JP2011007847A - Coloring composition for color filter, color filter, and color display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring composition for a color filter, which has excellent color properties, heat resistance, light resistance and solvent resistance, and to provide a color filter which is obtained by using the same and has good color properties, and superior heat resistance, light resistance and solvent resistance.SOLUTION: In the coloring composition for a color filter containing a colorant carrier composed of at least a transparent resin, its precursor or their mixture and a colorant, the colorant is a salt-formation compound composed of a triarylmethane-based basic dye and an organic sulfonated compound having at least two sulfone groups.

Description

  The present invention relates to a colored composition for a color filter used for manufacturing a color filter used for 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. is there. More preferably, it relates to a color filter comprising a blue or cyan filter segment.

  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.

  In addition, color image pickup tube elements typified by C-MOS (Complementary Metal Oxide Semiconductor: Complementary Metal Oxide Semiconductor), CCD (Charge Coupled Device: Charge Coupled Device), etc. have B (blue), G on the light receiving element. In general, color separation is performed by disposing color filters each having an additive mixed primary color filter segment of (green) and R (red). In recent years, there is an increasing demand for color characteristics of color filters, such as transmittance, brightness, and a wide color reproduction region, in color filters used in color image pickup tube elements.

  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 preparing a photosensitizer and additives in a pigment in which pigment particles as a colorant are dispersed in a transparent resin, and this color resist is applied on a substrate such as a spin coater. It is a method for forming a color filter by forming a coating film with an apparatus, selectively exposing through a mask with an aligner, a stepper, etc., patterning by alkali development and thermosetting, and repeating this operation. .

  Conventionally, as a colorant used for forming a blue filter segment (pixel) or a cyan filter segment (pixel), a phthalocyanine pigment generally excellent in durability 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, for example, Patent Document 1). It has also been proposed to use a triarylmethane dye, particularly a triarylmethane dye, as a colorant for a color filter used for a blue filter segment or a cyan filter segment (see, for example, 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.

  In order to improve heat resistance, light resistance, and solvent resistance, it has been proposed to use a salt of triarylmethane dye and aromatic sulfonic acid or a triarylmethane basic dye as a color filter colorant. (For example, refer to Patent Document 3). However, a salt-forming compound of a triarylmethane basic dye and an aromatic monosulfonic acid has a drawback in that sufficient brightness cannot be obtained because the ratio of the color forming component is small and the color developability is low.

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

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

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have determined that, as a colorant of a color filter coloring composition, a triarylmethane basic dye and an organic sulfonated product having at least two sulfone groups It has been found that the use of a salt-forming compound comprising: a high brightness and a wide color reproduction range, and excellent heat resistance, light resistance, and solvent resistance. It is a thing.

  That is, the present invention relates to a color filter coloring composition comprising at least a transparent resin, a precursor thereof or a mixture thereof and a color composition for a color filter, wherein the colorant comprises a triarylmethane basic dye and at least two sulfones. The present invention relates to a coloring composition for a color filter, which is a salt-forming compound comprising an organic sulfonated group having a group.

  The present invention also relates to the above color filter coloring composition, wherein the organic sulfonated product is at least one selected from the group consisting of naphtholsulfonic acid, naphthalenesulfonic acid, and naphthylaminesulfonic acid.

  The present invention also relates to the above color composition for color filter, wherein the colorant further contains a resin having an acid group.

  The present invention also relates to the above color filter coloring composition, wherein the resin having an acid group is a rosin-modified maleic resin.

  The present invention also relates to the above color filter color composition, wherein the colorant carrier contains a transparent resin precursor, and the color composition further contains a photopolymerization initiator.

  In the color filter comprising at least one red filter segment, at least one green filter segment, and at least one blue filter segment, at least one blue filter segment is formed of the coloring composition for a color filter. It relates to a color filter.

  The present invention also provides a color filter comprising at least one magenta color filter segment, at least one yellow color filter segment, and at least one cyan color filter segment, wherein at least one cyan color filter segment is the color filter coloring composition. The color filter formed by these.

  The transmittance spectrum of a coloring composition for a color filter combining a conventional copper phthalocyanine blue pigment and a dioxazine pigment, etc., has a peak position near 450 nm, and the transmittance sharply decreases on the short wavelength side of 450 nm or less. Yes. On the other hand, since the coloring composition for color filters of the present invention uses a salt-forming compound of a triarylmethane basic dye having a large proportion of color forming components as a colorant, copper phthalocyanine blue is used even on the short wavelength side of 450 nm or less. Compared with the pigment, it maintains a high transmittance. Therefore, it effectively acts on a peak in the vicinity of 425 to 440 nm of many backlights such as cold cathode fluorescent lamps, and high brightness can be obtained.

  In addition, since a salt-forming compound is used as a colorant, it is excellent in heat resistance, light resistance and solvent resistance. Therefore, by using the colored composition of the present invention for a color filter, it is possible to form a color filter having high brightness, a wide color reproduction region, and excellent heat resistance, light resistance, and solvent resistance.

It is an example of the emission spectrum of the used backlight.

  Hereinafter, the present invention will be described in detail. The coloring composition for a color filter of the present invention is a coloring composition for a color filter having a coloring agent carrier and a coloring agent comprising at least a transparent resin, a precursor thereof, or a mixture thereof. A coloring composition for a color filter, preferably a blue coloring composition for a color filter, which is a salt-forming compound comprising a dye and an organic sulfonated product having at least two sulfone groups.

(Coloring agent)
A salt-forming compound of a triarylmethane basic dye that can be preferably used in the present invention exhibits blue, purple, and green. When used as a pixel for a blue color filter, a pixel exhibiting blue or purple is used.
That is, C.I. I. Basic Blue, C.I. I. Basic Violet, C.I. I. Basic salt is a salt-forming compound obtained by using, as a counter, a basic dye classified as green or the like and an organic sulfonic acid having at least two sulfone groups.

