JP5790486B2 - Quinophthalone dye and its use - Google Patents

Description

  The present invention relates to a quinophthalone dye. The present invention also relates to a quinophthalone dye used in the production of a color filter used in a color liquid crystal display device, an organic EL display device, a color image pickup tube element, and the like, a coloring composition for a color filter formed by blending the same, and a color Regarding filters. The colored composition of the present invention can be applied to yellow, red, and green color filters.

  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. The liquid crystal display device can perform color display by providing a color filter between two polarizing plates. In recent years, since it has been used for televisions, personal computer monitors, and the like, demands for a wide color reproduction region and high reliability are increasing along with high contrast and high brightness for color filters.

  Other typical liquid crystal display devices include an in-plane switching (IPS) method in which a pair of electrodes is provided on one substrate and electrolysis is applied in a direction parallel to the substrate, negative dielectric anisotropy Vertical alignment (VA) method for vertically aligning nematic liquid crystal with optical properties, and Optical Convencence Bend (OCB) method in which the optical axes of uniaxial retardation films are orthogonal to each other to perform optical compensation Etc., and each has been put to practical use.

  In general, a color filter is formed in a fine strip (stripe) shape formed of a red filter layer (R), a green filter layer (G), and a blue filter layer (B) formed on the surface of a transparent substrate such as glass. The filter segments (pixels) are arranged in parallel or intersecting with each other, or the fine filter segments are arranged in a constant vertical and horizontal arrangement. 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. Recently, in addition to a red filter layer (R), a green filter layer (G), and a blue filter layer (B), a filter segment including a yellow filter layer (Y) is also used.

  One of the quality items required for the color filter is brightness. When a color filter with low brightness is used, the light transmittance is low, resulting in a dark screen. In order to obtain a bright screen, it is necessary to increase the number of backlights that are light sources. For this reason, from the viewpoint of suppressing an increase in power consumption, increasing the brightness of color filters has become a trend.

In addition, a color image pickup device represented by C-MOS (Complementary Metal Oxide Semiconductor: Complementary Metal Oxide Semiconductor), CCD (Charge Coupled Device), etc. has a red filter layer (R) on the light receiving element. In general, color filters each including a primary color filter segment of an additive mixture of a green filter layer (G) and a blue filter layer (B) are disposed and separated. Further, since high sensitivity can be obtained compared to the primary color filter, a color filter having filter segments of cyan, magenta, and yellow (CMY) corresponding to the complementary colors of red, green, and blue is often used. Complementary color filters are often used in video cameras and the like that are difficult to use an auxiliary light source such as a flash.
In recent years, there has been an increasing demand for high transmittance, that is, lightness and high reliability even 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 dye dispersion 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, an anthraquinone pigment (for example, CI Pigment Red 177) or a diketopyrrolopyrrole pigment (for example, CI Pigment Red 254) has been used as a colorant used for forming a red filter segment. It was. These pigments can be easily refined by mechanical treatment, and further, the refined pigment can be dispersed relatively easily. Therefore, these pigments are useful for improving contrast and brightness. Furthermore, in order to achieve high brightness and a wide color reproduction range, these red pigments and C.I. I. In general, yellow pigments such as CI Pigment Yellow 138, 139, 150, and 185 are used in combination as a colorant.

  In addition, as a colorant used for forming a green filter segment, a halogenated copper phthalocyanine pigment (for example, CI Pigment Green 36 or CI Pigment Green 7) has been conventionally used. A zinc halide phthalocyanine pigment (for example, CI Pigment Green 58), which is a color material that exhibits color tone and a wide color display area and has high coloring power, has been often used. Furthermore, in order to achieve high brightness and a wide color reproduction range, these green pigments and C.I. I. It is common to use yellow pigments such as CI Pigment Yellow 138, 139, 150, and 185 in combination.

  Dyes have attracted attention for some time as color materials that replace conventional pigments. Advantages of using a dye include high contrast ratio, suppression of color unevenness, and less dispersion. In fact, it is known that yellow dyes are used for the green and red filters of color filters. However, the pyridone azo dyes used are insufficient in heat resistance and dye solubility, and further improvements are desired.

  Further, as yellow pigments for color filters, quinophthalone dyes as shown in Patent Documents 2 and 3 have been proposed so far. Patent Document 2 has insufficient solubility, and Patent Document 3 has insufficient heat resistance, and solvent solubility and fastness are not compatible.

JP 2002-14223 JP-A-6-9891 JP 2006-91768 A

  An object of the present invention is to provide a dye that satisfies both fastness (heat resistance, light resistance, solvent resistance) and solvent solubility and has good color characteristics (brightness), and a coloring composition comprising the same It is an object to provide a color filter having good contrast characteristics and a good color characteristic using the product.

  As a result of intensive studies to solve the above problems, the present inventors satisfy both fastness (heat resistance, light resistance, solvent resistance) and solvent solubility, and also have color characteristics (lightness). A good quinophthalone dye was found, and the present invention was made based on this finding.

  That is, the present invention relates to a quinophthalone dye characterized by being represented by the following general formula (1).

General formula (1)

(Wherein R ₁ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.
In the formula, R _{2 to} R ₅ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or —COO—R ₆ . R ₆ is a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.
However, at least one of R _{2 to} R ₅ represents —COO—R ₆ . )

  The present invention also relates to a color filter dye comprising the quinophthalone dye.

The present invention also relates to a color filter coloring composition comprising at least a colorant and a binder resin, wherein the colorant contains the color filter dye .

  The present invention also relates to the above color composition for color filters, wherein the colorant further contains a pigment.

  The present invention also relates to a color filter including at least a red filter segment, a green filter segment, and a blue filter segment, wherein at least one filter segment is formed of the color filter coloring composition.

  In the present invention, a quinophthalone dye that satisfies both solvent solubility and fastness (heat resistance, light resistance, solvent resistance) and has good color characteristics (lightness) can be obtained. Furthermore, by producing a color filter with a color filter coloring composition containing this quinophthalone dye, it is possible to form a color filter having good color characteristics (brightness) and a high contrast ratio.

  Further, since the developed quinophthalone dye satisfies a sufficient solvent solubility, a dispersion-less process is possible and color unevenness caused by coarse particles is extremely small. Furthermore, since the fastness is also satisfied, the other physical properties (heat resistance, light resistance, solvent resistance) of the formed color filter are also good.

  Hereinafter, the present invention will be described in detail.

  The quinophthalone dye of the present invention can be represented by the following general formula (1).

General formula (1)

(Wherein R ₁ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.
In the formula, R _{2 to} R ₅ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or —COO—R ₆ . R ₆ is a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.
However, at least one of R _{2 to} R ₅ represents —COO—R ₆ . )

The substituted or unsubstituted alkyl group in R _{1 to} R ₆ is a linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 30 carbon atoms, or an ester bond having 2 to 30 carbon atoms. Examples thereof include a linear, branched, monocyclic or condensed polycyclic alkyl group containing at least one bond selected from (—COO—) and an ether bond (—O—).

  Here, a linear, branched, monocyclic or condensed polycyclic alkyl group having 2 to 30 carbon atoms and containing at least one ester bond (—COO—) is particularly preferable.

  Specific examples of the linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 30 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group. Group, nonyl group, decyl group, dodecyl group, octadecyl group, trifluoromethyl group, isopropyl group, isobutyl group, isopentyl group, 2-ethylhexyl group, 2-hexyldecyl group, sec-butyl group, tert-butyl group, sec -Pentyl group, tert-pentyl group, tert-octyl group, neopentyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, 4-decylcyclohexyl group, etc. However, it is not limited to these.

