JP5866787B2 - Blue coloring composition for color filter, and color filter - Google Patents

Description

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

  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, and a type using a twisted nematic (TN) type liquid crystal is mainly used. The liquid crystal display device can perform color display by providing a color filter between two polarizing plates. Therefore, liquid crystal display devices are being developed for use in televisions and personal computer monitors.

  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, the color filter is a red filter layer (R), green filter layer (G) and blue filter layer (B) formed on the surface of a transparent substrate such as glass, or a complementary color of red, green and blue. Corresponding fine band (striped) filter segments (pixels) composed of a cyan filter layer (C), a magenta filter layer (M), and a yellow color filter layer (Y) are arranged in parallel or crossing each other. Or fine filter segments 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.

  On the color filter used in the color liquid crystal display device, a transparent electrode for driving the liquid crystal is generally formed by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is formed thereon. Has been. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, it is necessary to perform the formation process at a high temperature of generally 200 ° C. or higher, preferably 230 ° C. or higher.

  Quality items required for the color filter include brightness and contrast ratio. When a color filter with a low contrast ratio is used, the degree of polarization controlled by the liquid crystal is disturbed, and when light must be blocked (OFF state), light must leak or be transmitted (ON) In other words, the transmitted light is attenuated in the state), resulting in a blurred screen. Therefore, in order to realize a high-quality liquid crystal display device, high contrast is indispensable.

  If 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 as 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. Furthermore, as described above, since the color liquid crystal device has been used for televisions, personal computer monitors, and the like, the demand for high reliability and high lightness and contrast for color filters has also increased.

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

  In general, the pigment particles are subjected to a micronization treatment and a pigment dispersion in which the micronized pigment is brought close to the primary particles as much as possible is used to suppress light scattering by the pigment and achieve high contrast. In addition, since the transparency of the dispersion is improved, the spectral spectrum of the dispersion has high transmittance, and high brightness is realized. By using this dispersion as a color resist, a color filter having high contrast and high brightness can be obtained.

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

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

  In order to solve the above problems, a technique has been proposed in which a dye, not a pigment, is dissolved as a colorant in a resin or the like (see, for example, Patent Document 1).

  Further, as a colorant used for a blue filter segment or a cyan filter segment, it has been proposed to use a triarylmethane dye, particularly a triarylmethane dye, as a color filter colorant (see, for example, Patent Document 2). Dyes have a problem that they are inferior in heat resistance, light resistance, and solvent resistance as compared with pigments.

  On the other hand, xanthene dyes are known as dyes exhibiting magenta color. Among them, xanthene dyes have excellent spectral characteristics and are therefore often used for magenta color filters (for example, patents). Reference 3).

In addition, since the spectrum of xanthene dyes has a high transmittance in the vicinity of 400 to 450 nm when compared with copper phthalocyanine pigments and cyanine pigments, a blue color filter was prepared in combination with the above pigments and other blue pigments. In this case, it has been proposed that a blue color filter with higher brightness that does not disturb the color balance can be obtained. (For example, see Patent Documents 4 and 5)
However, because of the high solubility of the dye, it was expected that a color filter with a high contrast ratio could be obtained without the occurrence of scattering, etc. as seen when using only pigments. When a fluorescent dye is used, there is a problem that the contrast ratio is low (see, for example, Patent Document 6), and a color filter capable of achieving both high brightness and high contrast ratio has not been realized. It was.

JP-A-6-75375 JP 2001-81348 A JP 2005-292305 A JP 2009-265641 A JP 2010-32999 A JP 2005-025175 A

  An object of the present invention is to provide a blue coloring composition for a color filter having high brightness, a high contrast ratio and excellent heat resistance, and a color filter using the same and having high brightness, high contrast ratio and excellent heat resistance. .

  As a result of intensive studies to solve the above problems, the present inventors have used a blue pigment and a xanthene dye as a colorant in a blue coloring composition for a color filter, and further an amine compound of phthalocyanine. It was found that when a color filter was added, it was possible to achieve high brightness, a wide color reproduction region, and a high contrast ratio, and it was also excellent in heat resistance. It was made.

  That is, the present invention provides a color filter comprising a colorant (A) containing a blue pigment [A1] and a xanthene dye [A2], a resin (B), and an amine compound (C) of phthalocyanine. The present invention relates to a blue coloring composition.

The present invention also relates to the blue coloring composition for a color filter, wherein the amine compound (C) of phthalocyanine has a structure represented by the following general formula (1).
General formula (1)
P-Lm
[In General Formula (1), P is an m-valent phthalocyanine pigment residue, m is an integer of 1 to 4, and L is General Formula (2), (3), or (4) Any of the substituents selected from the group shown. ]
General formula (2):

  General formula (3):

  General formula (4):

[In the general formulas (2) to (4), X represents —SO ₂ —, —CO—, —CH ₂ —,
_{-CH 2 NHCOCH 2 -, - CH} 2 NHSO 2 CH 2 -, or a direct bond,
Y ⁰ is —NH—, —O—, or a direct bond;
n is an integer of 1 to 10,
Y ¹ is —NH—, —NR ⁹ —Z—NR ¹⁰ —, or a direct bond;
R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 36 carbon atoms, an alkenyl group having 2 to 36 carbon atoms, or a phenyl group,
Z represents an alkylene group having 1 to 20 carbon atoms or an arylene group having 1 to 20 carbon atoms.

R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or a combination of R ¹ and R ² with further nitrogen, oxygen Or a heterocycle containing a sulfur atom,
R ³ , R ⁴ , R ⁵ , and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms. ,
R ⁷ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms,
R ⁸ is a substituent represented by the general formula (2) or a substituent represented by the general formula (3),
Q represents a hydroxyl group, an alkoxyl group having 1 to 20 carbon atoms, a substituent represented by the general formula (2), or a substituent represented by the general formula (3). ]
Further, the present invention provides the blue color filter according to the above, wherein the weight ratio (C / [A2]) of the xanthene dye [A2] and the amine compound (C) of phthalocyanine is 0.3 to 1.5. The present invention relates to a coloring composition.

  The present invention also relates to the blue coloring composition for a color filter, wherein the blue pigment [A1] is a copper phthalocyanine pigment.

  The present invention also relates to the blue coloring composition for a color filter, wherein the xanthene dye [A2] is a salt forming compound of a xanthene acid dye and / or a sulfonic acid amide compound of a xanthene acid dye.

  The present invention also relates to the blue coloring composition for a color filter, wherein the xanthene dye [A2] is a rhodamine dye.

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

  In this invention, the blue coloring composition for color filters containing the coloring agent (A) containing blue pigment [A1] and xanthene dye [A2], resin (B), and the phthalocyanine amine compound (C) is used. By using a color filter formed by the above method, a color image display device having excellent heat resistance and light resistance, high brightness, a wide color reproduction region, and a high contrast ratio by suppressing the generation of fluorescence is obtained. I can do it. The blue coloring composition for a color filter of the present invention is particularly preferably used for a blue color filter.

  The transmittance spectrum of a blue coloring composition for a color filter that is a combination of a copper phthalocyanine blue pigment and a dioxazine pigment used in a conventional blue color filter has a peak position near 450 nm and a short wavelength of 450 nm or less. On the side, the transmittance decreases rapidly.

  On the other hand, the blue coloring composition for a color filter of the present invention suppresses the fluorescence emitted in the region of 550 to 650 nm, and maintains a high transmittance even on the short wavelength side where the transmission spectrum is 450 nm or less. At the same time, the transmittance at 450 nm is higher than that of copper phthalocyanine blue pigment and dioxazine pigment, so it is effective when a cold cathode tube having a peak near 425 to 440 nm or an LED having a peak near 450 nm is a backlight. It is possible to obtain high brightness and high contrast ratio.

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

Hereinafter, the present invention will be described in detail. The blue coloring composition for a color filter of the present invention comprises a colorant (A) containing a blue pigment [A1] and a xanthene dye [A2], a resin (B), an amine compound of phthalocyanine, preferably copper phthalocyanine. And an amine compound (C).
<< Colorant (A) >>
The colorant (A) of the blue coloring composition for a color filter of the present invention contains at least a blue pigment [A1] and a xanthene dye [A2].

By combining and mixing the blue pigment [A1] and the xanthene dye [A2], the spectral spectrum has a high transmittance in the vicinity of 425 to 500 nm having the characteristic peaks of many backlights as described above. Therefore, higher brightness and wider color reproducibility can be obtained than a conventional color filter combining a copper phthalocyanine pigment and a dioxazine pigment.
<Blue pigment [A1]>
As the blue pigment, a phthalocyanine pigment, a triarylmethane lake pigment, or the like is used. As the phthalocyanine pigment, it is preferable to use a copper phthalocyanine blue pigment.

  Examples of the copper phthalocyanine blue pigment include C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, and the like. Among them, copper phthalocyanine blue pigments having ε-type and α-type structures are preferable. Such preferred pigments are specifically C.I. I. Pigment blue 15: 6 and C.I. I. Pigment Blue 15: 1.

  Examples of triarylmethane lake pigments include C.I. I. Pigment blue 1, 1: 2, 1: 3, C.I. I. Pigment Blue 2, 2: 1, 2: 2, C.I. I. Pigment blue 3, C.I. I. Pigment Blue 8, C.I. I. Pigment blue 9, C.I. I. Pigment Blue 10, 10: 1, C.I. I. Pigment blue 11, C.I. I. Pigment blue 12, C.I. I. Pigment blue 18, C.I. I. Pigment blue 19, C.I. I. Pigment blue 24, 24: 1, C.I. I. Pigment blue 53, C.I. I. Pigment blue 56, 56: 1, C.I. I. Pigment blue 57, C.I. I. Pigment blue 58, C.I. I. Pigment blue 59, C.I. I. Pigment blue 61, C.I. I. Pigment blue 62 and the like.

