solution. In the case of using a color composition for dispersed color filters, a color filter having a high spectral transmittance can be obtained.

  When a resin-type dispersant and a surfactant are added, the amount is preferably 0.1 to 55 parts by weight, more preferably 0.1 to 45 parts by weight with respect to 100 parts by weight of the blue pigment (A1). When the blending amount of the resin-type dispersant and the surfactant is less than 0.1 parts by weight, it is difficult to obtain the added effect. When the blending amount is more than 55 parts by weight, the dispersion is affected by an excessive dispersant. May affect.

  The resin-type dispersant has a pigment-affinity part having a property of adsorbing to the blue pigment (A1) and a part compatible with the resin and the solvent, and adsorbs to the blue pigment (A1) to give a resin of the blue pigment. It functions to stabilize dispersion in water and solvents. Specific examples of resin-type dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , Polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amides formed by reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group, and salts thereof Oil-soluble dispersants such as, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Resin, water-soluble polymer, polyester, modified poly Acrylate-based, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, they can be used alone or in admixture of two or more, not necessarily limited thereto.

  In the present invention, a basic resin type dispersant is particularly preferable. Examples of commercially available resin type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130 manufactured by Big Chemie Japan. 140, 154, 161, 162, 163, 164, 165, 166, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150 and 2155, Anti-Terra-U, 203 and 204, BYK-P104, P104S, 220S and 6919, Lactimon, Lactimon-WS and Bykumen, etc., and SOLPERSE-3000, 9000, 13 manufactured by Nippon Lubrizol Corporation 00, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000 and 76500, EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403 manufactured by Ciba Japan 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, And 010,5065,5066,5070,7500,7554,1101,120,150,1501,1502 and 1503, Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, such as PB822 and PB824, and the like.

  The basic resin type dispersant is preferable because 0.1 to 15 parts by weight is excellent in dispersion stability with respect to 100 parts by weight of the blue pigment (A1).

  The amine value of the basic resin type dispersant is preferably 5 mgKOH / g or more and 160 mgKOH / g or less, more preferably 10 mgKOH / g or more and 130 mgKOH / g or less. The amine value can be determined, for example, by using a 0.1N aqueous hydrochloric acid solution by potentiometric titration and then converting it to the equivalent of potassium hydroxide.

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

<< Photopolymerizable monomer (D) >>
The photosensitive coloring composition for color filters of this invention can add a photopolymerizable monomer (D), and can be used as a photosensitive blue coloring composition for color filters.
Examples of the photopolymerizable monomer (D) that can be used in the present invention include monomers or oligomers that are cured by ultraviolet rays or heat to form a resin. These may be used alone or in combination of two or more. Can be used. The blending amount of the monomer is preferably 5 to 400 parts by weight with respect to 100 parts by weight of the colorant (A), and more preferably 10 to 300 parts by weight from the viewpoint of photocurability and developability.

  Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce a resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) ) Acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycidyl -Terdi (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodeca Nyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate ester, epoxy (meth) acrylate, urethane acrylate and other acrylic esters and methacrylate esters, (meth) acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (Meth) acrylamide, N-vinylformamide, acrylonitrile and the like can be mentioned, but are not necessarily limited thereto.

<< Photopolymerization initiator (E) >>
When the blue coloring composition for a color filter of the present invention is cured by ultraviolet irradiation and a filter segment is formed by a photolithographic method, a photopolymerization initiator (E) or the like is added. The amount of the photopolymerization initiator (E) used is preferably 5 to 200 parts by weight with respect to 100 parts by weight of the colorant (A), and 10 to 150 from the viewpoint of photocurability and developability. More preferred are parts by weight.

  As photopolymerization initiator (E), 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl Acetophenone compounds such as 1- [4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or Benzoin compounds such as benzyldimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, or 3,3 ′, 4 Benzophenone compounds such as 4,4′-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthone, etc. 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) Nyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloro Methyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(4-Methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl- Triazine compounds such as (4′-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine and other oxime ester compounds; bis (2,4,6-trimethylbenzoyl) Phosphine compounds such as phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; carbazole compounds; An imidazole compound; or a titanocene compound or the like is used. These photopolymerization initiators can be used alone or in combination of two or more at any ratio as required.