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-based basic dye b) Triaminotriphenylmethane-based basic dye c) Rosolic acid-based basic dye having an OH group Triaminotriphenylmethane-based basic dye, Diaminotriphenylmethane-based basic dye The dye has a clear color tone and is preferable because it is more excellent in sunfastness than other dyes. Further, diphenylnaphthylmethane basic dye and / or triphenylmethane basic dye are preferable.

  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.), C.I. I. Basic Green 1 (Brilliant Green GX), 4 (Malachite Green) and the like. Among them, C.I. I. Basic Blue 7, Green 4, Green 1, and Violet 3 are preferably used.

The blue triarylmethane basic dye has spectral characteristics having a high transmittance at 400 to 440 nm. However, in spite of having good spectral characteristics, light resistance and heat resistance are very poor like general dyes, and the characteristics are required for use in image display devices using color filters that require high reliability. Is not enough. In addition, a salt-forming compound in which the ratio of basic dye to organic sulfonic acid is 1: 1 has a problem that the ratio of the coloring component in the compound decreases, the brightness decreases, and sufficient color development cannot be achieved.
Therefore, in order to improve the disadvantages of these dyes, it is preferable to make a triarylmethane basic dye with an organic sulfonic acid having at least two sulfone groups and further modify with a resin having an acid group.

Next, a salt-forming compound of a triarylmethane basic dye and an organic sulfonic acid will be described. The triarylmethane basic dye and the organic sulfonic acid can be reacted with each other by dissolving them in an aqueous solution or an alcohol solution to obtain a salt-forming compound.
Examples of organic sulfonic acids include disulfonated naphthalenes (naphthalenedisulfonic acid), trisulfonated naphthalenes (naphthalenetrisulfonic acid), disulfonated naphthols (naphtholdisulfonic acid), and trisulfonated naphthols (naphtholtrisulfonate). Sulfonic acid), disulfonated products of naphthylamines (naphthylamine disulfonic acid), trisulfonated products of naphthylamines (naphthylamine trisulfonic acid), aminohydroxynaphthalenedisulfonic acid, and the like can be used.

  The disulfonated product of naphthalene is a generic name for compounds in which two sulfonic acid groups are bonded to the carbon atom of naphthalene, and the trisulfonated product of naphthalenes is a generic term for compounds in which three sulfonic acid groups are bonded to the carbon atom of naphthalene. The naphthol disulfonate is a generic name for compounds in which two sulfonic acid groups are bonded to the naphthol carbon atom, and the trisulfonated naphthol is a generic name for compounds in which three sulfonic acid groups are bonded to the naphthol carbon atom. is there. The di (tri) sulfonated product of naphthylamines is a general term for compounds in which two (three) sulfonic acid groups are bonded to carbon atoms of naphthylamine.

  Specific examples of the disulfonated products of naphthalenes include 1,3-naphthalenedisulfonic acid, 1,5-naphthalenedisulfonic acid, 1,6-naphthalenedisulfonic acid, 1,7-naphthalenedisulfonic acid, and 2,6-naphthalene. There are disulfonic acid, 2,7-naphthalenedisulfonic acid, etc., and trisulfonated products of naphthalenes include 1,3,5-naphthalenetrisulfonic acid, 1,3,6-naphthalenetrisulfonic acid, 1,3,7 -Naphthalene trisulfonic acid. Further, these sulfonated products of naphthalenes can obtain the same effect even if they are a mixture containing a plurality of isomers. For example, 1,6-naphthalenedisulfonic acid and 2,7-naphthalenedisulfonic acid may coexist.

  Specific examples of disulfonated naphthylamines include 1,3,6-naphthylamine disulfonic acid (Freund acid), 1,3,7-naphthylamine disulfonic acid, 2,3,6-naphthylamine disulfonic acid (amino R acid). ), 2,4,6-naphthylamine disulfonic acid (C acid), 2,5,7-naphthylamine disulfonic acid (amino J acid), 2,6,8-naphthylamine disulfonic acid (amino G acid), 1,3, 6,8-naphthylamine trisulfonic acid (kofu acid) and the like. Moreover, the same effect is acquired even if these disulfonated products of naphthylamines are the mixture in which several isomers exist.

  Examples of disulfonated naphthols include 1-naphthol-2,4-disulfonic acid, 1-naphthol-3,6-disulfonic acid, 1-naphthol-3,8-disulfonic acid (ε acid), and 2-naphthol-3. , 6-disulfonic acid (R acid), 2-naphthol-3,8-disulfonic acid, 2-naphthol-6,8-disulfonic acid (G acid) and the like, and trisulfonated products of naphthols include 1- There are naphthol-2,4,7-trisulfonic acid, 1-naphthol-3,6,8-trisulfonic acid (oxycofolic acid), 2-naphthol-3,6,8-trisulfonic acid and the like. Further, these naphthol disulfonates can obtain the same effect even if they are a mixture containing a plurality of isomers.

Among these, naphthalene disulfonic acid, naphthol disulfonic acid, and naphthylamine disulfonic acid are preferable. Among them, 1,5-naphthalenedisulfonic acid, 2,7-naphthalenedisulfonic acid, 2-naphthol-3,6-disulfonic acid, 2-naphthol-3,8-disulfonic acid, 2,4,6-naphthylamine disulfonic acid (C Acid), 2,6,8-naphthylamine disulfonic acid (amino G acid), and 1,3,6-naphthylamine disulfonic acid (Freund acid) are preferable.
Furthermore, a salt-forming compound composed of Victoria Pure Blue BO (CI Basic Blue 7) and naphthalene disulfonic acid, and a salt-forming compound composed of Victoria Pure Blue BO (CI Basic Blue 7) and naphthol disulfonic acid are: Preferred salt-forming compounds.