Among these, C.I. I. It is particularly preferable to use CI Pigment Blue 15: 6.
<Other pigments>
In addition, other organic pigments can be added to the blue coloring composition of the present invention as long as the effect is not hindered.

  As other organic pigments, dioxazine pigments, anthraquinone pigments, azo pigments, and quinacridone pigments are preferably used in combination. Among them, it is preferable to use a dioxazine pigment in combination. Examples of the dioxazine pigment include C.I. I. Pigment Violet 23 is preferably used. By using a dioxazine pigment in combination with the blue coloring composition of the present invention, it is possible to obtain a stable and high-quality blue coloring composition which is further excellent in heat resistance, light resistance and solvent resistance.

[Miniaturization of pigment]
The blue pigment [A1] used in the blue coloring composition of the present invention, or other pigments that can be used in combination, can be refined by a salt milling treatment. The primary particle diameter of the pigment is preferably 20 nm or more because of good dispersion in the colorant carrier. Moreover, since it can form a filter segment with high contrast ratio, it is preferable that it is 100 nm or less. Therefore, it is preferable to have a range of 20 to 100 nm. A particularly preferable range is a range of 25 to 85 nm.

  The primary particle diameter of the pigment was measured by directly measuring the size of the primary particle from an electron micrograph of the pigment using a TEM (transmission electron microscope). Specifically, for 100 or more pigment particles, 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. At this time, the pigment particles were sampled on a grid mesh to prepare a sample for TEM observation.

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

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

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

When the salt is milled, a resin may be added as necessary. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin used is solid at room temperature, preferably insoluble in water, and more preferably partially soluble in the organic solvent. The amount of resin used is preferably in the range of 5 to 200% by weight based on the total weight of the pigment (100% by weight).
<Xanthene dye [A2]>
The xanthene dye [A2] that can be preferably used in the present invention is red or purple, and has any form of an oil-soluble dye, an acid dye, a direct dye, and a basic dye.

  A red or purple color means C.I. I. Solvent Red, C.I. Oil soluble dyes such as I. solvent violet, C.I. I. Basic Red, C.I. Basic dyes such as I. basic violet, C.I. I. Acid Red, C.I. Acid dyes such as I. Acid Violet, C.I. I. Direct Red, C.I. I. Direct belongs to direct dyes such as violet.

Here, the direct dye has a sulfonic acid group (—SO ₃ H, —SO ₃ Na) in the structure, and in the present invention, the direct dye is regarded as an acid dye.

  The xanthene dye [A2] used in the present invention has a transmittance of 90% or more in the region of 650 nm in the transmission spectrum, a transmittance of 75% or more in the region of 600 nm, and a transmittance of 5% in the region of 500 to 550 nm. Hereinafter, those having a transmittance of 70% or more in the 400 nm region are preferable. More preferably, the transmittance is 95% or more in the region of 650 nm, the transmittance is 80% or more in the region of 600 nm, the transmittance is 10% or less in the region of 500 to 550 nm, and the transmittance is 75% in the region of 400 nm. That's it.

  Xanthene-based basic dyes also have spectral characteristics with high transmittance at 400 to 450 nm, but display images using color filters that are further poor in light resistance and heat resistance and require high reliability. Its properties are not sufficient for use in devices. Therefore, in order to improve the disadvantages of these dyes, it is preferable to salt the xanthene-based basic dye using an organic acid. As the organic acid, organic sulfonic acid or organic carboxylic acid is preferably used. Among these, tobias acid is preferable in that light resistance and heat resistance are improved. In addition to organic acids, perchloric acid is preferably used.

  Further, xanthene acid dyes have spectral characteristics having high transmittance at 400 to 450 nm. However, in spite of having good spectral characteristics, light resistance and heat resistance are poor as in general dyes, and the characteristics are as follows for use in image display devices using color filters that require high reliability. Not enough. Therefore, in order to improve the drawbacks of these dyes, xanthene acid dyes can be chlorinated or sulfonamidated using quaternary ammonium salt compounds, tertiary amine compounds, secondary amine compounds, primary amine compounds, etc. It is preferably used as a sulfonic acid amide compound.

  Among these, as the xanthene dye [A2] that can be preferably used in the present invention, it is preferable to use a xanthene acid dye or a xanthene oil-soluble dye, and in particular, a counter component that functions as a counter ion. It is preferable to use a compound prepared by chlorination using a quaternary ammonium salt compound, or a sulfonic acid amide compound obtained by sulfonamidating a xanthene acid dye.

  Among the xanthene dyes [A2], rhodamine dyes are preferable because they are excellent in color developability and resistance.

  Hereinafter, the form of the xanthene dye [A2] used in the present invention will be specifically described in detail.

[Xanthene oil-soluble dye]
The oil-soluble dye of the xanthene dye will be described. Xanthene oil-soluble dyes include CI Solvent Red 35, CI Solvent Red 36, CI Solvent Red 42, CI Solvent Red 43, CI Solvent Red 44, and C.I. I. Solvent Red 45, C.I. Solvent Red 46, C.I. Solvent Red 47, C.I. Solvent Red 48, C.I. Solvent Red 49, C.I. Solvent Red 72, C.I. Solvent Red 73, CI Solvent Red 109, CI Solvent Red 140, CI Solvent Red 141, CI Solvent Red 237, CI Solvent Red 246, CI Solvent Violet 2, CI Solvent Violet 10 and the like.

  Among them, CI Solvent Red 35, CI Solvent Red 36, CI Solvent Red 49, CI Solvent Red 109, CI Solvent, which are rhodamine-based oil-soluble dyes having high coloring properties. Red 237, CI Solvent Red 246, and CI Solvent Violet 2 are more preferable.

[Xanthene basic dye]
The basic dye of the xanthene dye will be described. Examples of xanthene basic dyes include C.I. I. Basic Red 1 (Rhodamine 6 GCP), 8 (Rhodamine G), C.I. I. Basic violet 10 (Rhodamine B) and the like.
Among these, C.I. I. Basic Red 1, C.I. I. Basic violet 10 is preferably used.

[Xanthene acid dyes]
The acidic dye of the xanthene dye will be described. Examples of acidic dyes of xanthene dyes include C.I. I. Acid Red 51 (erythrosin (edible red No. 3)), C.I. I. Acid Red 52 (Acid Rhodamine), C.I. I. Acid Red 87 (Eosin G (edible red No. 103)), C.I. I. Acid Red 92 (Acid Phloxin PB (food red No. 104)), C.I. I. Acid Red 289, C.I. I. Acid Red 388, Rose Bengal B (edible red No. 5), Acid Rhodamine G, C.I. I. It is preferable to use Acid Violet 9.

  Among these, in terms of heat resistance and light resistance, C.I. I. Acid Red 87, C.I. I. Acid Red 92, C.I. I. Acid Red 388, or C.I. which is a rhodamine acid dye. I. Acid Red 52 (Acid Rhodamine), C.I. I. Acid Red 289, Acid Rhodamine G, C.I. I. It is more preferable to use Acid Violet 9.

  Among these, in particular, C.I., which is a rhodamine acid dye, is excellent in color developability, heat resistance and light resistance. I. Acid Red 52, C.I. I. Most preferably, Acid Red 289 is used.

Further, the xanthene-based acid dye can have both high heat resistance, light resistance and solvent resistance by chlorination and sulfonamidation as a quaternary ammonium salt.
(Salt-forming compound consisting of xanthene acid dye and quaternary ammonium salt compound)
The xanthene dye [A2] used in the present invention is preferably used as a salt-forming compound comprising the xanthene acid dye and the quaternary ammonium salt compound described above.
{Quaternary ammonium salt compound}
A quaternary ammonium salt compound becomes a counter of a xanthene type acid dye by having an amino group.

  A preferred form of the quaternary ammonium salt compound which is a counter component of the salt-forming compound is colorless or white. Here, colorless or white means a so-called transparent state, and is defined as a state where the transmittance is 95% or more, preferably 98% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Is. That is, it is necessary not to inhibit color development of the dye component and to cause no color change.

The molecular weight of the counter portion, which is a cation component of the quaternary ammonium salt compound, is preferably in the range of 190 to 900. Here, the cation moiety corresponds to the (NR ₁ R ₂ R ₃ R ₄ ) + moiety in the following general formula (5). When the molecular weight is smaller than 190, light resistance and heat resistance are lowered, and further, solubility in a solvent is lowered. On the other hand, when the molecular weight is larger than 900, the ratio of the color developing component in the molecule is lowered, the color developability is lowered, and the lightness is also lowered. More preferably, the molecular weight of the counter portion is in the range of 240-850. Particularly preferred is a counter portion with a molecular weight in the range of 350-800.

Here, the molecular weight was calculated based on the structural formula. The atomic weight of C was 12, the atomic weight of H was 1, and the atomic weight of N was 14.
Moreover, what is represented by following General formula (5) is used as a quaternary ammonium salt compound.
General formula (5)

(In General Formula (5), R _{1 to} R ₄ each independently represent an alkyl group having 1 to 20 carbon atoms or a benzyl group, and at least two of R ₁ , R ₂ , R ₃ , or R ₄ And C has 5 to 20. Y represents an inorganic or organic anion.)
R ₁ to R ₄ in by the a 5 to 20 the number of at least two and C, solubility in solvents is improved. When the number of alkyl groups having a C number of less than 5 is 3 or more, solubility in a solvent is deteriorated, and coating film foreign matter is likely to be generated. Further, if there is an alkyl group in which the number of C exceeds 20, the color forming property of the salt-forming compound is impaired.