Specific examples of the linear or branched chain having 2 to 30 carbon atoms include —CH ₂ —CH ₂ —CH—COO—CH ₂ —CH ₃ , —CH ₂ —CH (—CH ₃ ) —CH. _{2 -COO-CH 2 -CH 3,} -CH 2 -CH 2 -CH 2 -OCO-CH 2 -CH 3, -CH 2 -CH 2 -CH 2 -CH 2 -COO-CH 2 -CH (CH 2 _{-CH 3) -CH 2 -CH 2 -CH} 2 -CH 3, - (CH 2) 5 -COO- (CH 2) 11 -CH 3, -CH 2 -CH 2 -CH 2 -CH- (COO- CH ₂ -CH _{3) 2}

_{-CH 2 -O-CH 3, -CH} 2 -CH 2 -O-CH 2 -CH 3, -CH 2 -CH 2 -CH 2 -O-CH 2 -CH 3, - (CH 2 -CH 2 - O) _n —CH ₃ (where n is 1 to 8), — (CH ₂ —CH ₂ —CH ₂ —O) _m —CH ₃ (where m is 1 to 5), —CH _{2 -CH (CH 3) -O-CH} 2 -CH 3 -, - CH 2 -CH- (OCH 3) 2

_{-CH 2 -CH 3, -CH 2 -CH} 2 -COO-CH 2 -CH 2 -O-CH 2 -CH (CH 2 -CH 3) -CH 2 -CH 2 -CH 2 -CH 3, -CH _{2 -CH 3, -CH 2 -CH 2} -COO-CH 2 -CH 2 -O-CH 2 -CH 2 -O-CH 2 -CH (CH 2 -CH 3) -CH 2 -CH 2 -CH 2 it can be exemplified -CH _3, but is not limited thereto.

  Specific examples of monocyclic or condensed polycyclic alkyl groups having 2 to 30 carbon atoms and optionally containing at least one bond selected from an ester bond (—COO—) and an ether bond (—O—) Can include the following, but is not limited thereto.

The substituted or unsubstituted aryl group in R _{1 to} R ₆ is a monocyclic or condensed polycyclic aromatic group that may contain a substituted or unsubstituted heteroatom having 6 to 30 carbon atoms, such as a phenyl group 1-naphthyl group, 2-naphthyl group, p-biphenyl group, m-biphenyl group, 2-anthryl group, 9-anthryl group, 2-phenanthryl group, 3-phenanthryl group, 9-phenanthryl group, 2-fluorenyl group 3-fluorenyl group, 9-fluorenyl group, 1-pyrenyl group, 2-pyrenyl group, 3-perylenyl group, terphenyl group, thienyl group, benzothienyl group, naphthothienyl group, furyl group, pyranyl group, pyrrolyl group, imidazolyl Group, pyridyl group, indole group, thiazole group and the like.

Moreover, the hydrogen atom of the substituted or unsubstituted alkyl group in R < ₁ > -R < ₆ > and the substituted or unsubstituted aryl group may be further substituted with another substituent.

  Such substituents include halogen atoms, substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups, nitro groups, hydroxyl groups, substituted or unsubstituted alkoxyl groups, substituted or unsubstituted aryloxy groups. Can be mentioned.

Here, the substituted or unsubstituted alkyl group and the substituted or unsubstituted aryl group have the same meanings as the substituted or unsubstituted alkyl group and the substituted or unsubstituted aryl group in R _{1 to} R ₆ .

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The substituted or unsubstituted alkoxyl group is a group in which an oxygen atom is bonded to the substituted or unsubstituted alkyl group in R _{1 to} R ₆ .

The substituted or unsubstituted reeloxy group is a group in which an oxygen atom is bonded to the substituted or unsubstituted aryl group in R _{1 to} R ₆ .

  The quinophthalone dye of the present invention can be obtained by either one of the following two reaction formulas.

  One is a method in which a corresponding 2-methylquinoline and a corresponding phthalic anhydride are reacted in benzoic acid at a high temperature as shown in the following reaction formula.

  The other is a method in which the corresponding quinophthalone compound and the corresponding halide are reacted in N, N-dimethylacetamide under basic conditions as shown in the following reaction formula.

  The quinophthalone dye of the general formula (1) of the present invention has tautomers having structures such as the following general formulas (1A) and (1B). These tautomers also include the scope of rights of the present invention. It is in.

  Specific examples of the quinophthalone dye of the present invention include the following dyes, but the dye of the present invention is not limited thereto.

  The quinophthalone coloring matter of the present invention can be used as a coloring material for coloring printing ink, IJ ink, plastic, paint, fiber, stationery, writing instrument, cosmetics, and the like.

  Next, the coloring composition for a color filter of the present invention will be described in detail.

The coloring composition comprising the quinophthalone dye of the present invention has a yellow hue itself, and when used in combination with a pigment, it can be a colored composition exhibiting the same color yellow, further green and red. Thus, it is possible to obtain a colorant that is excellent in resistance, color development, and color reproducibility. Among them, the colored composition of the present invention can be used in combination with a green pigment and / or a blue pigment to obtain a green colorant used for a green filter segment having high brightness and a high CR ratio. Moreover, the coloring composition of this invention can obtain the red coloring agent used for a red filter segment which has high brightness and high CR ratio by using together with a red pigment. The colored composition of the present invention can be used in combination with a yellow pigment to obtain a yellow colorant for use in a yellow filter segment having excellent durability and color strength while maintaining high brightness and a high CR ratio. And since it has sufficient solubility, it is a quinophthalone dye which can be made dispersion-free.
The pigments that can be used for these are described below.

  The green colorant for forming the green filter segment is composed of the green pigment and / or blue pigment described below and the quinophthalone dye of the present invention.

(Pigment forming green filter segment)
[Green pigment]
As the green pigment, a polyhalogenated phthalocyanine pigment is preferably used. The polyhalogenated phthalocyanine pigment represents a phthalocyanine pigment having at least two or more halogen atoms. Specifically, C.I. I. Pigment green 7, 36, 37, 58, and the like.

[Blue pigment]
As the blue pigment forming the green filter segment, it is preferable to use an aluminum phthalocyanine pigment. Aluminum phthalocyanine pigments are preferred pigments because they have higher coloring power than halogenated phthalocyanine pigments. Thereby, the addition amount of a pigment can be reduced and the film thickness of a color filter can be made small. Moreover, the point which does not contain a halogen atom is also preferable in consideration of environmental safety. The hue of the aluminum phthalocyanine pigment changes when the axial substituent is changed. The axial substituent is preferably a phosphoric acid compound, a sulfonic acid compound, or a carboxylic acid compound.

  Particularly preferred pigments here are C.I. I. Pigment Green 36, 58, 79, aluminum phthalocyanines containing a shaft substitution product.

[Yellow pigment]
The green colorant may further use a yellow pigment. 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, Mention may be made of yellow pigments such as 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220 or 221.

  The usage ratio of the green pigment and / or blue pigment to the quinophthalone dye of the present invention is preferably 1 to 1200 parts by weight of the quinophthalone dye of the present invention with respect to 100 parts by weight of the pigment. More preferably, it is 5 to 600 parts by weight. When the addition amount of the quinophthalone dye of the present invention is less than 1 part by weight, the reproducible chromaticity region becomes narrow, and when it exceeds 1200 parts by weight, the hue changes, which is not preferable.

  When the yellow pigment and the quinophthalone dye of the present invention are used in combination, the usage ratio of the green pigment and / or the blue pigment and the yellow colorant (the yellow pigment, the color pigment and the quinophthalone dye mixture of the present invention) The yellow colorant is preferably 1 to 1200 parts by weight with respect to 100 parts by weight. More preferably, it is 5 to 600 parts by weight. If the addition amount of the yellow colorant is less than 1 part by weight, the reproducible chromaticity region becomes narrow, and if it exceeds 1200 parts by weight, the hue changes, which is not preferable.

  When the yellow pigment and the quinophthalone dye of the present invention are used in combination, the mixing ratio of the yellow pigment and the content of the quinophthalone dye of the present invention is 100 parts by weight of the yellow pigment in consideration of the color composition. The quinophthalone dye is preferably 1 to 400 parts by weight. More preferably, the quinophthalone dye of the present invention is in the range of 5 to 300 parts by weight with respect to 100 parts by weight of the yellow pigment. These blends can be appropriately adjusted and used in consideration of the heat resistance, light resistance, and brightness of the colorant.

(Pigment forming yellow filter segment)
[Yellow pigment]
When forming a yellow filter segment, in addition to the quinophthalone dye of the present invention, the following yellow pigment can be used in combination.