When a compound having two sulfone groups such as a disulfonated product of naphthalenes or a disulfonated product of naphthols is reacted with a triarylmethane basic dye to form the colorant of the present invention, the amount of the triarylmethane dye is 2 mol. 1 mol of disulfonate is reacted to form a salt. This is preferable because it neutralizes the charge and the colorant component has an amount twice the molar ratio of the counter ion component, so that it has high brightness and does not impair the color development of the dye as a colorant. Is. That is, it is preferable to use an organic sulfonated product (organic sulfonic acid) having at least two sulfonic acid groups.
In addition, by reacting the trisulfonated product with a triarylmethane-based basic dye, a preferable salt-forming compound can be obtained in the same manner as the disulfonated product, but considering the generation of by-products, it is more stable to use the disulfonated product. A salt-forming compound can be obtained.
Here, when a salt-forming compound is obtained using monosulfonic acid having only one sulfone group, the ratio of the portion derived from the dye in the salt-forming compound and the counter becomes 1: 1, which is sufficient. Cannot get lightness.

A salt-forming compound of a triarylmethane basic dye and an organic sulfonated product (organic sulfonic acid) can be synthesized by a conventionally known method. A specific method is disclosed in Japanese Patent Laid-Open No. 2003-215850.
As an example, after a triarylmethane basic dye is dissolved in water, a sulfonated product of naphthalenes and / or naphthols having at least two sulfonic groups is added, and the chlorination treatment can be performed while stirring. That's fine. Here, the amino group (—NHC ₂ H ₅ ) portion in the triarylmethane-based basic dye is bonded to the sulfonated product of naphthalene and / or the sulfonated group (—SO ₃ H) of the sulfonated product of naphthol. The obtained salt-forming compound is obtained. Here, 1 mol of an organic sulfonated product reacts and forms a salt as a counter component with respect to 2 mol of a triarylmethane-based basic dye.
Here sulfonated sulfonated and / or naphthols of naphthalenes before performing the salt formation process, is dissolved in an alkaline solution such as sodium hydroxide, also be used in the form of sodium sulfonate (-SO ₃ Na) it can. In the present invention, a sulfonic acid group (—SO ₃ H) and a functional group (—SO ₃ Na) which is sodium sulfonate are also synonymous.

The salt-forming compound of the present invention further comprises a resin having an acid group such as a carboxyl group, a rosin ester, a rosin-modified maleic acid resin (also synonymous with rosin-modified fumaric acid resin), and is compatible with the binder resin. Dispersibility and solvent dispersibility are greatly improved. As a result, the colorant, heat resistance, and light resistance are further improved as a colorant. Here, the acid group is preferably a carboxyl group (—COOH) or a sulfone group (—SO ₃ H).

Of these, rosin-modified maleic resin is preferably used. The rosin-modified maleic resin has an acid-containing polar group portion and a non-polar rosin skeleton portion. The polar group portion having the acid is a carboxyl group portion derived from unreacted abietic acid and a carboxyl group of maleic acid, and reacts and is compatible with the polar group portion of the binder resin. Further, the nonpolar rosin skeleton part is compatible with the nonpolar part of the binder resin.
Also, the effect of the reaction between the acid component of the rosin-modified maleic resin and the amino group of the triarylmethane basic dye (unreacted triarylmethane basic dye in the salt-forming compound) is also significant. It is.

When a resin having an acid group, particularly a rosin-modified maleic acid resin is added to and mixed with the salt-forming compound of the present invention, it can be obtained by the following method.
(1) A method in which a triarylmethane salt-forming compound is added after being dissolved in a solvent soluble in a rosin-modified maleic resin and mixed in the solution. (2) Rosin-modified malein using a kneader or the like. A method of adding and mixing a triarylmethane salt forming compound in a state in which the acid resin is melted may be mentioned, but it may be synthesized by any conventionally known method.

An example of these is as follows.
(1) A method in which a triarylmethane salt forming compound is added after being dissolved in a solvent soluble in rosin-modified maleic resin and mixed in the solution.

(1-1)
After the triarylmethane basic dye is dissolved in water, a chlorination treatment is performed while adding a disulfonated product of naphthalenes or a disulfonated product of naphthols and stirring them. Here, a salt-forming compound is obtained in which the amino group (—NHC ₂ H ₅ ) moiety in the triarylmethane-based basic dye and the two sulfonic acid group (—SO ₃ H) moieties in the counter are combined.
Here, a counter compound such as a sulfonated product of naphthalenes or a sulfonated product of naphthols is dissolved in an alkali solution such as sodium hydroxide before the salt formation treatment to obtain a sodium sulfonate form (—SO ₃ Na). It can also be used. In the present invention, a sulfonic acid group (—SO ₃ H) and a functional group (—SO ₃ Na) which is sodium sulfonate are also synonymous.

(1-2)
Next, it is a step of adding a rosin-modified maleic acid resin. After adding an aqueous alkali solution such as an aqueous sodium hydroxide solution to adjust to neutral, the rosin-modified maleic acid resin dissolved in the aqueous alkali solution is added and stirred. Mix while mixing. Next, a rosin-modified maleic resin is insolubilized by adding a mineral acid such as hydrochloric acid or sulfuric acid to make it acidic, and then filtered, washed and dried to obtain a composition. Moreover, what is necessary is just to obtain a desired particle size through a grinding | pulverization process if necessary.