Specifically, tetramethylammonium chloride (molecular weight of the cation moiety is 74), tetraethylammonium chloride (molecular weight of the cation moiety is 122), monostearyltrimethylammonium chloride (molecular weight of the cation moiety is 312), distearyldimethylammonium chloride ( Cation portion molecular weight 550), tristearyl monomethylammonium chloride (cation portion molecular weight 788), cetyltrimethylammonium chloride (cation portion molecular weight 284), trioctylmethylammonium chloride (cation portion molecular weight 368), dioctyl Dimethylammonium chloride (cation part molecular weight 270), monolauryltrimethylammonium chloride (cation part molecule) 228), dilauryldimethylammonium chloride (cation part molecular weight 382), trilaurylmethylammonium chloride (cation part molecular weight 536), triamylbenzylammonium chloride (cation part molecular weight 318), trihexylbenzylammonium Chloride (cation part molecular weight 360), trioctylbenzylammonium chloride (cation part molecular weight 444), trilaurylbenzylammonium chloride (cation part molecular weight 612), benzyldimethylstearyl ammonium chloride (cation part molecular weight 388) ), and benzyl dimethyl octyl ammonium chloride (molecular weight of the cationic portion 248), dialkyl (alkyl C ₁₄ -C ₁₈₎ di It is preferable to use methylammonium chloride (cured beef tallow) (the molecular weight of the cation moiety is 438 to 550).

  The Y-component constituting the anion may be an inorganic or organic anion, but is preferably a halogen, usually chlorine.

Specific examples of the quaternary ammonium salt compound products include Cotamin 24P, Cotamin 86P Conch, Cotamin 60W, Cotamin 86W, Cotamin D86P, Sanizole C, Sanizole B-50, etc. manufactured by Lion Corp. , 2C-75,2HT-75,2HT flakes, 2O-75I, 2HP-75,2HP flakes and the like, among others QUARTAMIN D86P (distearyldimethylammonium chloride), Arquad 2HT-75 (di (alkyl C ₁₄ ~ _C18 ) dimethylammonium chloride) is preferred.
{Chlorination process}
A salt-forming compound of a xanthene acid dye and a quaternary ammonium salt compound can be synthesized by a conventionally known method. A specific method is disclosed in Japanese Patent Laid-Open No. 11-72969.

For example, after dissolving a xanthene acid dye in water, a quaternary ammonium salt compound may be added and subjected to chlorination treatment with stirring. Here, the sulfonic acid group (—SO ₃ H) and sodium sulfonate group (—SO ₃ Na) in the xanthene acid dye are combined with the ammonium group (NH ₄ +) portion of the quaternary ammonium salt compound. A salt compound is obtained. In addition, instead of water, methanol and ethanol are also solvents that can be used for the chlorination.

Salt-forming compounds are especially C.I. I. Acid Red 289 and C.I. I. By adjusting the molecular weight of the counter, which is a cation component of Acid Red 52 and the quaternary ammonium salt compound, to 350 to 800, the solvent solubility is excellent, and when used in combination with a blue pigment, the heat resistance, light resistance, and solvent resistance are improved. It will be excellent. The reason why the salt-forming compound becomes favorable when used in combination with the blue pigment is that it is adsorbed on the blue pigment while being dissolved and dispersed in the solvent. From such a viewpoint, the primary particle size of the blue pigment is preferably 20 to 100 nm.
(Sulphonic acid amide compound of xanthene acid dye)
A sulfonic acid amide compound of a xanthene-based acid dye that can be preferably used for the xanthene-based dye of the present invention is obtained by chlorinating a xanthene-based acid dye having —SO ₃ H and —SO ₃ Na by a conventional method, to obtain —SO ₃ H was a -SO ₂ Cl, the compound may be prepared by reacting an amine with a -NH ₂ group.

  Specific examples of amine compounds that can be preferably used in sulfonamidation include 2-ethylhexylamine, dodecylamine, 3-decyloxypropylamine, 3- (2-ethylhexyloxy) propylamine, and 3-ethoxypropylamine. It is preferable to use cyclohexylamine or the like.

  For example, C.I. I. In the case of obtaining a sulfonic acid amide compound obtained by modifying Acid Red 289 with 3- (2-ethylhexyloxy) propylamine, C.I. I. Acid Red 289 was converted to a sulfonyl chloride and reacted with the theoretical equivalent of 3- (2-ethylhexyloxy) propylamine in dioxane to give C.I. I. What is necessary is just to obtain the sulfonic acid amide compound of Acid Red 289.

The usage ratio of the blue pigment [A1] and the xanthene dye [A2] is preferably 1 to 80 parts by weight of the xanthene dye [A2] with respect to 100 parts by weight of the blue pigment [A1]. More preferably, it is 5 to 60 parts by weight. If the addition amount of the xanthene dye [A2] is less than 1 part by weight, the reproducible chromaticity region becomes narrow, and if it exceeds 80 parts by weight, the hue changes, which is not preferable.
<< Amine compound of phthalocyanine (C) >>
When the blue pigment [A1] and the xanthene dye [A2] are used as the colorant (A), the transparency is high due to the high solubility of the dye compared to the case of using only the pigment. On the other hand, there was a problem that fluorescence was generated from the dye itself, and the contrast ratio was lowered. This is mainly due to the presence of fluorescence in the leakage light at the time of contrast measurement, and the luminance on the cross side increases.

  In the case of a blue coloring composition for a color filter using only a pigment, a copper phthalocyanine compound having an acidic substituent or a copper phthalocyanine compound having a basic substituent is added for the purpose of improving contrast by improving the dispersibility of the blue pigment. Has been known for some time.

  The phthalocyanine compound having the substituent is suitable as a component to be added to the blue coloring composition because it has transparency in the wavelength region of 400 to 450 nm. However, when a xanthene dye capable of higher brightness is used together with a blue pigment, a problem arises in that the contrast ratio decreases due to the fluorescence emission of the xanthene dye. When a copper phthalocyanine compound having a group (for example, a sulfonic acid compound of copper phthalocyanine) was used, no effect was observed.

  As a result of studies conducted by the present inventors to solve the problem of reduction in contrast due to fluorescence emission, in addition to the colorant (A) containing the blue pigment [A1] and the xanthene dye [A2], a detailed description will be given later. By using the amine compound (C) of phthalocyanine, it was possible to realize high contrast by eliminating the generation of fluorescence from the xanthene dye and lowering the luminance on the cross side.

  The reason why the fluorescence quenching effect becomes prominent when these substances are used is not clear, but when an amine compound (C) of phthalocyanine is used, it is fluorescent because of its high compatibility with xanthene dyes and copper phthalocyanine pigments. High quenching efficiency, especially when using a copper phthalocyanine sulfonic acid amide compound among the phthalocyanine amine compounds, in addition to the above action, it is easy to form a charge transfer complex with a xanthene dye, so that the fluorescence emission itself is remarkably suppressed, It is thought that the fluorescence is significantly quenched. In addition to the above-described fluorescence quenching effect, the high compatibility between the dye and the copper phthalocyanine blue pigment when using the copper phthalocyanine sulfonic acid amide compound is due to the light scattering due to the uneven distribution of the copper phthalocyanine particles and the dye in the resist. As a result, it is considered that the cross luminance becomes extremely low and the contrast ratio is particularly excellent.

  The amine compound (C) of phthalocyanine is preferably an amine compound of copper phthalocyanine, a basic compound having a basic substituent on the copper phthalocyanine pigment (copper phthalocyanine sulfonic acid amide compound), an acidic substituent and a quaternary ammonium salt. Or a compound in which a phthalimidomethyl group which may have a substituent is introduced. This will be specifically described below.

  As the phthalocyanine, in addition to the copper phthalocyanine, metal-free phthalocyanine, aluminum phthalocyanine, zinc phthalocyanine, cobalt phthalocyanine, nickel phthalocyanine and the like can also be used.

  As the amine compound (C) of phthalocyanine used in the present invention, among the above, basic compounds having a basic substituent on the copper phthalocyanine pigment, particularly copper phthalocyanine sulfonate ammonium salt, copper phthalocyanine tertiary amine compound, copper phthalocyanine sulfone Acid amide compounds are preferred. Similarly, a basic compound having a basic substituent on the zinc phthalocyanine pigment can also be preferably used.

  Specifically, a phthalocyanine amine compound (C) represented by the following general formula (1), which has a basic group represented by the following general formulas (2) to (4), is preferable. Can be used for

General formula (1):
P-Lm
[In General Formula (1), P is an m-valent phthalocyanine pigment residue, m is an integer of 1 to 4, and L is General Formula (2), (3), or (4) Any of the substituents selected from the group shown. ]
General formula (2):

  General formula (3):

  General formula (4):

[In the general formulas (2) to (4), X represents —SO ₂ —, —CO—, —CH ₂ —,
_{-CH 2 NHCOCH 2 -, - CH} 2 NHSO 2 CH 2 -, or a direct bond,
Y ⁰ is —NH—, —O—, or a direct bond;
n is an integer of 1 to 10,
Y ¹ is —NH—, —NR ⁹ —Z—NR ¹⁰ —, or a direct bond;
R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 36 carbon atoms, an alkenyl group having 2 to 36 carbon atoms, or a phenyl group,
Z represents an alkylene group having 1 to 20 carbon atoms or an arylene group having 1 to 20 carbon atoms.