C. 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 or the like. I. Pigment Yellow 138, 139, 150, and 185 are preferably used.

  The usage ratio of the yellow pigment and the quinophthalone dye of the present invention is preferably 1 to 1200 parts by weight of the quinophthalone dye of the present invention with respect to 100 parts by weight of the yellow pigment. More preferably, it is 5 to 600 parts by weight. In consideration of the color composition, the mixing ratio of the yellow pigment and the quinophthalone dye of the present invention is preferably 1 to 400 parts by weight of the quinophthalone dye of the present invention with respect to 100 parts by weight of the yellow pigment. More preferably, the dye for quinophthalone of the present invention is in the range of 5 to 300 parts by weight with respect to 100 parts by weight of the yellow pigment. These blends can be appropriately adjusted and used in consideration of the heat resistance, light resistance, and brightness of the colorant. Particularly preferred pigments here are C.I. I. Pigment Yellow 138, 139, 150, and 185.

(Pigment forming red filter segment)
[Red pigment]
The red colorant for forming the red filter segment is composed of the red pigment described below and the quinophthalone dye of the present invention.

Examples of red pigments 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, 149, 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, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, or 287 are used. Among them, C.I. I. Pigment Red 177, 179, 254 is preferably used.

  Also, red dyes such as xanthene, azo, disazo, and anthraquinone can be used. Specifically, C.I. I. Examples thereof include salt-forming compounds of xanthene acid dyes such as Acid Red 52, 87, 92, 289 and 338.

[Yellow pigment, Orange pigment]
The red colorant may be used in combination with the following yellow pigment and orange pigment.

  C. I. Pigment orange 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 221 and the like.

  The usage ratio of the red pigment and the quinophthalone dye of the present invention is preferably 1 to 800 parts by weight of the quinophthalone dye of the present invention with respect to 100 parts by weight of the red pigment. More preferably, it is 5 to 400 parts by weight. If the addition amount of the quinophthalone dye of the present invention is less than 1 part by weight, the reproducible chromaticity region becomes narrow, and if it exceeds 800 parts by weight, the hue changes, which is not preferable. In consideration of the color composition, the mixing ratio of the red pigment and the quinophthalone dye of the present invention is preferably 1 to 400 parts by weight of the quinophthalone dye of the present invention with respect to 100 parts by weight of the red pigment. More preferably, the quinophthalone dye of the present invention is in the range of 5 to 300 parts by weight with respect to 100 parts by weight of the red pigment. Particularly preferred pigments here are C.I. I. Pigment Red 177,254.

(Miniaturization of pigment)
The pigment used in the present invention is preferably finely used. There are no particular limitations on the method of miniaturization. For example, any of wet grinding, dry grinding, and dissolution precipitation can be used. As exemplified in the present invention, salt milling treatment by a kneader method, which is one type of wet grinding. Etc. can be made finer. The primary particle diameter of the pigment is preferably 10 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 10 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.

  Salt milling is a batch or continuous type of mixture of pigment, water-soluble inorganic salt and water-soluble organic solvent, such as a kneader, 2-roll mill, 3-roll mill, ball mill, attritor, sand mill, planetary mixer, etc. In this process, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water after mechanically kneading while heating using a kneader. 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 total 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 total 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 resin used is preferably in the range of 5 to 200 parts by weight with respect to 100 parts by weight of the total weight of the pigment.

  It is also preferable to add the quinophthalone dye of the present invention simultaneously with the salt milling (miniaturization) of the pigment. When the pigment is refined, a good colorant can be obtained by adding it together.

<Binder resin>
The binder resin is a colorant such as a pigment or a dye, particularly one that disperses the quinophthalone dye of the present invention, or a dye that penetrates the quinophthalone dye of the present invention, such as a thermoplastic resin or a thermosetting resin. It is done.

  The binder resin is preferably a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength 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. Furthermore, an active energy ray-curable resin having an ethylenically unsaturated double bond can be used for the purpose of further improving photosensitivity and improving solvent resistance.

  In particular, by using an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain for an alkali development resist for color filters, no coating film foreign matter is generated after the colorant is applied. The stability of the colorant is preferably improved. When a linear resin that does not have an ethylenically unsaturated double bond in the side chain is used, the colorant is not easily trapped in the resin and the colorant mixture, and has a degree of freedom. The colorant component easily aggregates and precipitates, but by using an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain, the colorant is converted into a resin in a mixture of resin and colorant. Because it is easily trapped, it is difficult for the dye to elute in the solvent resistance test, the colorant component does not easily aggregate and precipitate, and the resin is three-dimensionally crosslinked when exposed to active energy rays to form a film. It is estimated that the colorant component is less likely to aggregate and precipitate even if the colorant molecules are fixed and the solvent is removed in the subsequent development step.

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

  When the binder resin is used as a photosensitive coloring composition for a color filter, from the viewpoint of dispersibility, permeability, developability, and heat resistance of the pigment and the quinophthalone dye of the present invention, the colorant adsorbing group and the developing The balance of the carboxyl group that acts as an alkali-soluble group, the aliphatic group that acts as an affinity group for the colorant carrier and the solvent, and the aromatic group, dispersibility, penetrability, developability of the pigment and the quinophthalone dye of the present invention, It is important for durability, and it is preferable to use a resin having an acid value of 20 to 300 mgKOH / g. When the acid value is less than 20 mgKOH / g, the solubility in the developing solution is poor and it is difficult to form a fine pattern. When it exceeds 300 mgKOH / g, no fine pattern remains.

  The binder resin is preferably used in an amount of 30 parts by weight or more based on 100 parts by weight of the total weight of the colorant because the film formability and various resistances are good, and the colorant concentration is high, and good color characteristics are obtained. Since it can be expressed, it is preferably used in an amount of 500 parts by weight or less.

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

  Examples of the vinyl-based alkali-soluble resin copolymerized with 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.

  Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include resins having an unsaturated ethylenic double bond introduced by the following methods (a) and (b).

[Method (a)]
As the method (a), for example, a side chain epoxy group of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having an epoxy group and one or more other monomers is used. Then, the carboxyl group of the unsaturated monobasic acid having an unsaturated ethylenic double bond is subjected to an addition reaction, and the resulting hydroxyl group is reacted with a polybasic acid anhydride to convert the unsaturated ethylenic double bond and the carboxyl group into There is a way to introduce.

  Examples of the unsaturated ethylenic monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, 3,4 epoxybutyl (meth) acrylate, And 3,4 epoxy cyclohexyl (meth) acrylates, and these may be used alone or in combination of two or more. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth) acrylate is preferred.

  Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano substituted products, etc. Monocarboxylic acid etc. are mentioned, These may be used independently or may use 2 or more types together.

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., and these may be used alone or in combination of two or more. It doesn't matter. If necessary, use a tricarboxylic anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride to increase the number of carboxyl groups. The group can also be hydrolyzed. Moreover, when an etrahydrophthalic anhydride or maleic anhydride having an unsaturated ethylenic double bond is used as the polybasic acid anhydride, the number of unsaturated ethylenic double bonds can be increased.

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

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

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

  Examples of the unsaturated ethylenic monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis [(meth) acryloyloxy] ethyl isocyanate, and the like. In addition, two or more types can be used in combination.

(Thermosetting resin)
Examples of the thermosetting resin used for the binder resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, cardo resins, and phenol resins.

The thermosetting resin may be, for example, a low-molecular compound such as an epoxy compound, a benzoguanamine compound, a rosin-modified maleic acid compound, a rosin-modified fumaric acid compound, a melamine compound, a urea compound, a cardo compound, and a phenol compound. It is not limited to this. By including such a thermosetting resin, the resin reacts at the time of firing the filter segment, the cross-linking density of the coating film is increased, the heat resistance is improved, and the effect of suppressing pigment aggregation at the time of firing the filter segment is obtained. It is done.
Among these, an epoxy resin, a cardo resin, or a melamine resin is preferable.