<< Sensitizer >>
Furthermore, the coloring composition for a color filter of the present invention can contain a sensitizer. A sensitizer can be used in the quantity of 0.1-60 weight part with respect to 100 weight part of photoinitiators (E) in a coloring composition.
Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapirazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphyrin derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 ', or 4,4'-tetra (t-butylperoxycarbonyl) benzopheno And 4,4′-diethylaminobenzophenone. Two or more of these sensitizers may be used in any ratio as required.

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

《Amine compound》
Moreover, the blue coloring composition for color filters of this invention can be made to contain the amine compound which has a function which reduces the dissolved oxygen.
Such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate. Examples include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethylparatoluidine.

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

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

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

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

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

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

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

《Other additive ingredients》
The coloring composition for a color filter of the present invention can contain a storage stabilizer in order to stabilize the viscosity with time of the composition. Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained.

  Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Organic phosphines, phosphites and the like can be mentioned. A storage stabilizer can be used in the quantity of 0.1-10 weight part with respect to 100 weight part of coloring agents (A) in the blue coloring composition for color filters.

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

<Removal of coarse particles>
The colored composition for a color filter of the present invention is a coarse particle having a size of 5 μm or more, preferably a coarse particle having a size of 1 μm or more, more preferably a coarse particle having a size of 0.5 μm or more. It is preferable to remove the mixed dust. Thus, it is preferable that the coloring composition for color filters substantially does not contain particles of 0.5 μm or more. More preferably, it is 0.3 μm or less.

《Color filter》
Next, the color filter of the present invention will be described. The color filter of the present invention comprises at least one red filter segment, at least one green filter segment, and at least one blue filter segment on a substrate, and the blue filter segment is for the color filter of the present invention. It is formed using a blue coloring composition.

  The red filter segment can be formed using a normal red coloring composition containing a red pigment and a pigment carrier. Examples of the red coloring composition include C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 146, 166, 168, 169, 176, 177, 178, 179, 184, 185, 187, 200, 202, 208, 210, 221, 242, 246, 254, 255, 264, 270, 272, 273, 274, 276, Red pigments such as 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, or 287 are used. Further, a basic dye or a salt-forming compound of an acid dye exhibiting a red color can also be used.

The red coloring composition includes C.I. I. Pigment Orange 36, 38, 43, 71, or 73, and / or C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181 182,185,187,188,193,194,198,199,213,214,218,219,220, or may be used in combination of a yellow pigment 221, and the like. In addition, a salt forming compound of a basic dye or an acid dye that exhibits orange and / or yellow can be used.
The green filter segment can be formed using a normal green coloring composition including a green pigment and a pigment carrier. Examples of the green pigment include C.I. I. Pigment Green 7, 10, 36, 37, 58, etc. are used.

  A yellow pigment can be used in combination with the green coloring composition. Examples of yellow pigments that can be used in combination include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 9, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, Mention may be made of yellow pigments such as 218, 219, 220 or 221. Further, a basic dye exhibiting yellow and a salt-forming compound of an acid dye can be used in combination.

《Color filter manufacturing method》
The color filter of the present invention can be produced by a printing method or a photolithography method.
The formation of the filter segment by the printing method can be patterned simply by repeating the printing and drying of the coloring composition prepared as the printing ink. Therefore, the color filter manufacturing method is low in cost and excellent in mass productivity. Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. In order to perform printing, it is preferable that the ink does not dry and solidify on the printing plate or on the blanket. Control of ink fluidity on a printing press is also important, and ink viscosity can be adjusted with a dispersant or extender pigment.