(2) Method of adding and mixing a triarylmethane salt forming compound in a melted rosin modified maleic acid resin using a kneader or the like Resin having a salt forming compound of the present invention and an acid group (rosin modified maleic Acid resin, etc.) into a kneader such as a heating kneader, Banbury mixer, 3-roll mill, 2-roll mill, vibration mill, ball mill, attritor, extruder, etc. and thoroughly mixed to soften the rosin-modified maleic resin. Melt kneading is performed at the above temperature. As a result, the salt-forming compound is dispersed in the resin having an acid group (rosin-modified maleic acid resin). The composition obtained here is in a state where the salt-forming compound is coated with a resin having an acid group (rosin-modified maleic acid resin). Furthermore, the composition may be obtained by coarsely crushing and pulverizing the composition to adjust to a desired particle size.

Weight mixing ratio of triarylmethane salt forming compound and acid group-containing resin (rosin-modified maleic acid resin) (triarylmethane salt forming compound: resin having acid group) is in the range of 70:30 to 95: 5. If so, a good colorant can be obtained. When the ratio of the rosin-modified maleic resin is larger than 30%, the color developability is deteriorated, that is, the color defect derived from the rosin-modified maleic resin is caused, and the ratio of the rosin-modified maleic resin is smaller than 5%. If it becomes, the dispersibility of the salt-forming compound in binder resin will worsen.
More preferably, the weight mixing ratio of the triarylmethane-based salt-forming compound and the acid group-containing resin (rosin-modified maleic acid resin) (salt-forming compound: acid group-containing resin) is in the range of 75:25 to 90:10. It is.

The acid value of the acid group-containing resin, rosin ester, and rosin-modified maleic acid resin is preferably in the range of 20 to 200 mgKOH / g. When the acid value is less than 20 mgKOH / g, the compatibility with the salt-forming compound is deteriorated. On the other hand, if the acid value is larger than 200 mgKOH / g, it becomes unfavorable because it causes poor developability when used as an alkali developing type colored resist described later.
Here, the acid value is a value measured by the method of JIS K-0070.

The colored resin composition of the present invention may contain a pigment within a range not impairing the effects of the present invention in order to further improve heat resistance.
When added to the salt-forming compound of the present invention, pigments of various colors such as blue and purple can be used. 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. Hereinafter, specific examples of usable pigments are indicated by pigment numbers. The following “CI” means a color index (CI).

  Examples of blue pigments include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79. 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.

  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.

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

(Miniaturization of pigment)
The pigment that can be contained in combination with the colored composition of the present invention can be refined by performing a salt milling treatment. 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. The primary particle diameter of the pigment was measured by directly measuring the size of the primary particle from an electron micrograph of the pigment using a TEM (transmission electron microscope). Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle diameter of the pigment particles. Next, for 100 or more pigment particles, the volume of each particle is obtained by approximating it to a cube of the obtained particle size, and the volume average particle size is defined as the average primary particle size.

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

  As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000% by weight, and most preferably 300 to 1000% by weight based on the total weight of the pigment (100% by weight) 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% by weight, and most preferably 50 to 500% by weight, based on the total weight of the pigment (100% by weight).

  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 resin used is preferably in the range of 5 to 200% by weight based on the total weight of the pigment (100% by weight).

  It is also preferable to add the salt-forming compound of the present invention at the same time when the salt is milled (miniaturized). Since the salt-forming compound of the present invention is insoluble in water and alcohols, a good colorant can be obtained by adding it together when the pigment is refined.

(Colorant carrier)
The colorant carrier contained in the coloring composition of the present invention is one that disperses pigments and / or salt-forming compounds, or one that dyes and permeates dyes, and is composed of a transparent resin, a precursor thereof, or a mixture thereof. Is done. The form of the colorant here comprises a salt-forming compound, a mixture of the salt-forming compound and a pigment, or the like.
The transparent resin is 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. Resins include thermoplastic resins, thermosetting resins, and active energy ray curable resins, and precursors thereof include monomers or oligomers that are cured by irradiation with active energy rays to form transparent resins, These can be used alone or in admixture of two or more. The colorant carrier is preferably used in an amount of 30% by weight or more based on the total weight of the colorant (100% by weight) because the film formability and various resistances are good, and the colorant concentration is high and good. It is preferable to use it in an amount of 500% by weight or less because it can exhibit excellent color characteristics.
When the colorant carrier comprises a mixture of a transparent resin and its precursor, the colored composition of the present invention can be prepared in the form of a solvent development type or alkali development type color resist. When preparing in the form of an alkali developing type colored resist, an alkali-soluble resin having an acidic group such as a (meth) acrylic acid copolymer resin (alkali-soluble acrylic resin) is used as a part of the colorant carrier.

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

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

  Active energy ray-curable resins include (meth) acrylic compounds having reactive substituents such as isocyanate groups, aldehyde groups, and epoxy groups on polymers having reactive substituents such as hydroxyl groups, carboxyl groups, and amino groups. Or a resin in which a photocrosslinkable group such as a (meth) acryloyl group or a styryl group is introduced by reacting with cinnamate. Further, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is converted into a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. Half-esterified products are also used.

As a monomer or oligomer that is cured by active energy ray irradiation to produce a transparent resin,
Methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, and tricyclodecanyl Monofunctional (meth) acrylates such as (meth) acrylate;
Bifunctional (meth) acrylates such as polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tripropylene glycol di (meth) acrylate;
Trifunctional or more polyfunctional compounds such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate Functional (meth) acrylate;
1,6-hexanediol diglycidyl ether, bisphenol A diglycidyl ether, neopentyl glycol diglycidyl ether, and epoxy (meth) acrylate which is a reaction product of an epoxy compound such as phenol novolac resin and (meth) acrylic acid;
Various (meth) acrylic acid esters modified with polyester, polyurethane, isocyanurate, methylolated melamine, etc .; and (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, ( Examples include monomers other than (meth) acrylates such as (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, and acrylonitrile, and these can be used alone or in combination of two or more. However, it is not necessarily limited to these.