<Organic solvent>
In the coloring composition for a color filter of the present invention, a colorant is sufficiently dissolved in a monomer, a resin and the like, and applied on a substrate such as a glass substrate so as to have a dry film thickness of 0.2 to 5 μm. In order to make it easier to form, a solvent can be included.

  Examples of the organic solvent include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl -1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m -Diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N- Methylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, Ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol Monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol 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, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol mono Ethyl 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, Louis Seo ketone, methyl cyclohexanol, acetic acid n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.

  Among these, since the quinophthalone dye of the present invention has high solvent solubility, a wide variety of solvents from hydrophilic to hydrophobic can be used. Among them, alkyl lactates such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, glycol acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate, and aromatic alcohols such as benzyl alcohol It is preferable to use ketones such as cyclohexanone.

  These organic solvents can be used individually by 1 type or in mixture of 2 or more types. When it is set as 2 or more types of mixed solvents, it is preferable that said preferable organic solvent is contained 65 to 95 weight% in 100 weight part of the whole organic solvent. In particular, propylene glycol monomethyl ether acetate is preferably the main component, and preferably 65 to 100% by weight in all organic solvents.

  Moreover, since the organic solvent can adjust the coloring composition to an appropriate viscosity to form a filter segment having a desired uniform film thickness, the amount of the organic solvent is 500 to 4000 parts by weight with respect to 100 parts by weight of the total weight of the colorant. It is preferable to use in.

<Method for producing colored composition>
The coloring composition for a color filter of the present invention comprises a colorant containing the quinophthalone dye of the present invention in a colorant carrier comprising the resin and, if necessary, a solvent, preferably a dispersion aid such as a dye derivative. It can be produced by finely dispersing together using various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, a kneader, or an attritor. In addition, when the solubility of the quinophthalone dye of the present invention is high, specifically, it is highly soluble in the solvent to be used. There is no need to manufacture.

  The colored composition for a color filter of the present invention can also be produced by mixing pigments, the quinophthalone dye of the present invention, and other 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, and 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.

  In the present invention, the quinophthalone dye of the present invention can also serve as a dispersion aid for the pigment used in combination.

  Examples of the dye derivative include a compound obtained by introducing a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent into an organic pigment, anthraquinone, acridone, or triazine. 63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, etc. can be used. These can be used alone or in combination of two or more.

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

  The resin-type dispersant has a pigment-affinity part having a property of adsorbing to the colorant and a part compatible with the colorant carrier, and adsorbs to the colorant to stabilize dispersion in the colorant carrier. It works. 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 adduct, phosphoric ester or the like is used, they may be used alone or in combination, it is not necessarily limited thereto.

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167 manufactured by Big Chemie Japan. 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164 or Anti -Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, 21116, 21324 or LACTIMON, LACTIMON-WS, BYKUMEN, etc. 3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400 manufactured by Ciba Japan Co., Ltd., 41000, 41090, 53095, 55000, 56000, 76500, etc. , 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 45 0, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc. Etc.

  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 can be used alone or in admixture of two or more, but are not necessarily limited thereto.

  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 colorant. 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 coloring composition for a color filter of the present invention can be used as a photosensitive coloring composition for a color filter by further adding a photopolymerizable monomer and / or a photopolymerization initiator.

<Photopolymerizable monomer>
Photopolymerizable monomers that can be used in the present invention include monomers or oligomers that are cured by ultraviolet rays or heat to produce transparent resins, and these may be used alone or in combination of two or more. Can do. The blending amount of the monomer is preferably 5 to 400 parts by weight with respect to 100 parts by weight of the colorant, 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 transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 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 diglycy Luether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodeca 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 Examples include, but are not necessarily limited to, til (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.

<Photopolymerization initiator>
In the coloring composition for a color filter of the present invention, when the composition is cured by ultraviolet irradiation and a filter segment is formed by a photolithographic method, a photopolymerization initiator or the like is added to add a solvent developing type or an alkali developing type coloring. It can be adjusted in the form of a resist material. The blending amount when using the photopolymerization initiator is preferably 5 to 200 parts by weight with respect to 100 parts by weight of the total amount of the colorant, and 10 to 150 parts by weight from the viewpoint of photocurability and developability. It is more preferable.

  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 Benzoin compounds such as benzyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, or 3,3 ′, Benzophenone compounds such as 4,4′-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone Thioxanthone compounds such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-meth) Cyphenyl) -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-benzoyloxy) )], Or oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6 Phosphine compounds such as trimethylbenzoyl) phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; A carbazole compound; an imidazole compound; or a titanocene compound is used.

  These photopolymerization initiators can be used alone or in combination of two or more at any ratio as required. These photopolymerization initiators are preferably 5 to 200% by weight based on the total amount of the colorant in the color filter coloring composition (100% by weight), and 10 from the viewpoint of photocurability and developability. More preferably, it is -150 weight%.

<Sensitizer>
Furthermore, the coloring composition for a color filter of the present invention can contain a sensitizer. Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapirazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, or Michler's ketone derivatives, biimidazole derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, Camphorquinone, ethylanthraquinone, 4,4'-diethylisophthalophenone, 3,3 'or 4,4'-tetra (t-butylperoxy Carbonyl) benzophenone, 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 parts by weight with respect to 100 parts by weight of the total weight of the photopolymerization initiator contained in the colored composition, and is photocurable and developable. From the viewpoint, it is more preferably 5 to 50 parts by weight.

<Multifunctional thiol>
The coloring composition for a color filter of the present invention can contain a polyfunctional thiol that functions as a chain transfer agent.
The polyfunctional thiol may be a compound having two or more thiol groups. For example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene Glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, Pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercap -s- triazine, 2- (N, N- dibutylamino) -4,6-dimercapto -s- triazine.
These polyfunctional thiols can be used singly or in combination of two or more in any ratio as necessary.

The content of the polyfunctional thiol is preferably 0.1 to 30% by weight, more preferably 1 to 20% by weight based on the weight (100% by weight) of the total solid content of the color filter coloring composition. . If the content of the polyfunctional thiol is less than 0.1% by weight, the effect of adding the polyfunctional thiol is insufficient, and if it exceeds 30% by weight, the sensitivity is too high and the resolution is lowered.

<Antioxidant>
The coloring composition for a color filter of the present invention can contain an antioxidant. Antioxidants are used to prevent the photopolymerization initiators and thermosetting compounds contained in the color filter coloring composition from oxidizing and yellowing due to thermal processes during thermal curing and ITO annealing. Can be high. Therefore, by including an antioxidant, yellowing due to oxidation during the heating step can be prevented, and a high coating film transmittance can be obtained.

  The “antioxidant” in the present invention may be a compound having an ultraviolet absorbing function, a radical scavenging function, or a peroxide decomposing function. Specifically, as an antioxidant, a hindered phenol type, a hindered amine type are used. , Phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylate-based, and triazine-based compounds, and known ultraviolet absorbers, antioxidants, and the like can be used.

  Among these antioxidants, a hindered phenol antioxidant, a hindered amine antioxidant, a phosphorus antioxidant, or a sulfur antioxidant is preferable from the viewpoint of achieving both transmittance and sensitivity of the coating film. Agents. More preferably, they are hindered phenolic antioxidants, hindered amine antioxidants, or phosphorus antioxidants.

  These antioxidants can be used singly or in combination of two or more at any ratio as required.

  When the content of the antioxidant is 0.5 to 5.0% by weight based on the solid content weight of the color filter coloring composition (100% by weight), brightness and sensitivity are more preferable.

<Amine compound>
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.

<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 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. The content of the leveling agent is usually preferably 0.003 to 0.5% by weight in a total of 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 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 components>
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. 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 total amount of the colorant.

  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, based on 100 parts by weight of the total amount of the colorant in the 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 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 comprises at least one red filter segment, at least one green filter segment, and at least one blue filter segment.
The color filter may further comprise a magenta filter segment, a cyan filter segment, and a yellow filter segment, and the yellow filter segment is formed from the colored composition of the present invention. There may be.

  Preferably, at least one green filter segment is formed using the coloring composition for a color filter of the present invention.