R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or a combination of R ¹ and R ² with further nitrogen, oxygen Or a heterocycle containing a sulfur atom,
R ³ , R ⁴ , R ⁵ , and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms. ,
R ⁷ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms,
R ⁸ is a substituent represented by the general formula (2) or a substituent represented by the general formula (3),
Q represents a hydroxyl group, an alkoxyl group having 1 to 20 carbon atoms, a substituent represented by the general formula (2), or a substituent represented by the general formula (3). ]
Examples of the amine component used for forming the substituents represented by the general formulas (2) to (4) include dimethylamine, diethylamine, methylethylamine, N, N-ethylisopropylamine, N, N-ethyl. Propylamine, N, N-methylbutylamine, N,
N-methylisobutylamine, N, N-butylethylamine, N, N-tert-butylethylamine, diisopropylamine, dipropylamine, N, N-sec-butylpropylamine, dibutylamine, di-sec-butylamine, diisobutylamine , N, N
-Isobutyl-sec-butylamine, diamylamine, diisoamylamine, dihexylamine, dicyclohexylamine, di (2-ethylhexyl) amine, dioctylamine, N, N-methyloctadecylamine, didecylamine, diallylamine, N, N-ethyl- 1,2-dimethylpropylamine, N, N-methylhexylamine, dioleylamine, distearylamine, N, N-dimethylaminomethylamine, N, N-dimethylaminoethylamine, N, N-dimethylaminoamylamine, N , N-dimethylaminobutylamine, N, N-diethylaminoethylamine, N, N-diethylaminopropylamine, N, N-diethylaminohexylamine, N, N-diethylaminobutylamine, N
, N-diethylaminopentylamine, N, N-dipropylaminobutylamine, N, N
-Dibutylaminopropylamine, N, N-dibutylaminoethylamine, N, N-dibutylaminobutylamine, N, N-diisobutylaminopentylamine, N, N-methyl-laurylaminopropylamine, N, N-ethyl-hexylamino Ethylamine, N,
N-distearylaminoethylamine, N, N-dioleoylaminoethylamine, N, N
-Distearylaminobutylamine, piperidine, 2-pipecoline, 3-pipecoline, 4
-Pipecoline, 2,4-Lupetidine, 2,6-Lupetidine, 3,5-Lupetidine, 3-
Piperidinemethanol, pipecolic acid, isonipecotic acid, methyl isonipecotate, ethyl isonicopetinate, 2-piperidineethanol, pyrrolidine, 3-hydroxypyrrolidine, N-aminoethylpiperidine, N-aminoethyl-4-pipecholine, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl-2-pipecoline, N-aminopropyl-4-pipecoline, N-aminopropylmorpholine, N-methylpiperazine, N-butylpiperazine, N-methylhomopiperazine, 1-cyclopentylpiperazine 1-amino-4-methylpiperazine, 1-cyclopentylpiperazine, and the like.

  The amine compound of phthalocyanine having a basic substituent of the present invention can be synthesized by various synthetic routes. For example, after introducing the substituents represented by the following general formulas (6) to (9) into copper phthalocyanine or other metal phthalocyanines, they react with the above substituents and are represented by the general formulas (2) to (4). The amine component forming the substituent, for example, N, N-dimethylaminopropylamine, N-methylpiperazine, diethylamine, or 4- [4-hydroxy-6- [3- (dibutylamino) propylamino] -1, It can be obtained by reacting 3,5-triazin-2-ylamino] aniline or the like.

Formula (6): —SO ₂ Cl
General formula (7): -COCl
Formula (8): —CH ₂ NHCOCH ₂ Cl
Formula (9): —CH ₂ Cl
In the reaction of the substituents of the general formulas (6) to (9) with the amine component, a part of the substituents of the general formulas (6) to (9) are hydrolyzed so that chlorine is substituted with a hydroxyl group. It may be mixed. In that case, the general formula (6) and the general formula (7) are a sulfonic acid group and a carboxylic acid group, respectively, but any of them may be a free acid. Or a salt with a monoamine.

  Among the amine compounds (C) of the phthalocyanine of the present invention, the substituent represented by the general formula (4) can be synthesized by various synthetic routes. For example, starting from cyanuric chloride, an amine component that forms a substituent represented by the general formulas (2) and (3) on at least one chlorine of cyanuric chloride, such as N, N-dimethylaminopropylamine or N- It can be obtained by reacting methylpiperazine or the like and then reacting the remaining chlorine of cyanuric chloride with various amines or alcohols.

  The most preferred form of the phthalocyanine amine compound used in the present invention is a copper phthalocyanine sulfonic acid amide compound which is a copper phthalocyanine basic compound.

The copper phthalocyanine sulfonic acid amide compound is a general formula (2) to (4) among the copper phthalocyanine compounds having the above basic substituents.
X in the general formulas (2) to (4) is —SO ₂ —, —CH ₂ NHSO ₂ CH ₂ —,
Y ⁰ is —NH— or a direct bond;
n is an integer of 1 to 10,
Y ¹ is a compound that is —NH— or —NR ⁹ —Z—NR ¹⁰ —.
(Here, R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 36 carbon atoms, an alkenyl group having 2 to 36 carbon atoms, or a phenyl group, and Z is a group having 1 to 20 alkylene groups, preferably an alkylene group having 1 to 10 carbon atoms, or an arylene group having 1 to 20 carbon atoms, preferably an arylene group having 1 to 10 carbon atoms. Examples include a methylene group, an ethylene group, and propylene. Group and phenylene group.)
The phthalocyanine amine compound (C) used in the present invention can be used alone or in combination of two or more.

  The compounding amount of the amine compound (C) of phthalocyanine used in the present invention is based on the total amount of the colorant (A) (100% by weight), and the viewpoint of the quantum yield and solubility of fluorescence from the dye. To 0.01 to 200% by weight, more preferably 1 to 100% by weight.

In the colorant composition of the present invention, the compounding amount of the amine compound (C) of phthalocyanine is such that the weight ratio (C / [A2]) to the xanthene dye [A2] is 0.3 to 1.5. preferable. If it is less than 0.3, the contrast is lowered because the suppression of fluorescence and the dispersibility of the amine compound (C) of phthalocyanine are insufficient. A more preferred weight ratio (C / [A2]) is 0.4 to 1.2, and a most preferred weight ratio (C / [A2]) is 0.5 to 1.1.
<< Resin (B) >>
The resin disperses, dyes, and penetrates the colorant (A), and examples thereof include thermoplastic resins and thermosetting resins. In addition to the main resin, a rosin ester may be used as an auxiliary resin. The resin (B) is composed of a main resin and an optional auxiliary resin.

  The resin preferably has a spectral transmittance of 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Moreover, when using with the form of an alkali image development type colored resist material, it is preferable to use the alkali-soluble vinyl resin which copolymerized the acidic group containing ethylenically unsaturated monomer. In order to further improve the photosensitivity, an energy ray curable resin having an ethylenically unsaturated active double bond can also be used.

  In order to disperse the colorant (A) preferably, the weight average molecular weight (Mw) of the resin (B) is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 80,000. is there. 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 resin (B) is used in a blue coloring composition for a color filter, a colorant adsorbing group and a carboxyl group that acts as an alkali-soluble group during development, an aliphatic group that acts as an affinity group for the colorant carrier and solvent And the balance of the aromatic groups is important for the dispersibility, penetrability, developability, and durability of the colorant (A), 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. If it exceeds 300 mgKOH / g, no fine pattern remains.

  The resin (B) is preferably used in an amount of 30% by weight or more based on the total weight of the colorant (A) (100% by weight) in consideration of film formability and various resistances. It is preferably used in an amount of 500% by weight or less because it is high and can exhibit good color characteristics.

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

  Examples of the 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, and 2-glycidoxyethyl (meth).
An acrylate, 3,4 epoxy butyl (meth) acrylate, and 3,4 epoxy cyclohexyl (meth) acrylate are mentioned, These may be used independently or may use 2 or more types together. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth)
Acrylate is preferred.

As unsaturated monobasic acids, (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro,
Examples thereof include monocarboxylic acids such as cyano-substituted products, and these may be used alone or in combination of two or more.

Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride and the like.
More than one type may be used together. 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 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
-Hydroxyalkyl (meth) acrylates such as 4-hydroxybutyl (meth) acrylate, glycerol (meth) acrylate, or cyclohexanedimethanol mono (meth) acrylate may be mentioned. The above may be used in combination. 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 include epoxy resins, benzoguanamine resins, melamine resins, urea resins, and phenol resins.
[Rosin ester]
In the present invention, in addition to the resins described above, a rosin ester may be included as an auxiliary resin for the purpose of improving the dispersibility of the pigment, improving the resistance of the xanthene dye [A2], and maintaining it.

 Rosin esters are gum rosin, tall rosin, wood rosin, disproportionated rosin, hydrogenated rosin, partially rosin, mainly composed of abietic acid, neoabietic acid, levopimaric acid, hydroabietic acid, pimaric acid, dextropimalic acid, etc. It is an ester (glycerin ester, pentaerythritol ester, diethylene glycol ester, etc., particularly preferably pentaerythritol ester) of leveled rosin, maleated rosin and a mixture thereof with polyhydric alcohol.

 The rosin ester that may be used in the present invention is obtained by the following method.

 A rosin ester is obtained by esterifying a purified rosin such as purified gum rosin, purified wood rosin, purified polymerized rosin, purified disproportionated rosin or purified tall oil rosin with alcohol as a starting material. In the esterification reaction, normal conditions can be used as they are. For example, purified rosin and the following alcohol are reacted under heating at 150 to 300 ° C. under an inert gas stream, and the produced water is removed from the system. What is necessary is just to carry out by removing.