(dispersion)
The colored composition of the present invention is suitably used as a blue colored composition. Moreover, the possibility of use as a green coloring composition is not denied.
The coloring composition of the present invention comprises a salt-forming compound comprising a triarylmethane-based basic dye and an organic sulfonated product having at least two sulfone groups, preferably together with a pigment derivative, the resin, its precursor, or those In the colorant carrier composed of the above mixture, it can be produced by finely dispersing using various dispersing means such as the above-mentioned three roll mill, two roll mill, sand mill, kneader, or attritor. The colored composition of the present invention can also be produced by mixing several types of colorants separately dispersed in a colorant carrier.

(Dispersing aid)
When dispersing the colorant in the colorant carrier, a dispersion aid such as a pigment derivative, a resin-type dispersant, or a surfactant can be appropriately used. The dispersion aid is excellent in dispersion of the colorant and has a large effect of preventing reaggregation of the colorant after dispersion. Therefore, a dispersion composition is used to disperse the colorant in the colorant carrier using the dispersion aid. When used, a color filter having a high spectral transmittance can be obtained.

Examples of the pigment derivative include a compound in which a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent is introduced into an organic pigment (organic pigment, organic dye), anthraquinone, acridone or triazine. It is done.
In the present invention, a pigment derivative is particularly preferable, and the structure thereof is a compound represented by the following general formula (1).
P-Ln Formula (1)
(However,
P: organic pigment residue, anthraquinone residue, acridone residue or triazine residue L: basic substituent, acidic substituent, or optionally substituted phthalimidomethyl group n: an integer of 1 to 4 is there)
Examples of the organic pigment constituting the organic pigment residue of P include, for example, diketopyrrolopyrrole pigments; azo pigments such as azo, disazo and polyazo; phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine and metal-free phthalocyanine Anthraquinone pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone; quinacridone pigments; dioxazine pigments; perinone pigments; perylene pigments; thioindigo pigments; Indoline pigments; isoindolinone pigments; quinophthalone pigments; selenium pigments; metal complex pigments.

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. What is currently used can be used, These can be used individually or in mixture of 2 or more types.
The blending amount of the pigment derivative is preferably 1 part by weight or more, more preferably 3 parts by weight or more, and most preferably 5 parts by weight or more with respect to 100 parts by weight of the colorant from the viewpoint of improving dispersibility. From the viewpoint of heat resistance and light resistance, the amount is preferably 50 parts by weight or less, more preferably 30 parts by weight or less, and most preferably 25 parts by weight or less with respect to 100 parts by weight of the colorant.

  The resin-type dispersant has a colorant-affinity part having the property of adsorbing to the colorant and a part compatible with the colorant carrier, and adsorbs to the colorant to disperse the colorant to the colorant carrier. It works to stabilize. 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.

  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.

(Photopolymerization initiator)
When the colored 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 or the like is added. The blending amount when using the photopolymerization initiator is preferably 5 to 200% by weight based on the total amount of the colorant, and 10 to 150% by weight from the viewpoint of photocurability and developability. More preferred.

  Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 Acetophenone compounds such as-[4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; benzoin, benzoin Methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or ben Benzoin compounds such as rudimethyl 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-methoxyphene) ) -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. These photopolymerization initiators can be used in an amount of 5 to 200 parts by weight, preferably 10 to 150 parts by weight, with respect to 100 parts by weight of the colorant in the color filter coloring composition.

(Sensitizer)
Furthermore, the coloring composition for a color filter of the present invention can contain a sensitizer. The sensitizer can be used in an amount of 0.1 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator in the colored composition.

  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, tetraphylline 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) benzophen Enone, 4,4'-diethylaminobenzophenone, and the like.

  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.

  Two or more kinds of sensitizers may be used in any ratio as required. The blending amount when using the sensitizer is preferably 3 to 60% by weight based on the photopolymerization initiator contained in the colored composition, and 5 to 50 from the viewpoint of photocurability and developability. More preferably, it is% by weight.

(Other)
Moreover, the 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.

(solvent)
In the colored composition of the present invention, a colorant is sufficiently dispersed in a colorant carrier, and applied to a substrate such as a glass substrate so as to have a dry film thickness of 0.2 to 5 μm to form a filter segment. In order to facilitate this, 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 colorant of the present invention are good, glycol acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, It is preferable to use 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 to an appropriate viscosity and can form a filter segment having a desired uniform film thickness, it is 800 to 4000% by weight based on the total weight of the colorant (100% by weight). It is preferable to use it in the quantity.

(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 colored composition 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 (100% by weight) of the coloring composition.

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, 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 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. Of these, compounds having two or more phenolic hydroxyl groups in one molecule and amine curing agents are preferred. 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 to 15 weight% is preferable with respect to the thermosetting resin whole quantity.

(Other additive components)
The colored composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity of the composition over time. 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. The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the colorant in the coloring composition.

  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 in the coloring composition.

(Removal of coarse particles)
The coloring composition of the present invention is mixed with coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more and coarse particles by means of centrifugation, sintered filter, membrane filter or the like. It is preferable to remove dust. Thus, it is preferable that a coloring composition does not contain a particle | grain of 0.5 micrometer or more substantially. 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 is a color filter comprising at least one red filter segment, at least one green filter segment, and at least one blue filter segment, wherein at least one blue filter segment is colored for the color filter of the present invention. It is formed using a composition.