The blue filter segment can be formed using a normal blue coloring composition containing a blue pigment and a resin. Examples of the blue coloring composition 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,
A blue pigment such as 79 is used.

  In addition, 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, Purple pigments such as 37, 39, 42, 44, 47, 49, and 50 can be used in combination.

  In addition, a basic dye or a salt-forming compound of an acid dye exhibiting blue or purple can be used. When the dye is used, a triarylmethane dye or a xanthene dye is preferable in terms of lightness.

  As the transparent substrate constituting the color filter, a glass plate such as soda lime glass, low alkali borosilicate glass or non-alkali aluminoborosilicate glass, or a resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, or the like is used. In addition, a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate in order to drive the liquid crystal after forming the panel.

<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 filter segments by printing methods allows patterning by simply printing and drying the colored composition prepared as a printing ink, making it a low cost and excellent mass productivity as a color filter manufacturing method. Yes. 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. Further, it is important to control the fluidity of the ink on the printing press, and the viscosity of the ink can be adjusted with a dispersant or extender pigment.

  When the filter segment is formed by photolithography, the colored composition prepared as a solvent developing type or alkali developing type colored resist material is applied on a transparent substrate by spray coating, spin coating, slit coating, roll coating or the like. By a method, it applies so that a dry film thickness may be set to 0.2-5 micrometers. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. 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 material, 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 material, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Then, ultraviolet exposure can be performed.

  The color filter of the present invention can be produced by an electrodeposition method, a transfer method, an ink jet method or the like in addition to the above method, but the color filter coloring 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.

  The color filter is bonded to the counter substrate using a sealant, and after injecting liquid crystal from the injection port provided in the seal part, the injection port is sealed, and if necessary, a polarizing film or a retardation film is placed outside the substrate. A liquid crystal display panel is manufactured by bonding.

  Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically convented bend (OCB). It can be used in a liquid crystal display mode in which colorization is performed using a color filter such as the above.

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

<Method for producing quinophthalone dye>
Example 1 (Production of quinophthalone dye 1)

Reaction formula of quinophthalone dye 1

(Synthesis of Compound (A))
Trimellitic anhydride 5.0 parts, bromopropane 5.3 parts, sodium hydroxide 1.2 parts and N, N-dimethylacetamide 20 parts were mixed and stirred at 100 ° C. for 5 hours. After allowing to cool, 100 parts of toluene and 100 parts of ion-exchanged water were added and extracted. Further, the extracted toluene layer was washed twice with 100 parts of ion exchange water. Then, 10 parts of magnesium sulfate (anhydride) was added to the obtained toluene layer and dehydrated by stirring at room temperature for 30 minutes. Then, 5.8 parts of compounds (A) were obtained by filtering off magnesium sulfate by suction filtration and concentrating the obtained toluene layer. The yield was 95.0%.

(Synthesis of quinophthalone dye 1)
5.0 parts of 8-butoxy-2-methylquinoline, 5.1 parts of compound (A) and 30 parts of benzoic acid were mixed and stirred at 180 ° C. for 5 hours. After allowing to cool, 100 parts of methanol was added and stirred for 1 h. The precipitated solid was collected by suction filtration. Further, the solid was put into 200 parts of methanol, stirred for 1 hour, and then collected by suction filtration. Drying overnight in a vacuum dryer (40 ° C.) gave 8.2 parts of product. The yield was 82.0%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 431 (molecular weight 431.5).

Example 2 (Production of quinophthalone dye 2)

Reaction formula of quinophthalone dye 2

(Synthesis of Compound (B))
16.5 parts of 8-hydroxy-2-methylquinoline, 20.0 parts of trimellitic anhydride, and 60 parts of benzoic acid were mixed and stirred at 180 ° C. for 5 hours. After allowing to cool, 300 parts of methanol was added and stirred for 1 h. The precipitated solid was collected by suction filtration. Further, the solid was put into 500 parts of methanol and stirred for 1 hour, and then the solid was collected by suction filtration. It dried overnight with the vacuum dryer (40 degreeC), and obtained 31.9 parts of compounds (B). The yield was 92.0%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 333 (molecular weight 333.3).

(Synthesis of quinophthalone dye 2)
Compound (B) 5.0 parts, 1-bromo-2-ethylhexane 13.7 parts, sodium hydroxide 1.3 parts and N, N-dimethylacetamide 30 parts were mixed and stirred at 100 ° C. for 5 hours. After allowing to cool, 100 parts of chloroform and 100 parts of ion-exchanged water were added and extracted. Furthermore, the extracted chloroform layer was washed twice with 100 parts of ion exchange water. Then, 10 parts of magnesium sulfate (anhydride) was added to the resulting chloroform layer and dehydrated by stirring at room temperature for 30 minutes. Thereafter, magnesium sulfate was filtered off by suction filtration, and the obtained chloroform layer was concentrated and dried overnight in a vacuum dryer (40 ° C.) to obtain 6.8 parts of quinophthalone dye 2. The yield was 81.2%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 557 (molecular weight 557.3).

Example 3 (Production of quinophthalone dye 3)

Reaction formula of quinophthalone dye 3

(Synthesis of quinophthalone dye 3)
5.0 parts of 8- (2-ethoxyethoxy) -2-methylquinoline, 5.1 parts of compound (A) and 30 parts of benzoic acid were mixed and stirred at 180 ° C. for 5 hours. After allowing to cool, 100 parts of methanol was added and stirred for 1 h. The precipitated solid was collected by suction filtration. Further, the solid was put into 200 parts of methanol, stirred for 1 hour, and then collected by suction filtration. Drying overnight in a vacuum dryer (40 ° C.) gave 7.3 parts of product. The yield was 75.5%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 447 (molecular weight 447.5).

Example 4 (Production of quinophthalone dye 4)

Reaction formula of quinophthalone dye 4

(Synthesis of Compound (C))
Trimellitic anhydride 5.0 parts, 1-bromo-2-ethylhexane 5.0 parts, sodium hydroxide 1.6 parts and N, N-dimethylacetamide 20 parts were mixed and stirred at 100 ° C. for 5 hours. . After allowing to cool, 100 parts of toluene and 100 parts of ion-exchanged water were added and extracted. Further, the extracted toluene layer was washed twice with 100 parts of ion exchange water. Then, 10 parts of magnesium sulfate (anhydride) was added to the obtained toluene layer and dehydrated by stirring at room temperature for 30 minutes. Then, magnesium sulfate was separated by suction filtration, and the obtained toluene layer was concentrated to obtain 7.9 parts of compound (C). The yield was 97.3%.

(Synthesis of quinophthalone dye 4)
10.0 parts of 2-ethylhexyl-5- (2-methylquinolin-8-yloxy) pentanoate, 8.2 parts of compound (C) and 30 parts of benzoic acid were mixed and stirred at 180 ° C. for 5 hours. After allowing to cool, 100 parts of methanol was added and stirred for 1 h. The precipitated solid was collected by suction filtration. Further, the solid was put into 200 parts of methanol, stirred for 1 hour, and then collected by suction filtration. Drying overnight in a vacuum dryer (40 ° C.) gave 15.2 parts of product. The yield was 85.6%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 657 (molecular weight 657.8).

Example 5 (Production of quinophthalone dye 5)

Reaction formula of quinophthalone dye 5

(Synthesis of quinophthalone dye 5)
Compound (B) 5.0 parts, 2-ethylhexyl-4-bromobutanoate 10.5 parts, sodium hydroxide 1.3 parts and N, N-dimethylacetamide 30 parts are mixed and stirred at 100 ° C. for 5 hours. did. After allowing to cool, 100 parts of chloroform and 100 parts of ion-exchanged water were added and extracted. Furthermore, the extracted chloroform layer was washed twice with 100 parts of ion exchange water. Then, 10 parts of magnesium sulfate (anhydride) was added to the resulting chloroform layer and dehydrated by stirring at room temperature for 30 minutes. Thereafter, magnesium sulfate was filtered off by suction filtration, and the resulting chloroform layer was concentrated and dried overnight in a vacuum dryer (40 ° C.) to obtain 10.1 parts of quinophthalone dye 5. The yield was 91.3%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 729 (molecular weight 729.9).