 Although it does not specifically limit as an alcohol component used for esterification, For example, monohydric alcohol like n-octyl alcohol, 2-ethylhexyl alcohol, decyl alcohol, or lauryl alcohol; Ethylene glycol, diethylene glycol, propylene glycol, neopentyl glycol Alternatively, a dihydric alcohol such as cyclohexanedimethanol; a trihydric alcohol such as glycerin, trimethylolethane or trimethylolpropane; and a tetrahydric alcohol such as pentaerythritol or diglycerin can be used. Of these, trivalent and tetravalent polyhydric alcohols are preferably used. These can be used individually by 1 type or in combination of 2 or more types.

 Moreover, an esterification catalyst or antioxidant can also be used as needed. Examples of the esterification catalyst include acid catalysts such as acetic acid or paratoluenesulfonic acid, alkali metal hydroxides such as calcium hydroxide, and metal oxides such as calcium oxide or magnesium oxide.

 Specific examples of rosin esters that can be used as commercially available products include the following.

(Rosin ester)
Pencel A, AZ, ester gum AAG, AAL, A, AAV, 105, HS, AT, etc. manufactured by Arakawa Chemical Industries, Ltd. Neotor G2, 101K, NT-15, 125HK, Harrier Star TF, NL, S, P, C, DS-70L, DS-90, DS-130, etc. manufactured by Harima Kasei Co., Ltd.

(Polymerized rosin ester)
Pencel D-125, D-135, D-160, etc. manufactured by Arakawa Chemical Industries, Ltd. Harima Star KT-2 manufactured by Harima Chemicals.

(Disproportionated rosin ester)
Arakawa Chemical Industries, Ltd. Superester A-75, A-100, A-115, -125, T-125, etc.

(Rosin-modified maleic acid resin, rosin-modified fumaric acid resin)
ARUKAWA CHEMICAL INDUSTRIES CO., LTD. Marquide NO. 1, 2, 5, 6, 8, 30A, 31, 32, 33, 34, 3002, etc. Harima Chemical Co., Ltd. Harimac T-80, R-100, M-453, M-130A, 135GN, 145P, R-120AH, etc. (hydrogenated rosin ester)
Among the ester gums H, HP, HD, etc. manufactured by Arakawa Chemical Industries, Inc., it is preferable to use polymerized rosin ester, disproportionated rosin ester, rosin-modified maleic resin (including rosin-modified fumaric acid resin).

  The rosin ester that can be preferably used in the present invention preferably has an acid value of 100 mgKOH / g or less. More preferably, it is 40 or less (mgKOH / g). A particularly preferred range is from 5 to 40 (mg KOH / g), and in this range, it is effective for maintaining the performance of the xanthene dye [A2].

 In consideration of compatibility with the main resin, storage stability, and productivity, the softening point of the rosin ester by the ring and ball method is preferably in the range of 70 to 150 ° C. When the temperature is lower than 70 ° C., the storage stability is lowered and the blue colored composition tends to aggregate, and when the temperature exceeds 150 ° C., the adhesion of the color filter is lowered. Here, the main resin is the above-described thermoplastic resin and / or thermosetting resin.

The amount of rosin ester added is preferably 0.3 to 5 parts by weight with respect to 100 parts by weight of the main resin. If the amount of rosin ester added is less than 0.3 parts by weight, the effect cannot be obtained. Moreover, when it exceeds 5 weight part, the performance of resin will be inhibited.
"solvent"
In the blue coloring composition of the present invention, the colorant (A) is sufficiently dispersed and permeated in the colorant carrier, and is applied on a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. In order to facilitate the formation of the filter segment, a solvent can be included.

  Examples of the solvent include 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-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-alkyl Silene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene Glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol mono Hexyl ether, ethylene glycol monomethyl ether , Ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone , Dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipro Lenglycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether , Propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, vinegar Isobutyl, propyl acetate, dibasic esters, butyl lactate and the like.

  Among these, since the dispersibility, solubility, and permeability of the colorant (A) of the present invention are good, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate It is preferable to use glycol acetates such as, aromatic alcohols such as benzyl alcohol, and ketones such as cyclohexanone. Of these, cyclohexanone is preferably used.

A solvent can be used individually by 1 type or in mixture of 2 or more types. Moreover, since the solvent can adjust the coloring composition to an appropriate viscosity and can form a filter segment with a desired uniform film thickness, the total weight of the colorant (A) is set to 800 to It is preferably used in an amount of 4000% by weight.
"dispersion"
The blue coloring composition of the present invention comprises a colorant carrier comprising a resin (B) as a colorant (A), an amine compound (C) of phthalocyanine, and, if necessary, a three-roll mill, two-roll mill. Further, it can be produced by finely dispersing using various dispersing means such as a sand mill, a kneader, or an attritor. The blue coloring composition of the present invention can also be produced by mixing several types of colorants separately dispersed in a colorant carrier.
[Dispersing aid]
When the colorant (A) is dispersed in the colorant carrier, a dispersion aid such as a resin-type dispersant and a surfactant can be appropriately used. The dispersion aid is excellent in dispersing the pigment component in the colorant (A) and has a great effect of preventing reaggregation of the colorant after dispersion. When a blue coloring composition dispersed therein is used, a color filter having high spectral transmittance can be obtained.

(Resin type dispersant)
The resin-type dispersant has a colorant affinity part having a property of adsorbing to a colorant, particularly a pigment, and a part compatible with the colorant carrier, and adsorbs to the colorant to provide a colorant carrier for the colorant. It works to stabilize dispersion in the water. Specific examples of resin-type dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , Polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amides formed by reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group, and salts thereof Oil-soluble dispersants such as, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Resin, water-soluble polymer, polyester, modified poly Acrylate-based, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, it can be used alone or in admixture of two or more.

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, and 170 manufactured by Big Chemie Japan. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155 or Anti-Terra-U, 203, 204, or BYK- P104, P104S, 220S, 6919, or SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 1600 manufactured by Nihon Lubrizol Corporation, such as Lactimon, Lactimon-WS, or Bykumen. 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc. EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, manufactured by Japan 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 75 4,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

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

  When a resin-type dispersant and a surfactant are added, the total amount of the colorant (A) is preferably 0.1 to 55% by weight, more preferably 0.1 to 45% by weight based on the total amount (100% by weight). %. When the blending amount of the resin type dispersant and the surfactant is less than 0.1% by weight, it is difficult to obtain the added effect. When the blending amount is more than 55% by weight, the dispersion is affected by an excessive dispersant. May affect.

The blue colored composition of the present invention can be used as a photosensitive blue colored composition (blue resist material) for color filters 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 amount of the monomer is preferably 5 to 400% by weight based on the total weight of the colorant (A) (100% by weight), and 10 to 300% by weight from the viewpoint of photocurability and developability. It is more preferable.

Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce a resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) ) Acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycidyl -Terdi (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodeca Nyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate ester, epoxy (meth) acrylate, urethane acrylate and other acrylic esters and methacrylate esters, (meth) acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (Meth) acrylamide, N-vinylformamide, acrylonitrile and the like can be mentioned, but are not necessarily limited thereto.
<< Photopolymerization initiator >>
In the blue 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. It can be adjusted in the form of a colored resist material. The blending amount when using the photopolymerization initiator is preferably 5 to 200% by weight based on the total amount of the colorant (A), and 10 to 150% by weight from the viewpoint of photocurability and developability. More preferably.

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

These photopolymerization initiators can be used alone or in combination of two or more at any ratio as required. These photopolymerization initiators are preferably 5 to 200% by weight based on the total amount of the colorant (A) in the blue coloring composition for color filters (100% by weight), and are photocurable and developable. From the viewpoint of the above, it is more preferably 10 to 150% by weight.
<< Sensitizer >>
Furthermore, the blue 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, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 ', or 4,4'-tetra (t-butylperoxycarbonyl) benzophen Enone, 4,4'-diethylaminobenzophenone, and the like.

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

Two or more kinds of sensitizers may be used in any ratio as required. The blending amount when using the sensitizer is preferably 3 to 60% by weight based on the total weight of the photopolymerization initiator contained in the colored composition (100% by weight). From the viewpoint of developability, it is more preferably 5 to 50% by weight.
《Oxygen-reducing amine compound》
The blue colored composition of the present invention can contain an oxygen-reducing amine compound that functions to reduce dissolved oxygen.

Such oxygen-reducing amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-benzoic acid 2- Examples include dimethylaminoethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethylparatoluidine.
《Leveling agent》
In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the blue coloring composition of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by Big Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. In general, the leveling agent is preferably used in an amount of 0.003 to 0.5% by weight based on the total weight of the blue coloring composition (100% by weight).

  As a particularly preferred leveling agent, it is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, has a hydrophilic group but has low solubility in water, and when added to a blue coloring composition, It has the feature that its surface tension lowering ability is low, and it is useful to have good wettability to the glass plate despite its low surface tension lowering ability, and the added amount that does not cause coating film defects due to foaming In this case, 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 blue coloring composition of this invention may contain the hardening | curing agent, the hardening accelerator, etc. as needed. As the curing agent, phenol resins, amine curing agents, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but are not particularly limited to these, and are thermosetting. Any curing agent may be used as long as it can react with the resin. 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 to 15 weight% is preferable with respect to the thermosetting resin whole quantity.
(Other additive components)
The blue colored composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity of the composition with time. Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained.

  Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Organic phosphines, phosphites and the like can be mentioned. The storage stabilizer can be used in an amount of 0.1 to 10% by weight based on the colorant (A) in the coloring composition (100% by weight).