  The color filter of the present invention is a color filter including at least one magenta color filter segment, at least one cyan color filter segment, and at least one yellow color filter segment. It is formed with the coloring composition for color filters of the invention.

  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, 168, 169, 177, 178, 184, 185, 187, 200, 202, 208, 210, 242, 246, 254, 255, 264, 270, 272, 273, 274, 276, 277, 278, 279, 280, Red pigments such as 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 43, 71, 73 or the like 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, or may be used in combination of a yellow pigment 214, and the like. In addition, a basic dye or orange dye salt-forming compound that exhibits orange and / or yellow can be used in combination.

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 2, 7, 10, 36, 37, 58, etc. are used.
In addition, the aforementioned C.I. I. It is also preferable to use a salt-forming compound composed of a green basic dye such as Basic Green 1 or 4 and an organic sulfonated product having at least two sulfone groups. This green salt-forming compound can also be diverted in the same manner as the blue salt-forming compound.

  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, 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, 221 and the like. Further, a basic dye exhibiting yellow and a salt-forming compound of an acid dye can be used in combination.

  The magenta color filter segment can be formed using a normal magenta color coloring composition including a magenta color pigment and a pigment carrier. Examples of the magenta coloring composition include C.I. I. Pigment Red 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 192, 202, 207, 209, C.I. I. Pigment Violet 19 or the like is used. Further, a basic dye having a magenta color or a salt-forming compound of an acid dye can also be used.

  The yellow filter segment can be formed using a normal yellow coloring composition containing a yellow pigment and a pigment carrier. As a yellow pigment, the pigment illustrated as a yellow pigment which can be used together with a red pigment or a green pigment can be used. Further, a basic dye or a salt forming compound of an acid dye exhibiting yellow can be used.

(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.

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

First, the preparation of acrylic resin solutions used in Examples and Comparative Examples will be described.
(Preparation of 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.
Here, the polymerization average molecular weight (Mw) of the acrylic resin was measured by using TSKgel column (manufactured by Tosoh Corporation) and GPC equipped with RI detector (manufactured by Tosoh Corporation, HLC-8120GPC) using THF as a developing solvent. The weight average molecular weight (Mw) in terms of polystyrene.

(Preparation of Triarylmethane Salt Formation Compound 1)
A triarylmethane salt-forming compound was prepared by the following procedure.
2-Naphthol-3,6-disulfonic acid (R acid) is dissolved in 7 to 15 mol% sodium hydroxide solution, and sufficiently mixed and stirred to obtain its sodium salt. After heating this R-acid sodium salt aqueous solution to 70-90 degreeC, Victoria pure blue dye (CI basic blue 7) is dripped little by little. The Victoria Pure Blue dye may be dissolved in water and used as an aqueous solution. After dripping Victoria pure blue dye, it stirs at 70-90 degreeC for 40-60 minutes, and fully reacts. In order to confirm the end point of the reaction, it can be judged that the salt-forming compound was obtained with the reaction solution dropped on the filter paper and the point where the bleeding disappeared as the end point. The mixture is allowed to cool to room temperature with stirring, and then suction filtered and washed with water. After washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer, and a salt-forming compound of Victoria pure blue dye and 2-naphthol-3,6-disulfonic acid (R acid), Salt-forming compound 1 was obtained.

(Preparation of Triarylmethane Salt Formation Compound 2)
Instead of using 2-naphthol-3,6 disulfonic acid (R acid) used in the triarylmethane-based salt-forming compound 1, tria, except that 2,4,6-naphthylamine disulfonic acid (C acid) is used, tria is used. Preparation was carried out in the same manner as in the reel methane salt forming compound 1 to obtain a salt forming compound of Victoria pure blue dye and C acid, and a salt forming compound 2.

(Preparation of Triarylmethane Salt Formation Compound 3)
Triarylmethane salt formation except that 1,3-naphthalenedisulfonic acid is used instead of 2-naphthol-3,6 disulfonic acid (R acid) used in the triarylmethane salt formation compound 1 Preparation was carried out in the same manner as for Compound 1 to obtain a salt-forming compound and salt-forming compound 3 of Victoria pure blue dye and 1,3, -naphthalenedisulfonic acid.

(Preparation of triarylmethane salt formation compound 4)
2-Naphtylamine-5,7-disulfonic acid (amino J acid) is dissolved in a 7 to 15 mol% sodium hydroxide solution, and sufficiently mixed and stirred to obtain a sodium salt thereof. After heating this amino J acid sodium salt aqueous solution to 70-90 degreeC, Victoria pure blue dye (CI basic blue 7) is dripped little by little. The Victoria Pure Blue dye may be dissolved in water and used as an aqueous solution. After dripping Victoria pure blue dye, it stirs at 70-90 degreeC for 40-60 minutes, and fully reacts. In order to confirm the end point of the reaction, it can be judged that the salt-forming compound was obtained with the reaction solution dropped on the filter paper and the point where the bleeding disappeared as the end point. The mixture is allowed to cool to room temperature with stirring, and then suction filtered and washed with water. After washing with water, the salt-forming compound remaining on the filter paper was dried by removing moisture with a dryer to obtain a salt-forming compound of Victoria Pure Blue dye and amino J acid. Furthermore, 20 parts by mass of rosin-modified maleic acid resin (acid value: 130, Marquide No. 32 manufactured by Arakawa Chemical Co., Ltd.) is added to 100 parts by mass of the salt-forming compound, and mixed with a pressure kneader (at a material temperature of 120 ° C. 30 minutes), and after cooling, the mixture was finely pulverized by a mechanical pulverizer (Kryptron KTM1 type manufactured by Earth Technica Co., Ltd.) to obtain particles having an average particle diameter of 10 μm. At this time, the measurement of the average particle diameter was calculated as the volume average particle diameter using a multisizer 3 manufactured by Beckman Coulter, Inc. under the condition of an aperture diameter of 100 μm.