Example 6 (Production of quinophthalone dye 6)

(Synthesis of quinophthalone dye 6)
Compound (B) (5.0 parts), 2-ethylhexyl-4-bromopentanoate (12.5 parts), sodium hydroxide (1.3 parts) and N, N-dimethylacetamide (30 parts) were mixed and stirred at 100 ° C. for 5 hours. did. After allowing to cool, 100 parts of chloroform and 100 parts of ion-exchanged water were added and extracted. Furthermore, the extracted chloroform layer was washed twice with 100 parts of ion exchange water. Then, 10 parts of magnesium sulfate (anhydride) was added to the resulting chloroform layer and dehydrated by stirring at room temperature for 30 minutes. Thereafter, magnesium sulfate was filtered off by suction filtration, and the resulting chloroform layer was concentrated and dried overnight in a vacuum dryer (40 ° C.) to obtain 10.5 parts of quinophthalone dye 6. The yield was 92.3%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 757 (molecular weight 758.0).

Example 7 (Production of quinophthalone dye 7)

(Synthesis of quinophthalone dye 7)
Compound (B) 5.0 parts, 2-ethylhexyl-2-bromobutanoate 11.8 parts, sodium hydroxide 1.3 parts and N, N-dimethylacetamide 30 parts are mixed and stirred at 100 ° C. for 5 hours. did. After allowing to cool, 100 parts of chloroform and 100 parts of ion-exchanged water were added and extracted. Furthermore, the extracted chloroform layer was washed twice with 100 parts of ion exchange water. Then, 10 parts of magnesium sulfate (anhydride) was added to the resulting chloroform layer and dehydrated by stirring at room temperature for 30 minutes. Then, magnesium sulfate was separated by suction filtration, and the obtained chloroform layer was concentrated and dried overnight in a vacuum dryer (40 ° C.) to obtain 8.5 parts of quinophthalone dye 7. The yield was 77.6%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 729 (molecular weight 729.9).

Example 8 (Production of quinophthalone dye 8)

(Synthesis of quinophthalone dye 8)
Compound (B) (5.0 parts), 2-ethylhexyl-2-bromohexanoate (12.5 parts), sodium hydroxide (1.3 parts) and N, N-dimethylacetamide (30 parts) were mixed and stirred at 100 ° C. for 5 hours. did. After allowing to cool, 100 parts of chloroform and 100 parts of ion-exchanged water were added and extracted. Furthermore, the extracted chloroform layer was washed twice with 100 parts of ion exchange water. Then, 10 parts of magnesium sulfate (anhydride) was added to the resulting chloroform layer and dehydrated by stirring at room temperature for 30 minutes. Thereafter, magnesium sulfate was filtered off by suction filtration, and the resulting chloroform layer was concentrated and dried overnight in a vacuum dryer (40 ° C.) to obtain 7.5 parts of quinophthalone dye 8. The yield was 63.6%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 785 (molecular weight 786.0).

Example 9 (Production of quinophthalone dye 9)

(Synthesis of quinophthalone dye 9)
Compound (B) 5.0 parts, butyl-2-bromohexanoate 10.1 parts, sodium hydroxide 1.3 parts, and N, N-dimethylacetamide 30 parts were mixed and stirred at 100 ° C. for 5 hours. After allowing to cool, 100 parts of chloroform and 100 parts of ion-exchanged water were added and extracted. Furthermore, the extracted chloroform layer was washed twice with 100 parts of ion exchange water. Then, 10 parts of magnesium sulfate (anhydride) was added to the resulting chloroform layer and dehydrated by stirring at room temperature for 30 minutes. Thereafter, magnesium sulfate was filtered off by suction filtration, and the resulting chloroform layer was concentrated and dried overnight in a vacuum dryer (40 ° C.) to obtain 8.2 parts of quinophthalone dye 9. The yield was 81.1%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 673 (molecular weight 673.8).

Example 10 (Production of quinophthalone dye 10)

(Synthesis of quinophthalone dye 10)
Compound (B) 5.0 parts, 2- (2- (2-ethylhexyloxy) ethoxy) ethyl-5-bromopentanoate 15.1 parts, sodium hydroxide 1.3 parts, N, N-dimethylacetamide 30 The parts were mixed and stirred at 100 ° C. for 5 hours. After allowing to cool, 100 parts of chloroform and 100 parts of ion-exchanged water were added and extracted. Furthermore, the extracted chloroform layer was washed twice with 100 parts of ion exchange water. Then, 10 parts of magnesium sulfate (anhydride) was added to the resulting chloroform layer and dehydrated by stirring at room temperature for 30 minutes. Then, magnesium sulfate was separated by suction filtration, and the resulting chloroform layer was concentrated and dried overnight in a vacuum dryer (40 ° C.) to obtain 8.0 parts of quinophthalone dye 10. The yield was 57.1%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 933 (molecular weight 934.0).

Example 11 (Production of quinophthalone dye 11)

(Synthesis of quinophthalone dye 11)
Compound (B) 5.0 parts, 2- (2- (2-ethylhexyloxy) ethoxy) ethyl-2-bromobutanoate 14.8 parts, sodium hydroxide 1.3 parts, N, N-dimethylacetamide 30 The parts were mixed and stirred at 100 ° C. for 5 hours. After allowing to cool, 100 parts of chloroform and 100 parts of ion-exchanged water were added and extracted. Furthermore, the extracted chloroform layer was washed twice with 100 parts of ion exchange water. Then, 10 parts of magnesium sulfate (anhydride) was added to the resulting chloroform layer and dehydrated by stirring at room temperature for 30 minutes. Thereafter, magnesium sulfate was removed by suction filtration, and the resulting chloroform layer was concentrated and dried overnight in a vacuum dryer (40 ° C.) to obtain 8.5 parts of quinophthalone dye 11. The yield was 62.5%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 905 (molecular weight 906.1).

Example 12 (Production of quinophthalone dye 12)

(Synthesis of quinophthalone dye 12)
2-ethylhexyl-5- (2-methylquinolin-8-yloxy) pentanoate 5.0 parts, 6.9 parts of 4- (2-phenoxyethoxycarbonyl) phthalic anhydride and 30 parts of benzoic acid were mixed and mixed at 200 ° C. Stir for 5 hours. After allowing to cool, 100 parts of methanol was added and stirred for 1 h. The precipitated solid was collected by suction filtration. Further, the solid was put into 200 parts of methanol, stirred for 1 hour, and then collected by suction filtration. Drying overnight in a vacuum dryer (40 ° C.) gave 6.6 parts of product. The yield was 73%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 666 (molecular weight 665.77).

Example 13 (Production of quinophthalone dye 13)

Bis (2-ethylhexyl) 4-hydroxy-5- (2-methylquinolin-8-yloxy) cyclohexane-1,2-dicarboxylic acid 5.0 parts and 4- (methoxycarbonyl) phthalic anhydride 3.4 parts, benzoic acid 30 parts of the acid was mixed and stirred at 200 ° C. for 5 hours. After allowing to cool, 100 parts of methanol was added and stirred for 1 hour. The precipitated solid was collected by suction filtration. Further, the solid was put into 200 parts of methanol, stirred for 1 hour, and then collected by suction filtration. Drying overnight in a vacuum dryer (40 ° C.) gave 6.2 parts of product. The yield was 70%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 757 (molecular weight 757.91), which confirmed the intended product.

Comparative Example 1 (quinophthalone dye 14)

  The synthesis was carried out based on the synthesis method of dye (IV) described in JP-A-6-009891.

Comparative Example 2 (Quinophthalone Dye 15)

  A dye specific example 97 of JP-A-2006-91768 was synthesized based on Synthesis Example 5.

Comparative Example 3 (Quinophthalone Dye 16)

Disperse Yellow 54 was used.

Comparative Example 4 (Quinophthalone Dye 17)

Disperse Yellow 64 was used.

<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 an RI detector (manufactured by Tosoh Corporation, HLC-8120GPC) using THF as a developing solvent. The weight average molecular weight (Mw) in terms of polystyrene.