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% by weight, preferably 0.05 to 5% by weight, based on the total amount of the colorant in the coloring composition (100% by weight).
<< Production of photosensitive blue coloring composition >>
When the blue coloring composition for color filter of the present invention is used as a photosensitive blue coloring composition in the form of a solvent development type or alkali development type coloring resist material, a blue pigment [A1] and a xanthene dye [A2] A three-roll mill, a two-roll mill, and a sand mill in which a colorant (A), a resin (B), a phthalocyanine amine compound (C), and a colorant carrier such as an organic solvent are mixed as necessary. , Disperse and dissolve in resin solvent liquid finely using various dispersing means such as kneader, attritor, open roll type continuous kneader, etc. It can be adjusted by mixing an agent, and if necessary, other resins, solvents, dispersants and additives.
<Removal of coarse particles>
The blue colored composition for a color filter of the present invention is 5 μm or more coarse particles, preferably 1 μm or more coarse particles, more preferably 0.5 μm or more coarse particles by means of centrifugation, sintered filter, membrane filter or the like. It is preferable to remove particles and mixed dust. Thus, it is preferable that the blue coloring composition for color filters does not substantially contain particles of 0.5 μm or more. More preferably, all the particles are substantially 0.3 μm or less. Here, the measurement was performed using a particle size distribution measuring apparatus “Nano-S (Sysmex Corporation)” using a dynamic light scattering method.
《Color filter》
The color filter of the present invention includes at least one red filter segment, at least one green filter segment, and at least one blue filter segment, and the at least one blue filter segment is for the color filter of the present invention. It is formed using a blue coloring composition.

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

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

  The green filter segment can be formed using a normal green coloring composition including a green pigment and a pigment carrier. Examples of the green pigment include C.I. I. Pigment Green 7, 10, 36, 37, 58, etc. are used.

A yellow pigment can be used in combination with the green coloring composition. Examples of yellow pigments that can be used in combination include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 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. Further, a basic dye exhibiting yellow and a salt-forming compound of an acid dye can be used in combination.
《Color filter manufacturing method》
The color filter of the present invention can be produced by a printing method or a photolithography method.

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

  When forming a filter segment by photolithography, the photosensitive coloring composition containing the blue coloring composition of the present invention prepared as the solvent development type or alkali development type coloring resist is spray-coated or spin-coated on a transparent substrate. By a coating method such as coating, slit coating, roll coating or the like, the coating is applied so that the dry film thickness is 0.2 to 5 μm. If necessary, the dried film is exposed to ultraviolet rays through a mask having a predetermined pattern provided in contact with or not in 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, or the like in addition to the above method, but the blue coloring composition for a color filter of the present invention can be used in any method. The electrodeposition method is a method for producing a color filter by using a transparent conductive film formed on a substrate and forming each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. . The transfer method is a method in which a filter segment is formed in advance on the surface of a peelable transfer base sheet, and this filter segment is transferred to a desired substrate.

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

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

  First, acrylic resin solutions, colorants (xanthene dyes, fine pigments), pigment dispersions, dye-containing resin solutions, phthalocyanine amine compounds (C) used in Examples and Comparative Examples, and color filters are used. The manufacturing method of the red and green resist materials will be described.

  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.

  The degree of fineness of the pigment was evaluated by the specific surface area of pigment particles and the average primary particle size. The specific surface area was measured with an automatic vapor adsorption amount measuring apparatus (“BELSORP18” manufactured by Nippon Bell Co., Ltd.) using the BET method of nitrogen adsorption.

A method for measuring the contrast ratio of the coating film will be described.
(Measurement method of contrast ratio of coating film)
The light emitted from the backlight unit for liquid crystal display passes through the polarizing plate, is polarized, passes through the dried coating film of the colored composition applied on the glass substrate, and reaches the polarizing plate. If the polarizing planes of the polarizing plate and the polarizing plate are parallel, light is transmitted through the polarizing plate, but if the polarizing plane is perpendicular, the light is blocked by the polarizing plate. However, when the light polarized by the polarizing plate passes through the dried coating film of the colored composition, scattering by the pigment particles occurs, resulting in deviation in a part of the polarization plane. When the amount of light transmitted through the plate is reduced and the polarizing plate is perpendicular, a part of the light is transmitted through the polarizing plate. This transmitted light was measured as the luminance on the polarizing plate, and the ratio (contrast ratio) between the luminance when the polarizing plate was parallel and the luminance when it was orthogonal was calculated.

(Contrast ratio) = (Luminance when parallel) / (Luminance when direct)
Accordingly, when scattering occurs due to the pigment in the coating film, the brightness when parallel is reduced and the brightness when perpendicular is increased, the contrast ratio is lowered.

A color luminance meter ("BM-5A" manufactured by Topcon Corporation) was used as the luminance meter, and a polarizing plate ("NPF-G1220DUN" manufactured by Nitto Denko Corporation) was used as the polarizing plate. In the measurement, a black mask with a 1 cm square hole was applied to the measurement portion in order to block unnecessary light.
<Method for producing acrylic resin solutions 1 to 4 and 1B and 2B>
(Preparation of acrylic resin solution 1)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirring device was charged with 69.4 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 continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight (Mw) of 26000. Thereafter, 0.6 part of a polymerized rosin ester “Pencel D-125” (manufactured by Arakawa Chemical Industries, Ltd.) was added and stirred at 80 ° C. for 30 minutes.

After cooling the resin solution 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 non-volatile content, so that the non-volatile content was 20% by weight in the previously synthesized resin solution. Acrylic resin solution 1 was prepared by adding cyclohexanone.
(Preparation of acrylic resin solution 1B)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirring device was charged with 69.4 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 continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight (Mw) of 26000.

After cooling this resin solution 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, so that the nonvolatile content in the previously synthesized resin solution was 20% by weight. Acrylic resin solution 1B was prepared by adding cyclohexanone.
(Preparation of acrylic resin solution 2)
In a separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe, and a stirring device, 205 parts of cyclohexanone was charged, heated to 80 ° C., and the atmosphere in the flask was replaced with nitrogen. 20 parts of acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toa Gosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2′-azobisisobutyronitrile 1.33 parts of the mixture was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a copolymer resin solution.

Next, after the nitrogen gas was stopped and stirred while injecting dry air for 1 hour with respect to the total amount of the copolymer solution obtained, the mixture was cooled to room temperature, and then 2-methacryloyloxyethyl isocyanate (Karenz manufactured by Showa Denko KK). MOI) A mixture of 6.5 parts, 0.08 part dibutyltin laurate and 26 parts cyclohexanone was added dropwise at 70 ° C. over 3 hours. Thereafter, 2.0 parts of a polymerized rosin ester “Pencel D-125” (manufactured by Arakawa Chemical Industries, Ltd.) was added and stirred at 80 ° C. for 30 minutes.

After cooling the resin solution 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. Acrylic resin solution 2 was prepared by adding cyclohexanone. The weight average molecular weight (Mw) was 18000.
(Preparation of acrylic resin solution 2B)
In a separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe, and a stirring device, 205 parts of cyclohexanone was charged, heated to 80 ° C., and the atmosphere in the flask was replaced with nitrogen. 20 parts of acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toa Gosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2′-azobisisobutyronitrile 1.33 parts of the mixture was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a copolymer resin solution.

Next, after the nitrogen gas was stopped and stirred while injecting dry air for 1 hour with respect to the total amount of the copolymer solution obtained, the mixture was cooled to room temperature, and then 2-methacryloyloxyethyl isocyanate (Karenz manufactured by Showa Denko KK). MOI) A mixture of 6.5 parts, 0.08 part dibutyltin laurate and 26 parts cyclohexanone was added dropwise at 70 ° C. over 3 hours.

After cooling the resin solution 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 non-volatile content, so that the non-volatile content was 20% by weight in the previously synthesized resin solution. Cyclohexanone was added to prepare an acrylic resin solution 2B. The weight average molecular weight (Mw) was 19000.
(Preparation of acrylic resin solution 3)
207 parts of cyclohexanone was charged into a separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe, and a stirring device, heated to 80 ° C., and the flask was purged with nitrogen. 20 parts of acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toa Gosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of glycerol monomethacrylate, and 2,2′-azobisisobutyronitrile.
33 parts of the mixture was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a copolymer resin solution.

Next, after the nitrogen gas was stopped and stirred while injecting dry air for 1 hour with respect to the total amount of the copolymer solution obtained, after cooling to room temperature, 6.5 parts of 2-methacryloyloxyl ethyl isocyanate, 7 parts of a mixture of 0.08 parts dibutyltin laurate and 26 parts cyclohexanone
The solution was added dropwise at 0 ° C over 3 hours. Thereafter, 2.0 parts of a polymerized rosin ester “Pencel D-125” (manufactured by Arakawa Chemical Industries, Ltd.) was added and stirred at 80 ° C. for 30 minutes.

After cooling the resin solution 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. Acrylic resin solution 3 was prepared by adding cyclohexanone. The weight average molecular weight (Mw) was 19000.
(Preparation of acrylic resin solution 4)
A separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirring device was charged with 370 parts of cyclohexanone, heated to 80 ° C., and the atmosphere in the flask was replaced with nitrogen. 18 parts of milphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2,2′-azobisisobutyronitrile 2.0 Part of the mixture was added dropwise over 2 hours. After dropping, the reaction was further carried out at 100 ° C. for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour. Next, the inside of the container is replaced with air, and 0.5 part of trisdimethylaminophenol and 0.1 part of hydroquinone are put into 9.3 parts of acrylic acid (100% of glycidyl group) and the container is placed at 120 ° C. The reaction was continued for 6 hours, and when the acid value of the solid content reached 0.5, the reaction was terminated to obtain an acrylic resin solution. Further, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl group) and 0.5 parts of triethylamine were added and reacted at 120 ° C. for 3.5 hours to obtain an acrylic resin solution. Thereafter, 2.0 parts of a polymerized rosin ester “Pencel D-125” (manufactured by Arakawa Chemical Industries, Ltd.) was added and stirred at 80 ° C. for 30 minutes.