(Preparation of Triarylmethane Salt Formation Compound 5)
2-Naphtylamine-5,7-disulfonic acid (amino J acid) is dissolved in a 7 to 15 mol% sodium hydroxide solution, and sufficiently mixed and stirred to obtain a sodium salt thereof. After heating this amino J acid sodium salt aqueous solution to 70-90 degreeC, crystal violet dye (CI basic violet 3) is dripped little by little. Crystal violet dye may be dissolved in water and used as an aqueous solution. After the crystal violet dye is dropped, the mixture is stirred at 70 to 90 ° C. for 40 to 60 minutes to sufficiently react. In order to confirm the end point of the reaction, it can be judged that the salt-forming compound was obtained with the reaction solution dropped on the filter paper and the point where the bleeding disappeared as the end point. The mixture is allowed to cool to room temperature with stirring, and then suction filtered and washed with water. After washing with water, the salt-forming compound remaining on the filter paper was dried by removing moisture with a dryer to obtain a salt-forming compound of crystal violet dye and amino J acid. Furthermore, 20 parts by mass of rosin-modified maleic acid resin (acid value: 130, Marquide No. 32 manufactured by Arakawa Chemical Co., Ltd.) is added to 100 parts by mass of the salt-forming compound, and mixed with a pressure kneader (at a material temperature of 120 ° C. 30 minutes), and after cooling, the mixture was finely pulverized by a mechanical pulverizer (Kryptron KTM1 type manufactured by Earth Technica Co., Ltd.) to obtain particles having an average particle diameter of 10 μm. At this time, the measurement of the average particle diameter was calculated as the volume average particle diameter using a multisizer 3 manufactured by Beckman Coulter, Inc. under the condition of an aperture diameter of 100 μm. The salt-forming compound 5 is a violet colorant and is preferably used in combination with the salt-forming compounds 1 to 4.

(Preparation of Triarylmethane Salt Formation Compound 6)
8-amino-1-naphthol-3,6-disulfonic acid (H acid) is dissolved in 7 to 15 mol% sodium hydroxide solution, and sufficiently mixed and stirred to obtain its sodium salt. This aqueous H acid sodium salt aqueous solution was heated to 70 to 90 ° C. and then malachite green dye (C.I.
. Drip basic green 4) little by little. Malachite green dye may be dissolved in water and used as an aqueous solution. After the malachite green dye is dropped, the mixture is stirred at 70 to 90 ° C. for 40 to 60 minutes to sufficiently react. In order to confirm the end point of the reaction, it can be judged that the salt-forming compound was obtained with the reaction solution dropped on the filter paper and the point where the bleeding disappeared as the end point. The mixture is allowed to cool to room temperature with stirring, and then suction filtered and washed with water. After washing with water, the salt-forming compound remaining on the filter paper was dried by removing moisture with a dryer to obtain a salt-forming compound of malachite green dye and amino J acid. Furthermore, 20 parts by mass of rosin-modified maleic acid resin (acid value: 130, Marquide No. 32 manufactured by Arakawa Chemical Co., Ltd.) is added to 100 parts by mass of the salt-forming compound, and mixed with a pressure kneader (at a material temperature of 120 ° C. 30 minutes), and after cooling, the mixture was finely pulverized by a mechanical pulverizer (Kryptron KTM1 type manufactured by Earth Technica Co., Ltd.) to obtain particles having an average particle diameter of 10 μm. At this time, the measurement of the average particle diameter was calculated as the volume average particle diameter using a multisizer 3 manufactured by Beckman Coulter, Inc. under the condition of an aperture diameter of 100 μm.

(Preparation of colored composition 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. The colored composition 1 was produced by filtration using a filter.
Triarylmethane salt-forming compound 1: 11.0 parts Acrylic resin solution prepared previously: 40.0 parts Propylene glycol monomethyl ether acetate (PGMAC): 48.0 parts Resin type dispersant (EFKA4300): 1.0 parts

(Preparation of colored compositions 2 to 13)
Hereinafter, colored compositions 2 to 12 were produced in the same manner as colored composition 1 except that triarylmethane salt-forming compound 1 was replaced with the colorant shown in Table 1.

(Adjustment of resist material 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 1.
Coloring composition 1: 50.0 parts Coloring composition 5: 10.0 parts The previously prepared acrylic resin solution: 11.0 parts Trimethylolpropane triacrylate: 4.2 parts ("NK ester ATMPT made by Shin-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 Propylene glycol monomethyl ether acetate (PGMAC): 23 .2 parts

(Adjustment of resist materials 2 to 11)
Thereafter, alkali-developing resist materials 2 to 11 were obtained in the same manner as in the resist material 1 except that the colored composition 1 and the blending amount shown in Table 2 were changed. Although some resist materials use a colored composition in combination, the total amount of the colored composition is 60 parts in all resist materials.

[Examples 1-7 and Comparative Examples 1-2: Evaluation of resist material]
The color characteristics (brightness) and weather resistance (heat resistance, light resistance, solvent resistance) tests of the obtained resist materials 1 to 9 were performed by the following methods.

(Evaluation of color characteristics)
A resist material was applied on a glass substrate so that x = 0.150 and y = 0.06 with a C light source, and this substrate was heated at 230 ° C. for 20 minutes. Thereafter, the brightness of the obtained substrate was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.).