<Pigment production method>
(Preparation of blue pigment 1)
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 (“LIONOL BLUE ES” manufactured by Toyo Ink Manufacturing Co., Ltd.) 200 parts, sodium chloride 1400 parts, and diethylene glycol 360 parts were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. did. 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 blue pigment 1 were obtained. The average primary particle diameter of the obtained pigment was 79 nm.

(Preparation of purple pigment 1)
Dioxazine-based purple pigment C.I. I. 200 parts of Pigment Violet 23 (“LIONOGEN VIOLET RL” 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 violet pigment 1 were obtained. The average primary particle diameter of the obtained pigment was 28 nm.

(Preparation of green pigment 1)
Phthalocyanine green pigment C.I. I. Pigment Green 58 (“FASTGEN GREEN A110” manufactured by DIC Corporation) was used as it was on the market. The average primary particle diameter of the green pigment 1 was 22 nm.

(Preparation of yellow pigment 1)
Quinophthalone yellow pigment C.I. I. 270 parts of Pigment Yellow 138 (trade name Paliotor Yellow K0961HD, manufactured by BASF), 1350 parts of sodium chloride, and 500 parts of diethylene glycol were charged into a stainless 1 gallon kneader (Inoue Seisakusho) and kneaded at 120 ° 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. 250 parts of yellow pigment 3 were obtained. The average primary particle diameter of the obtained pigment was 36 nm.

(Preparation of yellow pigment 2)
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 120 ° 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 yellow pigment 2 were obtained. The obtained pigment had a volume average primary particle size of 67 nm.

(Preparation of yellow pigment 3)
Isoindoline yellow pigment C.I. I. Pigment Yellow 139 (“Irgafore Yellow 2R-CF” manufactured by Ciba Japan), 500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C. for 8 hours. did. Next, this kneaded product is poured into 5 liters of warm water, stirred for 1 hour 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. 490 parts of Yellow Pigment 1 were obtained. The average primary particle diameter of the obtained pigment was 92 nm.

(Preparation of red pigment 1)
Anthraquinone red pigment C.I. I. 200 parts of Pigment Red 177 (“Chromophthalred A2B” manufactured by Ciba Japan Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of red pigment 1 were obtained. The average primary particle diameter of the obtained pigment was 54 nm.

A colored composition Q-1 was obtained by preparing a dye solution having the following composition.
Quinophthalone dye 1: 11.0 parts Acrylic resin solution prepared previously: 40.0 parts Cyclohexanone: 48.0 parts

Hereinafter, colored compositions Q-2 to 13 were produced in the same manner as colored composition Q-1, except that quinophthalone dye 1 was replaced with the quinophthalone dye shown in Table 3.

  The following evaluation was implemented about the obtained coloring compositions Q-1 to 13, and the results are shown in Table 3.

<Coating foreign matter test of colored compositions Q-1 to 13>
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.
A: Less than 5 ○: 5 or more, less than 20 Δ: 20 or more, less than 100 ×: 100 or less, Table 3 shows the results.

<The heat resistance test of coloring composition Q-1-13>
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. Then, as a heat resistance test, it was heated in an oven at 250 ° C. for 1 hour, and chromaticity 2 (L * (2), a * (2), b * (2)) with a C light source was measured.
Using the measured color difference value, the color difference ΔEab * was calculated by the following formula, and the heat resistance of the coating film was evaluated in the following four stages. Moreover, if evaluation is more than (circle), it is a level which is satisfactory practically.
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 5.0 ×: ΔEab * is 5.0 or more Table 3 shows the results.

<Spectroscopic evaluation of coloring composition Q-1-13>
A coating film is prepared on a transparent substrate so that the transmittance at a wavelength of 450 nm is 5%, and the transmittance value at 550 nm at that time is shown. The higher the transmittance at 550 nm, the better the brightness. In the following evaluation results, the transmittance at 550 nm when the quinophthalone dye and the yellow pigment are standardized is as follows: ○ is 99% or more, Δ is 97 or more and less than 99%, and × is less than 97%. It is preferable that it is 99% or more because the brightness becomes high.
The results are shown in Table 3 below.

<Presence / absence of dispersion step of colored compositions Q-1 to 13>
About the presence or absence of the dispersion | distribution process at the time of producing Examples 14-26, Comparative Examples 5-8, DP-4-6, the result is shown in Table 3 below.

The following mixture was stirred and mixed so as to be uniform, 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 colored composition Q-14 was produced by filtration using a filter.
Quinophthalone dye 14: 11.0 parts The previously prepared acrylic resin solution: 40.0 parts Cyclohexanone: 48.0 parts

  Hereinafter, colored compositions Q-15 to 17 were produced in the same manner as colored composition Q-14, except that quinophthalone dye 14 was replaced with the quinophthalone dye shown in Table 3.

  The obtained colored compositions Q-14 to 17 were evaluated in the same manner as the colored compositions Q-1 to 13, and the results are shown in Table 3.

(Preparation of colored composition DP-1)
The following mixture was stirred and mixed so as to be uniform, 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 colored composition (DP-1) was produced by filtration using a filter.
Blue Pigment 1 (CI Pigment Blue 15: 6): 11.0 parts previously prepared acrylic resin solution: 40.0 parts propylene glycol monomethyl ether acetate (PGMAC): 48.0 parts Resin-type dispersant (Ciba・ "EFKA4300" manufactured by Japan Co., Ltd.): 1.0 part

(Preparation of colored compositions DP-2 to 7)
Hereinafter, colored compositions DP-2 to 7 were produced in the same manner as colored composition DP-1, except that blue pigment 1 was replaced with the pigment shown in Table 2.

Table 2

Table 3

  In Examples 14 to 26, there were few coating film foreign matters, and good results were obtained. Among them, Examples 17 to 26 were particularly excellent because there were very few foreign substances on the coating film.

And regarding heat resistance, Examples 14-26 showed the favorable result compared with the comparative dye (Comparative Examples 5-8). Among them, in particular, Examples 17 to 26 had very high heat resistance, and showed the same results as the pigments of Comparative Examples 9 to 11.

In Examples 14 to 26, the transmittance at 550 nm is good, and the existing pigments C.I. I. Compared with Pigment Yellow 138 (Comparative Example 9), it showed a spectral shape that could expect the same or better color characteristics.

  In Examples 14 to 26, since quinophthalone dyes 1 to 13 having very high solvent solubility are used as the colorant, it is possible to obtain the colored compositions Q1 to 13 without a dispersion step. On the other hand, a dispersion process is indispensable for dyes (Comparative Examples 5 to 8) and pigments (Comparative Examples 9 to 11) that have insufficient solvent solubility.

<Method for producing blue resist material>
The following mixture was stirred and mixed to be uniform and then filtered through a 1.0 μm filter to obtain a blue resist material B-1.
Colored composition (DP-1): 48.0 parts Colored composition (DP-2): 12.0 parts previously prepared 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): 1.2 parts sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts propylene glycol monomethyl ether acetate (PGMAC): 23 .2 parts

[Example 27]
<Adjustment of resist material G-1>
The following mixture was stirred and mixed to be uniform and then filtered through a 1.0 μm filter to obtain a green resist material (G-1).
Colored composition (DP-3): 12.0 parts Colored composition (Q-1): 48.0 parts previously prepared 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 propylene glycol monomethyl ether acetate (PGMAC): 23 .2 parts

[Examples 28 to 45, Comparative Examples 12 to 18]
<Adjustment of resist materials G-2 to 18, R-1 to 4, Y-1 to 4>
Hereinafter, the resist materials G-2 to 18, R-1 to 4, Y-1 to Y are similar to the resist material G-1, except that the types and blending amounts of the colored compositions are changed as shown in Tables 4 and 5. 4 was obtained.

Table 4

Table 5

<Evaluation of resist material> Color characteristics (Y: brightness) of coating films of the obtained resist materials G-1 to 18, R-1 to 4, and Y-1 to 4, coating film foreign matter, heat resistance, light resistance, Each test of solvent resistance and contrast ratio evaluation were performed by the following methods. The test results are shown in Tables 6 and 7.