After cooling the resin solution 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 non-volatile content, so that the non-volatile content was 20% by weight in the previously synthesized resin solution. Acrylic resin solution 4 was prepared by adding cyclohexanone. The weight average molecular weight (Mw) was 19000.
<Method for producing xanthene dye [A2]>
(Xanthene dye ([A2] -1); Rhodamine salt-forming compound)
In the following procedure, C.I. I. A xanthene dye ([A2] -1) consisting of Acid Red 289 and dialkyl (alkyl is C14 to C18) dimethylammonium chloride (Arcade 2HT-75) (the molecular weight of the cation moiety is 438 to 550) was prepared.

In a 7-15 mol% sodium hydroxide solution, C.I. I. Acid Red 289 is dissolved, mixed and stirred thoroughly, heated to 70-90 ° C., and then Arcard 2HT-75 is added dropwise little by little. Arcade 2HT-75 may be dissolved in water and used as an aqueous solution. After dropping Arcade 2HT-75, the mixture is stirred at 70 to 90 ° C. for 60 minutes to sufficiently react. In order to confirm the end point of the reaction, it can be judged that the salt-forming compound was obtained with the reaction solution dropped on the filter paper and the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer. I. A xanthene dye ([A2] -1) which is a salt-forming compound of Acid Red 289 and dialkyl (alkyl is C14 to C18) dimethylammonium chloride was obtained.
(Xanthene dye ([A2] -2); Rhodamine salt forming compound)
In the following procedure, C.I. I. A xanthene dye ([A2] -2) composed of Acid Red 289 and distearyldimethylammonium chloride (Cotamine D86P) (the molecular weight of the cation moiety was 550) was prepared.

In a 7-15 mol% sodium hydroxide solution, C.I. I. Acid Red 289 is dissolved, thoroughly mixed and stirred, heated to 70-90 ° C., and then Cotamine D86P is added dropwise little by little. Coatamine D86P may be dissolved in water and used as an aqueous solution. After adding Cotamine D86P dropwise, the mixture is stirred at 70 to 90 ° C. for 60 minutes to sufficiently react. In order to confirm the end point of the reaction, it can be judged that the salt-forming compound was obtained with the reaction solution dropped on the filter paper and the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer. I. A xanthene dye ([A2] -2), which is a salt-forming compound of Acid Red 289 and distearyldimethylammonium chloride, was obtained.
(Xanthene dye ([A2] -3); rhodamine sulfonic acid amide compound)
C. I. Acid Red 289 was converted to a sulfonyl chloride by a conventional method and then reacted with a theoretical equivalent of 2-ethylhexylamine in dioxane to obtain C.I. I. A xanthene dye ([A2] -3) which is a sulfonic acid amide compound of Acid Red 289 was obtained. (Based on the description of JP-A-6-194828)
(Xanthene dye ([A2] -4); xanthene salt forming compound)
In the following procedure, C.I. I. A xanthene dye ([A2] -4) consisting of Acid Red 87 and distearyldimethylammonium chloride (Coatamine D86P) (the molecular weight of the cation moiety was 550) was prepared.

In a 7-15 mol% sodium hydroxide solution, C.I. I. Acid Red 87 is dissolved, mixed and stirred thoroughly, heated to 70 to 90 ° C., and then Cotamine D86P is added dropwise little by little. Coatamine D86P may be dissolved in water and used as an aqueous solution. After adding Cotamine D86P dropwise, the mixture is stirred at 70 to 90 ° C. for 60 minutes to sufficiently react. In order to confirm the end point of the reaction, it can be judged that the salt-forming compound was obtained with the reaction solution dropped on the filter paper and the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer. I. A xanthene dye ([A2] -4) which is a salt-forming compound of Acid Red 87 and distearyldimethylammonium chloride was obtained.
<Production method of fine pigment>
(Preparation of blue fine pigment ([A1] -1))
Triphenylmethane blue pigment C.I. I. 200 parts of Pigment Blue 1 (“Fanal Blue D 6340” manufactured by BASF), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of a blue fine pigment ([A1] -1) were obtained. The specific surface area of the blue fine pigment ([A1] -1) was 65 m ² / g, and the average primary particle size by TEM observation was 55 nm.
(Preparation of blue fine pigment ([A1] -2))
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 a blue fine pigment ([A1] -2). The specific surface area of the blue fine pigment ([A1] -2) was 80 m ² / g, and the average primary particle size by TEM observation was 50 nm.
(Preparation of red fine pigment)
Diketopyrrolopyrrole red pigment C.I. I. 200 parts of Pigment Red 254 (“IRGAZIN RED 2030” manufactured by Ciba Japan), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of a red fine pigment were obtained. The specific surface area of the red fine pigment was 65 m ² / g, and the average primary particle size by TEM observation was 54 nm.
(Production of green fine pigment)
Phthalocyanine green pigment C.I. I. 200 parts of Pigment Green 36 (“Lionol Green 6YK” manufactured by Toyo Ink Manufacturing Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. . Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of a green fine pigment were obtained. The specific surface area of the green fine pigment was 75 m ² / g, and the average primary particle size by TEM observation was 51 nm.
(Preparation of yellow fine pigment 1)
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, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 490 parts of yellow fine pigment 1 were obtained. The specific surface area of the yellow fine pigment 1 was 80 m ² / g, and the average primary particle diameter by TEM observation was 49 nm.
(Preparation of yellow fine 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 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 yellow fine pigment 2 were obtained. The specific surface area of the yellow fine pigment 2 was 70 m ² / g, and the average primary particle size by TEM observation was 53 nm.
there were.
(Production of purple fine pigment)
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 a violet fine pigment were obtained. The specific surface area of the purple fine pigment was 95 m ² / g, and the average primary particle size by TEM observation was 45 nm.
there were.
<Method for producing pigment dispersion>
(Preparation of pigment dispersion (P-1))
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. A pigment dispersion (P-1) was produced by filtration using a filter.
Blue fine pigment ([A1] -1): 11.0 parts (CI Pigment Blue 1)
Acrylic resin solution 1: 40.0 parts propylene glycol monomethyl ether acetate (PGMAC): 48.0 parts Resin type dispersant: 1.0 part (“EFKA4300” manufactured by Ciba Japan)
(Preparation of pigment dispersion (P-2 to 7))
Hereinafter, pigment dispersions (P-2 to 7) were produced in the same manner as the pigment dispersion (P-1) except that the pigments were changed to the pigments shown in Table 1.

<Preparation of dye-containing resin solution>
(Dye-containing resin solution (DA-1))
4. The following mixture is stirred and mixed so as to be uniform, and then dispersed for 5 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm. A dye-containing resin solution (DA-1) was prepared by filtration through a 0 μm filter.
Xanthene dye [A2] -1: 11.0 parts Acrylic resin solution 1: 40.0 parts Cyclohexanone: 49.0 parts Hereinafter, except that salt forming compound 1 is changed to xanthene dye [A2] shown in Table 2 The dye-containing resin solutions (DA-2 to DA-4) were prepared in the same manner as the dye-containing resin solution (DA-1).

  Moreover, except having changed the acrylic resin solution 1 into the acrylic resin solution 1B, it carried out similarly to said dye containing resin solution (DA-1), and produced the dye containing resin solution (DA-5).

  Moreover, except having changed the acrylic resin solution 1 into the acrylic resin solution 2B, it carried out similarly to said dye containing resin solution (DA-1), and produced the dye containing resin solution (DA-6).

<Method for producing red and green resist materials>
(Preparation of red resist material)
The following mixture was stirred and mixed to be uniform and then filtered through a 1.0 μm filter to obtain a red resist material.
Pigment dispersion (P-3): 50.0 parts Pigment dispersion (P-5): 10.0 parts Acrylic resin solution 1: 11.0 parts Trimethylolpropane triacrylate: 4.2 parts (Shin Nakamura Chemical Co., Ltd.) "NK ester ATMPT"
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 ethylene glycol monomethyl ether acetate: 23.2 parts (Preparation of green resist material)
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.
Pigment dispersion (P-4): 45.0 parts Pigment dispersion (P-6): 15.0 parts Acrylic resin solution 1: 11.0 parts Trimethylolpropane triacrylate: 4.2 parts (Shin Nakamura Chemical Co., Ltd.) "NK ester ATMPT"
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 ethylene glycol monomethyl ether acetate: 23.2 parts <Method for Producing Phthalocyanine Amine Compound (C)>
Commercially available materials were used for the amine compounds (C-1) and (C-2) of copper phthalocyanine. Specific substance names and chemical structures are shown in Table 3.
(Production of amine compound (C-3) of copper phthalocyanine; copper phthalocyanine sulfonic acid amide compound)
After adding 30 parts of copper phthalocyanine to 300 parts of chlorosulfonic acid and completely dissolving it, 24 parts of thionyl chloride was added, and the temperature was gradually raised and reacted at 101 ° C. for 3 hours. The reaction solution was poured into 9000 parts of ice water, stirred, filtered and washed with water. The obtained press cake was made into a slurry with 300 parts of water, then 15 parts of N, N-dimethylaminopropylamine was added, and the mixture was stirred at room temperature for 3 hours, then at 60 ° C. for 2 hours, filtered, washed with water and dried. , 36 parts of a copper phthalocyanine sulfonic acid amide compound (C-3) was obtained. The obtained copper phthalocyanine sulfonic acid amide compound (C-3) was subjected to composition analysis using a liquid chromatograph / mass spectrometer platform LCZ manufactured by Waters. Copper phthalocyanine sulfonic acid amide compound (C-3-D1) having one substituent of (11) and copper phthalocyanine sulfonic acid amide compound (C-3-D2) having two substituents of the following general formula (11) The weight ratio of each was 85:15.
Formula (11)