  When forming a filter segment by a photolithography method, a coating composition such as spray coating, spin coating, slit coating, roll coating, or the like is applied to the transparent composition on the transparent composition prepared as the solvent developing type or alkali developing type coloring resist. To apply a dry film thickness of 0.2 to 5 μm. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Then, after immersing in a solvent or alkali developer or spraying the developer by spraying or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate the polymerization of the colored resist, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the above printing method can be manufactured.

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

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

  A black matrix can be formed in advance before forming each color filter segment on a transparent substrate or a reflective substrate. As the black matrix, a chromium, chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but is not limited thereto. In addition, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then each color filter segment may be formed. In addition, an overcoat film, a transparent conductive film, or the like is formed on the color filter of the present invention as necessary.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. Unless otherwise specified, “parts” and “%” in the examples represent “parts by weight” and “% by weight”, respectively.

  Prior to the examples, a method for measuring the weight average molecular weight (Mw) of the resin, the pulverized average particle diameter of the salt-forming compound, and the specific surface area of the pigment will be described.

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

(Crushed average particle diameter of salt-forming compound)
The volume average particle diameter was calculated using a multisizer 3 manufactured by Beckman Coulter, Inc. under the condition of an aperture diameter of 100 μm.

(Specific surface area of pigment)
The measurement was performed by an automatic vapor adsorption amount measuring apparatus (“BELSORP18” manufactured by Nippon Bell Co., Ltd.) by the BET method of nitrogen adsorption.

  First, an acrylic resin solution, a salt-forming compound, a fine pigment, a pigment derivative, a salt-forming compound-containing resin solution, a pigment dispersion, a resist material, and a color filter used in Examples and Comparative Examples will be described.

<Method for producing acrylic resin solution>
(Acrylic resin solution)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer was charged with 70.0 parts of cyclohexanone, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), A mixture of 0.4 part of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight of 26000. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. The methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. Addition to prepare an acrylic resin solution.

<Method for producing salt-forming compound>
(Salt-forming compound 1)
2-Amino-1-naphthalenesulfonic acid (tobias acid) (molecular weight 223) was added to a 9 mol% sodium hydroxide solution, and this solution was sufficiently stirred to obtain its sodium salt. This 2-amino-1-naphthalenesulfonic acid (tobias acid) (molecular weight 223) aqueous sodium solution was heated to 85 ° C., and then Victoria Pure Blue dye (CI Basic Blue 7) was added dropwise little by little. The Victoria pure blue dye may be used as an aqueous solution. After completion of the dropwise addition of the Victoria pure blue dye, the mixture was stirred at 85 ° C. for 55 minutes in order to sufficiently react. The end point of the reaction was the time when the reaction solution was dropped on the filter paper and no bleeding occurred. That is, it was judged that the salt-forming compound was obtained when the bleeding disappeared. The mixture was allowed to cool to room temperature with stirring, filtered with suction, and further washed with water. After washing with water, water is removed from the salt-forming compound remaining on the filter paper using a dryer, and the triarylmethane is a salt-forming compound of Victoria Pure Blue dye with 2-amino-1-naphthalenesulfonic acid (tobias acid) A system salt-forming compound 1 was obtained.

(Salt-forming compound 2)
To 100 parts by weight of the salt-forming compound 1, 20 parts by weight of rosin-modified maleic resin (acid value 200, weight average molecular weight 750, Marquide No. 31 manufactured by Arakawa Chemical Co., Ltd.) was added and mixed with a pressure kneader. This mixing was performed for 30 minutes with the material temperature set at 120 ° C. After cooling, fine pulverization was performed using a mechanical pulverizer (Earth Technica Kryptron KTM1 type) to obtain particles having an average particle diameter of 10 μm as the salt-forming compound 2.