<Color characteristics (Y: brightness)>
On a glass substrate, in a C light source, the resist materials G-1 to 18 were coated with a resist material having a thickness such that x = 0.264 and y = 0.600, and this substrate was heated at 230 ° C. for 20 minutes. . Resist materials R-1 to 4 were coated with a resist material in such a thickness that x = 0.340 and y = 0.640, and this substrate was heated at 230 ° C. for 20 minutes. The resist material Y-1 to 4 was coated with a resist material so that x = 0.440 and y = 0.506, and the substrate was heated at 230 ° C. for 20 minutes. Thereafter, the brightness (Y) of the obtained substrate was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.).
The results are shown in Tables 6 and 7 below.

<Coating foreign matter test>
A resist material was applied on the transparent substrate so that the dried coating film became about 2.5 μm, and the whole surface was exposed to ultraviolet light, and then heated in an oven at 230 ° C. for 20 minutes and allowed to cool to obtain an evaluation substrate. The evaluation was performed by observing the surface using a metal microscope “BX60” manufactured by Olympus System. The magnification is 500 times, and the number of particles that can be confirmed in any five visual fields 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 due to the foreign matters.
未 満: Less than 5 ○: 5 or more, less than 20 Δ: 20 or more, less than 100 ×: 100 or more, Tables 6 and 7 show the results.

<Film heat resistance test>
A resist material is applied on a transparent substrate so that the dry coating thickness is about 2.5 μm, and after UV exposure through a mask having a predetermined pattern, an alkali developer is sprayed to remove uncured parts. Thus, a desired pattern was formed. Then, after heating in an oven at 230 ° C. for 20 minutes and allowing to cool, the chromaticity 1 (L * (1), a * (1), b * (1)) of the obtained coating film with a C light source is microspectrophotometric. Measurement was performed using a meter (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.). Further, as a heat resistance test, it was heated in an oven at 250 ° C. for 1 hour, and chromaticity 2 (L * (2), a * (2), b * (2)) with a C light source was measured.
Using the measured color difference value, the color difference ΔEab * was calculated by the following formula, and the heat resistance of the coating film was evaluated in the following four stages. Moreover, if evaluation is more than (circle), it is a level which is satisfactory practically.
ΔEab * = √ ((L * (2)-L * (1)) 2+ (a * (2)-a * (1)) 2+ (b * (2)-b * (1)) 2)
A: ΔEab * is less than 1.5 ○: ΔEab * is 1.5 or more and less than 5.0 ×: ΔEab * is 5.0 or more Tables 6 and 7 show the results.

<Coating light resistance test>
A test substrate was prepared in the same procedure as the coating heat resistance test, and the chromaticity 1 (L * (1), a * (1), b * (1)) with a C light source was measured with a microspectrophotometer (Olympus Optics) It measured using "OSP-SP200" by a company. Thereafter, the substrate was placed in a light resistance tester (“SUNTSTCPS +” manufactured by TOYOSEIKI) and left for 500 hours. After removing the substrate, measure chromaticity 2 (L * (2), a * (2), b * (2)) with a C light source, and calculate the color difference ΔEab * in the same manner as the coating film heat resistance test. Then, the light resistance of the coating film was evaluated according to the same criteria as heat resistance.
The results are shown in Tables 6 and 7 below.

<Film resistance test>
A test substrate is prepared in the same procedure as the heat resistance test, and the chromaticity 1 (L * (1), a * (1), b * (1)) with a C light source is measured with a microspectrophotometer (manufactured by Olympus Optical Co., Ltd.) It measured using "OSP-SP200"). Thereafter, the substrate was immersed in N-methylpyrrolidone for 30 minutes. After removing the substrate, measure chromaticity 2 (L * (2), a * (2), b * (2)) with a C light source, and calculate the color difference ΔEab * in the same manner as the coating film heat resistance test. Then, the solvent resistance of the coating film was evaluated according to the same criteria as the heat resistance.
The results are shown in Tables 6 and 7 below.

<Contrast ratio test>
The obtained resist material was applied onto a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater, then dried at 70 ° C. for 20 minutes and allowed to cool to prepare a coating film substrate. . The initial contrast ratio (initial CR) of the obtained coated substrate was measured.
The results are shown in Tables 6 and 7 below.

Table 6

Table 7

In Examples 27 to 39, color unevenness was suppressed to the maximum in order to exhibit high solvent solubility, and good results were shown. Among them, Examples 30 to 39 show very good results. Moreover, also about heat resistance, Example 27-39 has shown the favorable result. Among them, Examples 30 to 39 using the quinophthalone dyes 4 to 13 having a plurality of ester bonds show very good heat resistance. Regarding lightness (Y), Examples 27 to 39 showed higher lightness than the comparative dye resist materials (Comparative Examples 12 to 15). I. The brightness is equal to or higher than that of Pigment Yellow 138 (Comparative Example 16). Regarding the contrast ratio, Examples 27 to 39 showed higher values than the pigment, and the merit of using the dye was confirmed. Examples 27 to 39 show good results in light resistance and solvent resistance.
From these results, it can be said that Examples 27 to 39 are resist materials having fastness equivalent to that of pigments, good lightness, and excellent contrast ratio.

  Since the same results as described above were obtained for the red and yellow resist materials, the quinophthalone dye developed this time can also be used for the red and yellow resist materials.

[Example 46 ]
<Color filter (CF-1)>
A black matrix is patterned on a glass substrate, and a red resist material (R-1) is applied on the substrate with a spin coater to a film thickness such that x = 0.640, y = 0.340. A colored coating was formed. The film was irradiated with ultraviolet rays of 300 mJ / cm @ 2 using a super high pressure mercury lamp through a photomask. 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 (G-1) is formed to a thickness such that x = 0.264 and y = 0.600, and x = 0.150 using the blue resist material (B-1). 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 color display device was produced on the other surface of this glass substrate in combination with a three-wavelength CCFL light source of a polarizing plate. Formed. 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 47 and 48 , Comparative Examples 19 and 20]
(Color filter (CF-2 ~ 6)
Hereinafter, the color filters (CF-2 to CF-2) of Examples 47 and 48 and Comparative Examples 19 and 20 were combined with the resist material shown in Table 8 and a three-wavelength CCFL light source by the same method as the production of the color filter (CF-1). 6) and a color display device were produced.

Thereafter, in the obtained color display device, a light source was emitted to display a color image, and the brightness (Y) 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 8.

Table 8

Examples 46 and 47 and Comparative Example 19 were compared to show the same brightness. This is because the resistance of the quinophthalone dye developed this time is very high. A color filter can be produced by the same process as when using a pigment, and since it is a highly resistant dye, there is no change in the color characteristics after the color filter is produced. Therefore, it can be said that the stability at the time of creating the color filter is high. The same applies to Example 48 as compared to Comparative Example 20.

  From the above results, it can be said that by using the quinophthalone coloring matter of the present invention and a coloring composition containing the same, it is possible to create a color filter having a stable color characteristic using a dye.

Claims (5)

A quinophthalone dye represented by the following general formula (1):
General formula (1)

(In the formula, R ₁ has 2 to 30 carbon atoms and contains at least one bond selected from an ester bond (—COO—) and an ether bond (—O—)). , Monocyclic or condensed polycyclic alkyl groups.
Wherein, R ₂ to R ₅ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl groups, it was or represents -COO-R _6.
R ₆ is a substituted or unsubstituted alkyl group .
However, at least one of R _{2 to} R ₅ represents —COO—R ₆ . )   A color filter dye comprising the quinophthalone dye according to claim 1.   A color filter coloring composition comprising at least a colorant and a binder resin, wherein the colorant comprises the color filter pigment according to claim 2.   Furthermore, a coloring agent contains a pigment, The coloring composition for color filters of Claim 3 characterized by the above-mentioned. A color filter comprising at least a red filter segment, a green filter segment, and a blue filter segment, wherein at least one filter segment is formed by the color filter coloring composition according to claim 3 or 4.