(Method of coating heat resistance test)
A resist material is applied on a transparent substrate so that the dry coating thickness is about 2.5 μm, and UV exposure is performed through a mask having a predetermined pattern, and then an alkali developer is sprayed to remove uncured portions. Thus, a desired pattern was formed. Then, after heating in an oven at 230 ° C. for 1 hour and allowing to cool, the color difference 1 (L * (1), a * (1), b * (1)) of the obtained coating film with a C light source was measured by a microspectrophotometer. (Olympus Optical Co., Ltd. “OSP-SP200”). 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, and the heat resistance of the coating film was evaluated in the following four stages.
ΔEab * = √ ((L * (2)-L * (1)) ² + (a * (2)-a * (1)) ² + (b * (2)-b * (1)) ² )
◎: 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

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

(Method of coating solvent resistance test)
A test substrate was prepared in the same procedure as the heat resistance test, and a color difference 1 (L * (1), a * (1), b * (1)) with a C light source was measured with a microspectrophotometer (manufactured by Olympus Optical Co., Ltd.). OSP-SP200 "). Thereafter, the substrate was immersed in N-methylpyrrolidone for 30 minutes. After taking out the substrate, the color difference 2 (L * (2), a * (2), b * (2)) with a C light source is measured, and the color difference change rate ΔEab * is calculated in the same manner as in the coating heat resistance test. The solvent resistance of the coating film was evaluated in four stages according to the same criteria as the heat resistance.

  Table 3 shows the results of color characteristics (brightness) and resistance (heat resistance, light resistance, solvent resistance) tests.

  Comparing Examples 1 to 7 and Comparative Example 2, the resist containing a triarylmethane salt-forming compound has higher brightness than the resist containing a copper phthalocyanine pigment and a dioxazine pigment that have been suitably used in the past. It was obtained. Moreover, the resist material of Examples 1-7 and Comparative Example 2 was a result with favorable tolerance. In particular, in the resist material of Example 4 using the triarylmethane salt forming compound 4 added with a rosin-modified maleic acid resin and mixed by a pressure kneader, good resistance results were obtained. On the other hand, since the resist material of Comparative Example 1 uses Pigment Violet 23 as a colorant and Basic Blue 7 as a dye, the lightness is slightly higher than that of a resist containing a copper phthalocyanine pigment and a dioxazine pigment. Although it was a value, the result of the tolerance of a coating film was bad.

[Examples 8 to 14 and Comparative Examples 3 to 4: Evaluation of Color Filter]
A color filter was produced using the obtained resist material, and its quality was confirmed. First, a method for manufacturing a color filter will be described.

(Production of color filter)
A black matrix is patterned on a glass substrate, and a red resist material (resist material 10) is applied to the substrate by 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 is performed with an alkali developer composed of a 2% by weight aqueous sodium carbonate solution to remove unexposed portions, and then the substrate is washed with ion-exchanged water. The substrate is heated at 230 ° C. for 20 minutes to form a red filter segment. did. In the same manner, the green resist material (resist material 11) is formed to a thickness such that x = 0.300 and y = 0.600, and x = 0.150 using the blue resist material (resist material 1). Each was applied to a thickness such that y = 0.06 to form a green filter segment and a blue filter segment to obtain a color filter.

(Production of liquid crystal display device)
A transparent ITO electrode layer was formed on the obtained 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. The liquid crystal display device thus produced was combined with a backlight unit to obtain a liquid crystal panel (Example 8).
Hereinafter, the color filters and color liquid crystal devices of Examples 9 to 14 and Comparative Examples 3 to 4 were manufactured using the resist materials shown in Table 4 by the same method. The emission spectrum of the backlight used is shown in FIG.

  Thereafter, in the obtained color display device, a light source is emitted to display a color image, and the brightness of the red, green, and blue filter segment portions is measured with a microspectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.) The brightness of white display in the color filter was obtained from the obtained brightness. The results are shown in Table 5.

  When Examples 8 to 14 and Comparative Example 4 are compared, the triarylmethane salt forming compound is compared with a color filter using a resist material containing a copper phthalocyanine pigment and a dioxazine-based pigment, which has been conventionally suitably used for the blue filter segment. High brightness was obtained in a color filter using a resist material containing. Further, since the color filter of Comparative Example 3 uses a resist material in which a dye is used in combination with a colorant, slightly higher brightness is obtained than the color filter of Comparative Example 4, but as described above, this resist material has poor resistance. It was.

  From the above, by using the triarylmethane salt-forming compound of the present invention, it is possible to obtain a color filter coloring composition and a color filter excellent in both color characteristics and heat resistance, light resistance, and solvent resistance. Become.

Claims (7)

  A color filter coloring composition comprising a colorant carrier comprising at least a transparent resin, a precursor thereof or a mixture thereof and a colorant, wherein the colorant has a triarylmethane basic dye and an organic sulfone having at least two sulfone groups A coloring composition for a color filter, which is a salt-forming compound comprising a chemical compound.   The colored composition for a color filter according to claim 1, wherein the organic sulfonated product is at least one selected from the group consisting of naphthol sulfonic acid, naphthalene sulfonic acid, and naphthylamine sulfonic acid.   The coloring composition for a color filter according to claim 1 or 2, wherein the colorant further contains a resin having an acid group.   The colored composition for a color filter according to claim 3, wherein the resin having an acid group is a rosin-modified maleic acid resin.   The color composition for color filters according to claim 1, wherein the colorant carrier contains a transparent resin precursor, and the color composition further contains a photopolymerization initiator.   A color filter comprising at least one red filter segment, at least one green filter segment and at least one blue filter segment, wherein the at least one blue filter segment is a coloring composition for a color filter according to any one of claims 1 to 5. The color filter formed by.   6. A color filter comprising at least one magenta color filter segment, at least one yellow color filter segment and at least one cyan color filter segment, wherein the at least one cyan color filter segment is a color filter according to any of claims 1-5. A color filter formed from a coloring composition for use.