(Salt-forming compound 3)
2,8-Diamino-1-naphthol-5,7-disulfonic acid (molecular weight 334) was added to a 7-15 mol% sodium hydroxide solution, and this solution was sufficiently stirred to obtain the sodium salt. Obtained. This 2,8-diamino-1-naphthol-5,7-disulfonic acid sodium salt aqueous solution was heated to 70 to 90 ° C., and then Victoria Pure Blue dye (CI Basic Blue 7) was added dropwise little by little. . The Victoria Pure Blue dye may be used as an aqueous solution. After completion of the dropwise addition of the Victoria pure blue dye, the mixture was stirred at 70 to 90 ° C. for 40 to 60 minutes in order to sufficiently react. The end point of the reaction was the time when the reaction solution was dropped on the filter paper and no bleeding occurred. That is, it was judged that the salt-forming compound was obtained when the bleeding disappeared. The mixture was allowed to cool to room temperature with stirring, filtered with suction, and further washed with water. After washing with water, water is removed from the salt-forming compound remaining on the filter paper using a dryer, and the salt-forming compound of Victoria Pure Blue dye and 2,8-diamino-1-naphthol-5,7-disulfonic acid Salt-forming compound 3 was obtained.

(Salt-forming compound 4)
20 parts by weight of rosin-modified maleic resin (acid value 130, weight average molecular weight 1000, Marquide No. 32 manufactured by Arakawa Chemical Co., Ltd.) was added to 100 parts by weight of the salt-forming compound 3 and mixed with a pressure kneader. This mixing was performed for 30 minutes with the material temperature set at 120 ° C. After cooling, fine pulverization was performed using a mechanical pulverizer (Earth Technica Kryptron KTM1 type) to obtain particles having an average particle diameter of 10 μm as the salt-forming compound 4.

(Salt making compound 5)
1-Hydroxy-4-naphthalenesulfonic acid (NW acid) (molecular weight 224) was added to a 9 mol% sodium hydroxide solution, and this solution was sufficiently stirred to obtain its sodium salt. This 1-hydroxy-4-naphthalenesulfonic acid (NW acid) (molecular weight 224) sodium salt aqueous solution was heated to 85 ° C., and then Victoria Pure Blue Dye (CI Basic Blue 7) was added dropwise little by little. The Victoria Pure Blue dye may be used as an aqueous solution. After completion of the dropwise addition of the Victoria pure blue dye, the mixture was stirred at 85 ° C. for 55 minutes in order to sufficiently react. The end point of the reaction was the time when the reaction solution was dropped on the filter paper and no bleeding occurred. That is, it was judged that the salt-forming compound was obtained when the bleeding disappeared. The mixture was allowed to cool to room temperature with stirring, filtered with suction, and further washed with water. After washing with water, water is removed from the salt-forming compound remaining on the filter paper using a dryer, and a salt-forming compound of Victoria pure blue dye and 1-hydroxy-4-naphthalenesulfonic acid (NW acid) (molecular weight 224) is used. A salt-forming compound 5 was obtained.

(Salt-forming compound 6)
To 100 parts by weight of the salt-forming compound 5, 20 parts by weight of rosin-modified maleic resin (acid value 200, weight average molecular weight 750, Marquide No. 31 manufactured by Arakawa Chemical Co., Ltd.) was added and mixed with a pressure kneader. This mixing was performed for 30 minutes with the material temperature set at 120 ° C. After cooling, fine pulverization was performed using a mechanical pulverizer (Earth Technica Kryptron KTM1 type) to obtain particles having an average particle diameter of 10 μm as the salt-forming compound 6.

<Production method of fine pigment>
(Blue fine pigment)
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 (“LIONOL BLUE ES” manufactured by Toyo Ink Co., Ltd., specific surface area 60 m ² / g), 200 parts of sodium chloride, 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho). And kneading at 80 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of a blue fine pigment were obtained. The specific surface area of the blue fine pigment was 80 m ² / g.

(Purple fine pigment)
Dioxazine-based purple pigment C.I. I. Pigment Violet 23 (Toyo Ink Mfg. Co., Ltd. “LIONOGEN VIOLEET RL” 75 m ² / g) 200 parts, sodium chloride 1400 parts, and diethylene glycol 360 parts were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho), 6 at 80 ° C. Kneaded for hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of a violet fine pigment were obtained. The specific surface area of the purple fine pigment was 95 m ² / g.

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

(Green fine pigment)
Phthalocyanine green pigment C.I. I. 200 parts of Pigment Green 36 (“Lionol Green 6YK” manufactured by Toyo Ink Manufacturing Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. . Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of a green fine pigment were obtained.

(Yellow fine pigment)
Nickel complex yellow pigment C.I. I. 200 parts of Pigment Yellow 150 (“E-4GN” manufactured by LANXESS), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of a yellow fine pigment were obtained.

<Method for producing pigment derivative>
The pigment derivatives shown in Table 1 can be produced, for example, by the method described in JP-A-06-306301.

<Method for producing salt-forming compound-containing resin solution>
(Salt-forming compound-containing resin solution (D-1))
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 5.0 μm filter to prepare a salt-forming compound-containing resin solution (D-1).
Salt-forming compound 1: 11.0 parts acrylic resin solution: 40.0 parts propylene glycol monomethyl ether acetate (PGMAC): 49.0 parts

(Salt-forming compound-containing resin solution (D-2 to 6))
A salt-forming compound-containing resin solution (D-2 to 6) was prepared in the same manner as the salt-forming compound-containing resin solution (D-1) except that the salt-forming compound 1 was changed to the salt-forming compound shown in Table 2. .

<Method for producing pigment dispersion>
(Blue pigment dispersion (BP-1 to 18))
After stirring and mixing the mixture of the composition (parts by weight) shown in Table 3 so as to be uniform, it was 5 using an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm. After time dispersion, the mixture was filtered through a 5.0 μm filter to prepare blue pigment dispersions (BP-1 to 18).

In Table 3, EFKA4300 and PB821 are as follows.
EFKA4300: EFKA Chemical Co., amine value 56 mgKOH / g
PB821: Ajinomoto Fine Techno Co., amine value 10 mgKOH / g
The amine value was determined by potentiometric titration using a 0.1N aqueous hydrochloric acid solution, and then converted to an equivalent of potassium hydroxide. The amine value of the following resin solution shows the amine value of solid content.

(Purple pigment dispersion (VP-1))
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. A pigment dispersion (P-1) was produced by filtration using a filter.
Purple fine pigment 1: 11.0 parts (CI Pigment Violet 23)
Acrylic resin solution: 40.0 parts propylene glycol monomethyl ether acetate (PGMAC): 48.0 parts Resin type dispersant: 1.0 part ("EFKA4300" manufactured by Ciba Japan)

(Red, green, yellow pigment dispersion (RP-1, GP-1, YP-1))
Pigment dispersions (RP-1, GP-1, YP-1) were produced in the same manner as the purple pigment dispersion (VP-1) except that the pigments were changed to the pigments shown in Table 4.

<Method for producing red and green resist materials>
(Red resist material (RR-1))
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to obtain an alkali developing resist material (RR-1).
Colorant dispersion (60 parts in total)
Red pigment dispersion (RP-1): 50.0 parts Yellow pigment dispersion (YP-1): 10.0 parts Acrylic resin solution: 11.0 parts Trimethylolpropane triacrylate: 4.2 parts (Shin Nakamura Chemical) "NK ester ATMPT"
Photopolymerization initiator ("Irgacure 907" manufactured by Ciba Japan): 1.2 parts sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts propylene glycol monomethyl ether acetate (PGMAC): 23 .2 parts

(Green resist material (GR-1))
A green resist material (GR-1) was obtained in the same manner as the red resist material (RR-1) except that the red pigment dispersion (RP-1) was changed to the green pigment dispersion (GP-1).

[Example 1]
(Blue coloring composition (DP-1))
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 5.0 μm filter to obtain a mixed coloring composition (DP-1).

Salt-forming compound-containing resin solution (D-1): 2.2 parts Blue pigment dispersion (BP-1): 8.8 parts Acrylic resin solution: 40.0 parts Propylene glycol monomethyl ether acetate (PGMAC): 49.0 Part

[Examples 2 to 10, Comparative Examples 1 to 10]
(Blue coloring composition (DP-2 to 20))
The blue colored composition (DP-) was changed except that the salt-forming compound-containing resin solution (D-1) and the pigment dispersion (BP-1) were changed to the salt-forming compound-containing resin solution and the blue pigment dispersion shown in Table 5, respectively. Blue colored compositions (DP-2 to 20) were prepared in the same manner as 1).

[Evaluation of blue coloring composition]
About the obtained coloring composition (DP-1-20), the color characteristic, tolerance (heat resistance, light resistance, solvent resistance) test, and the test regarding a coating-film foreign material were done by the following method. The results are shown in Table 6.

(Evaluation of color characteristics)
A colored composition obtained by coating the glass substrate with a film thickness such that the hue after heating at 230 ° C. for 20 minutes was x = 0.150 and y = 0.06 with a C light source was produced. . Thereafter, the brightness (Y) of the obtained substrate was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.).

(Coating film heat resistance test)
The obtained colored composition (DP-1 to 18) was applied on a glass substrate so that the film thickness was 2.0 μm, and the substrate was heated at 230 ° C. for 20 minutes. Thereafter, the color difference 1 (L * (1), a * (1), b * (1)) with a C light source was measured using a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.). Then, as a heat resistance test, the sample was heated in an oven at 250 ° C. for 1 hour, and a color difference 2 (L * (2), a * (2), b * (2)) with a C light source was measured.
Using the measured color difference value, the color difference change rate ΔEab * was calculated by the following formula.
ΔEab * = √ ((L * (2)-L * (1)) ² + (a * (2)-a * (1)) ² + (b * (2)-b * (1)) ² )
And based on color difference change rate (DELTA) Eab *, the heat resistance of the coating film was evaluated in the following four steps.
◎: ΔEab * is less than 1.5 ○: ΔEab * is 1.5 or more and less than 3.0 Δ: ΔEab * is 3.0 or more and less than 5.0 ×: ΔEab * is 5.0 or more

(Coating light resistance test)
A test substrate was prepared in the same procedure as the coating heat resistance test, and the color difference 1 (L * (1), a * (1), b * (1)) under a C light source was measured using a microspectrophotometer. (Olympus Optical Co., Ltd. “OSP-SP200”). Thereafter, the substrate was placed in a light resistance tester (“SUNTEST CPS +” manufactured by TOYOSEIKI) and left for 500 hours. After the substrate was taken out, the color difference 2 (L * (2), a * (2), b * (2)) under a C light source was measured. Using these color difference values, the color difference change rate ΔEab * was calculated in the same manner as in the coating film heat resistance test, and the light resistance of the coating film was evaluated in four stages according to the same criteria as for heat resistance.

(Coating solvent resistance test)
A test substrate is prepared in the same procedure as the heat resistance test, and the color difference 1 (L * (1), a * (1), b * (1)) under a C light source is measured with a microspectrophotometer (Olympus). It measured using "OSP-SP200" by the optical company. Thereafter, the substrate was immersed in N-methylpyrrolidone for 30 minutes. After the substrate was taken out, the color difference 2 (L * (2), a * (2), b * (2)) under a C light source was measured. Using these color difference values, the color difference change rate ΔEab * was calculated in the same manner as in the coating film heat resistance test, and the solvent resistance of the coating film was evaluated in four stages based on the same criteria as for heat resistance.

(Coating foreign matter test)
The evaluation was performed by preparing a test substrate and counting the number of particles. The coloring composition was applied onto the transparent substrate so that the dried coating film was about 2.0 μm, and heated in an oven at 230 ° C. for 20 minutes to obtain a test substrate. The evaluation was performed using a Olympus system metal microscope “BX60”). The magnification is 500 times, and the number of particles that can be observed in any five fields of view through transmission is counted. In the following evaluation results, ◎ and ○ are good, Δ is a level that does not cause a problem in use although there are many foreign matters, and × indicates coating unevenness (spots) due to foreign matters.
◎: Less than 5 ○: 5 or more, less than 20 △: 20 or more, less than 100 ×: 100 or more

  For a color filter of the present invention comprising a salt-forming compound (A1) of a triarylmethane basic dye, a blue pigment (A2), and a pigment derivative (B1) having an acidic group having a copper phthalocyanine structure or a dioxazine structure as a base skeleton Each of the blue colored compositions had high brightness and excellent resistance.

  Of these, the blue coloring compositions (DP-1 to DP-10), in which the pigment derivative (B1) is an organic amine salt represented by the general formula (2), have better heat resistance and contain a salt-forming compound. The coloring compositions (DP-1, DP-2, DP-4, DP-6, DP-8) using the resin solution (D-1) showed excellent color characteristics with a lightness of 7.1 or more. .

  On the other hand, the blue colored compositions (DP-11 to 17 and 19) not containing the pigment derivative (B1) had poor dispersion or poor heat resistance and low brightness. The blue colored composition (DP-18) consisting only of the pigment dispersion had good resistance but low brightness. In the colored composition (DP-20), only the salt-forming compound-containing resin solution was used, so that the resistance surface was extremely deteriorated.

  That is, when only a pigment derivative having a basic group is included, the counter compound of the salt formation compound of the triarylmethane basic dye is attracted to the amine group of the basic derivative, and the original triarylmethane basic dye As a result, it can be seen that the heat resistance is remarkably lowered and the lightness is lowered by using the dye and the pigment in combination as compared with the case of using the dye alone.

[Example 11]
(Blue resist material (R-1))
The following mixture was stirred and mixed to be uniform, and then filtered through a 1.0 μm filter to obtain an alkali developing blue resist material (R-1).

Salt-forming compound-containing resin solution (D-1): 12.0 parts Blue pigment dispersion (BP-1): 48.0 parts Acrylic resin solution: 11.0 parts Trimethylolpropane triacrylate: 4.2 parts (new "NK ESTER ATMPT" manufactured by Nakamura Chemical Co., Ltd.)
Photopolymerization initiator (“Irgacure 907” manufactured by Ciba Japan Co., Ltd.): 1.2 parts Sensitizer (“EAB-F” manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts Cyclohexanone: 23.2 parts

[Examples 12 to 23, Comparative Examples 11 to 15]
(Blue resist material (R-2 to 18))
Hereinafter, the alkali developing type blue resist material (R-2 to 18) was used in the same manner as the blue resist material (R-1) except that the colorant-containing resin solution and the type of the blue pigment dispersion were changed as shown in Table 7. ) In all of these blue resist materials, the total amount of the colorant-containing resin solution and the blue pigment dispersion is 60 parts.

[Evaluation of blue resist material]
Evaluation of the color characteristics, resistance (heat resistance, light resistance, solvent resistance), and coating film foreign matter test in the blue resist material (R-1 to 18) was evaluated using the same method as the blue coloring composition. The results are shown in Table 8.

  Similar to the evaluation results of the blue coloring composition, the salt-formation compound (A1) of the triarylmethane basic dye, the blue pigment (A2), and the pigment derivative having an acidic group having a copper phthalocyanine structure or dioxazine structure as a base skeleton ( All of the blue resist materials of the present invention containing B1) had high brightness and excellent resistance.

  On the other hand, the blue resist material (R-14 to 17) had a heat-resistant color difference change of more than 5 and a low brightness value. The blue resist material (R-18) had no problem with durability, but had a low brightness.

[Example 24]
(Color filter (CF-1))
A black matrix is patterned on a glass substrate, and a red resist material (RR-1) is applied to the substrate with a spin coater in a C light source (hereinafter also used for green and blue) x = 0.640, y = 0. The film was applied to a film thickness of 330 to form a colored film. The film was irradiated with ultraviolet rays of 300 mJ / cm ² through a photomask using an ultrahigh pressure mercury lamp. Next, spray development was performed with an alkaline developer composed of a 0.2% by weight aqueous sodium carbonate solution to remove unexposed portions, followed by washing with ion-exchanged water. The substrate was heated at 230 ° C. for 20 minutes to obtain a red filter segment. Formed. In the same manner, the green resist material (GR-1) is formed to a thickness such that x = 0.300 and y = 0.600, and the blue resist material (R-1) is used, x = 0.150, Each was applied to a film thickness such that y = 0.060, and a green filter segment and a blue filter segment were formed to obtain a color filter (CF-1).

(Production of liquid crystal display device)
A transparent ITO electrode layer was formed on the obtained RGB color filter, and a polyimide alignment layer was formed thereon. A polarizing plate was formed on the other surface of this glass substrate. On the other hand, a TFT array and a pixel electrode were formed on one surface of another (second) glass substrate, and a polarizing plate was formed on the other surface. The two glass substrates prepared in this way are arranged facing each other so that the electrode layers face each other, and are aligned using spacer beads while keeping the distance between the two substrates constant, and an opening for injecting a liquid crystal composition The periphery was sealed with a sealant so as to leave After injecting the liquid crystal composition from the opening, the opening was sealed. A liquid crystal display device thus produced was combined with a three-wavelength CCFL light source of a backlight unit to produce a color display device.

[Examples 25-36, Comparative Examples 16-20]
(Color filter (CF-2 to 18))
A color filter (CF-2 to 18) and a liquid crystal display device were produced in the same manner as in Example 24 (color filter (CF-1)) except that the blue resist material shown in Table 9 was used.

[Evaluation of color filter]
(Evaluation of color characteristics (brightness) of white display)
In the obtained color display device, a light source was emitted to display a color image, and the brightness of each color filter segment portion was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.). The results are shown in Table 9.

  The blue filter segment of the color filter (CF-18) uses a copper phthalocyanine pigment and a dioxazine pigment that have been suitably used conventionally. On the other hand, in the color filter (CF-1 to 13), in addition to the blue pigment (A1), an acid group having a base skeleton of a salt compound (A2) of a triarylmethane basic dye, a copper phthalocyanine structure or a dioxazine structure is used. By including the pigment derivative (B1) it has, higher brightness could be confirmed for each of blue and white.

  As described above, for a color filter including a blue pigment (A1), a salt-forming compound of a triarylmethane basic dye (A2), and a pigment derivative (B1) having an acidic group having a copper phthalocyanine structure or a dioxazine structure as a base skeleton. A blue coloring composition can obtain a blue filter segment excellent in all of color characteristics (lightness) and heat resistance, light resistance and solvent resistance.

Claims (5)

A blue coloring composition for a color filter containing a colorant (A), a pigment derivative (B), a resin (C), and a solvent,
The colorant (A) includes a salt-forming compound (A1) of a triarylmethane basic dye and a blue pigment (A2),
A blue coloring composition for a color filter, wherein the pigment derivative (B) contains a pigment derivative represented by the general formula (2) .
General formula (2)
P-SO ₃ ^- X ⁺
[In General Formula (2), P represents a copper phthalocyanine structure residue or a dioxazine structure residue, and X is any one of a hydrogen atom, a 1-3 valent metal atom, or an organic amine. ] The blue coloring composition for a color filter according to claim 1 , wherein X in the general formula (2) is an organic amine represented by the general formula (3).
General formula (3)

[R ₁ is an alkyl group having 1 to 20 carbon atoms, and R ₂ , R ₃ , and R ₄ each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. ] At least one of R _1, R _2, R ₃ or R _4, in the general formula (3) is a blue colored composition for a color filter according to claim 2, characterized in that an alkyl group having 10 to 20 carbon atoms object. Furthermore, a photopolymerizable monomer (D) and a photoinitiator (E) are contained, The blue coloring composition for color filters of any one of Claims 1-3 characterized by the above-mentioned. A color filter comprising a filter segment formed on the substrate with the blue coloring composition for a color filter according to any one of claims 1 to 4 .