(Production of amine compounds (C-4) to (C-6) of copper phthalocyanine; copper phthalocyanine sulfonic acid amide compound)
The above copper phthalocyanine sulfonic acid amide compound (C) was used except that N, N-dimethylaminopropylamine, which is a raw material used in the method for producing the copper phthalocyanine sulfonic acid amide compound (C-3), was changed to the raw material shown in Table 3. -3), copper phthalocyanine sulfonic acid amide compounds (C-4) to (C-6) were produced.
(Production of amine compound (C-7) of zinc phthalocyanine; zinc phthalocyanine sulfonic acid amide compound)
After charging 30 parts of zinc phthalocyanine in 300 parts of chlorosulfonic acid and completely dissolving it, 24 parts of thionyl chloride was added, and the temperature was gradually raised and reacted at 101 ° C. for 3 hours. The reaction solution was poured into 9000 parts of ice water, stirred, filtered and washed with water. The obtained press cake was made into a slurry with 300 parts of water, then 15 parts of N, N-dimethylaminopropylamine was added, and the mixture was stirred at room temperature for 3 hours, then at 60 ° C. for 2 hours, filtered, washed with water and dried. 36 parts of zinc phthalocyanine sulfonic acid amide compound (C-7) were obtained. The obtained zinc phthalocyanine sulfonic acid amide compound was subjected to a composition analysis using a liquid chromatograph mass spectrometer platform LCZ manufactured by Waters. The compound having 3 or more substituents was not included, and the substitution of the following formula (12) A mixture of a zinc phthalocyanine sulfonic acid amide compound (C-7-D1) having one group and a copper phthalocyanine sulfonic acid amide compound (C-7-D2) having two substituents of the following general formula (12), The weight ratio of each was 80:20.
Formula (12)
_{ZnPc - (- SO 2 NH -} (- CH 2) -N (CH 3) 2) m
m = 1, 2
Meaning of Abbreviations in General Formula (12) ZnPC: Zinc Phthalocyanine Residue

Meaning of Abbreviations in Table 3 CuPC: Copper phthalocyanine residue (copper phthalocyanine compound (D-1))
"SOLSPERSE 12000" (Nippon Lubrizol Corporation)
[Examples 1-11, 51, 52, Comparative Examples 1-4]
<Preparation of blue coloring composition>
(Example 1; blue coloring composition (DB-1)
4. The following mixture is stirred and mixed so as to be uniform, and then dispersed for 5 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm. It filtered with a 0 micrometer filter and produced the coloring composition for color filters (DB-1).
Dye-containing resin solution (DA-1): 10.0 parts Pigment dispersion (P-1): 50.0 parts Acrylic resin solution 1: 11.0 parts Cyclohexanone: 27.4 parts Resin-type dispersant: 1.0 (Ciba Japan "EFKA4300")
Copper phthalocyanine amine compound (C-1): 0.6 parts (“SOLPERSE 5000” manufactured by Nippon Lubrizol Corporation; copper phthalocyanine sulfonate ammonium salt)
Hereinafter, the blue colored composition (DB-1) described above except that the dye-containing resin solution (DA-1) is changed to the dye-containing resin solution and pigment dispersion shown in Table 4 and the amine compound (C) of copper phthalocyanine. In the same manner, blue colored compositions (DB-2) to (DB-15) and DB-21, 22 were produced. In some blue coloring compositions, two or more types of pigment dispersions are used, but the total weight part of the dye-containing resin solution and the pigment dispersion is 60 parts in all the blue coloring compositions. The produced blue coloring composition is shown in Table 4.
However, Examples 1 and 2 are reference examples.

[Example 61]
A blue colored composition DB-31 was prepared and evaluated in the same manner as in Example 1 except that the zinc phthalocyanine amine compound (C-7) was used instead of the copper phthalocyanine amine compound (C-1). As a result, the contrast ratio was 4970, which was preferable.
[Evaluation of Blue Colored Composition for Color Filter (DB-1 to DB-15, DB-21)]
Blue colored compositions (DB-1 to DB-15, DB-21, DB-22) obtained in Examples 1 to 11, 51 and 52 and Comparative Examples 1 to 4 were 100 mm × 100 mm and 1.1 mm thick. Each blue coloring composition was apply | coated to the film thickness which becomes y = 0.06 in C light source using a spin coater on the glass substrate of this, and this board | substrate was heated at 230 degreeC for 20 minutes. Then, the contrast ratio of the obtained substrate is shown in Table 4.

Examples 1 to 11, 51 and 52 containing a colorant (A) containing a blue pigment [A1] and a xanthene dye [A2] and an amine compound (C) of copper phthalocyanine are used as amine compounds of copper phthalocyanine The contrast ratio was higher than that of Comparative Examples 1 to 4 that did not contain (C). Among these, Examples 3 to 11, 51 and 52 (blue coloring compositions (DB-3 to DB-11, DB-21, 22)) using a copper phthalocyanine sulfonic acid amide compound show a higher contrast ratio. It was.
[Examples 12 to 26, 53, 54, Comparative Examples 5 to 8]
<Preparation of resist material>
(Example 12: Resist material (R-1))
The following mixture was stirred and mixed to be uniform, and then filtered through a 1.0 μm filter to obtain a resist material (R-1).
Blue coloring composition (DB-1): 60.0 parts acrylic resin solution 1: 11.6 parts trimethylolpropane triacrylate: 3.6 parts (“NK ester ATMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.)
Photopolymerization initiator (“Irgacure 907” manufactured by Ciba Japan Co., Ltd.): 1.2 parts sensitizer (“EAB-F” manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts ethylene glycol monomethyl ether acetate: 23.2 parts

(Examples 13-26, 53, 54, Comparative Examples 5-8; resist materials (R-2 to R-19, R-21, 22))
Hereinafter, the alkali developing resist is the same as the resist material (R-1) except that the blue coloring composition (DB-1) and the acrylic resin solution 1 are changed to the blue coloring composition and the acrylic resin solution shown in Table 5. Materials (R-2 to R-19, 21, 22) were obtained. Table 5 shows the compositions of the resist materials prepared in Examples 12 to 26, 53, and 54 and Comparative Examples 5 to 8.
[Evaluation of resist materials (R-1 to R-19, 21, 22)]
The color characteristics (brightness), contrast ratio, and heat resistance test of the resist materials (R-1 to R-19, 21, 22) obtained in Examples and Comparative Examples were performed by the following methods.
(Evaluation of color characteristics)
Each resist material was coated on a glass substrate to a thickness such that y = 0.06 for the blue resist material in a C light source, and this substrate was heated at 230 ° C. for 20 minutes. Thereafter, the brightness of the obtained substrate was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.). The results are shown in Table 5.
(Contrast ratio evaluation)
The contrast ratio was measured using the same substrate on which the color characteristics were measured. The results are shown in Table 5.
(Method of coating heat resistance test)
A resist material is applied on a transparent substrate so that the dry coating thickness is about 2.5 μm, and UV exposure is performed through a mask having a predetermined pattern, and then an alkali developer is sprayed to remove uncured portions. Thus, a desired pattern was formed. Then, after heating in an oven at 230 ° C. for 1 hour and allowing to cool, the 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, the sample 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. The results are shown in Table 5.
Using the measured color difference value, a chromaticity change ΔEab * was calculated by the following formula, and the heat resistance of the coating film was evaluated in the following four stages. The results are shown in Table 5.
However, Examples 12 and 13 are reference examples.

ΔEab * = √ ((L * (2)-L * (1)) ² + (a * (2)-a * (1)) ² + (b * (2)-b * (1)) ² )
◎: ΔEab * is less than 1.5 ○: ΔEab * is 1.5 or more and less than 3.0 Δ: ΔEab * is 3.0 or more and less than 5.0 ×: ΔEab * is 5.0 or more

  Similar to the evaluation results of the coloring composition, Examples 12 to 26 and 53 containing a coloring agent (A) containing a blue pigment [A1] and a xanthene dye [A2] and an amine compound (C) of copper phthalocyanine , 54 showed a high contrast ratio compared to Comparative Examples 5 to 8 which did not contain the copper phthalocyanine amine compound (C). Among these, Examples 14 to 26, 53, and 54 using a copper phthalocyanine sulfonic acid amide compound showed a higher contrast ratio. This is because the electrostatic attraction between the xanthene dye and the copper phthalocyanine sulfonic acid amide compound effectively quenches the fluorescence of the dye, and the compatibility between the dye and the copper phthalocyanine blue pigment is good. Therefore, it is considered that the copper phthalocyanine particles and the dye are not unevenly distributed in the resist and light scattering is suppressed, so that the cross luminance becomes extremely low, and as a result, the contrast ratio is improved.

  In Example 3 where the weight ratio ((C) / [A2]) of the phthalocyanine amine compound (C) to the xanthene dye [A2] is in the range of 0.3 to 1.5, the phthalocyanine amine compound (C ) Has a small influence on the color characteristics of the blue coating film, and ((C) / [A2]) is superior to Example 4 in which ((C) / [A2]) is greater than 1.5, and ((C) / [A2]) is 0. Since the ability to suppress fluorescence was superior to that of Example 5 smaller than .3, the contrast ratio was high.

  In Examples 13 to 26, 53 and 54, C.I. which is a copper phthalocyanine pigment as a blue pigment. I. Pigment Blue 15: 6 is used, and therefore triarylmethane-based C.I. I. The heat resistance was superior to that in the case of using CI Pigment Blue 1.

  On the other hand, in Comparative Example 8 using a fine pigment (CI Pigment Violet 23) instead of xanthene dye, a decrease in lightness and a decrease in heat resistance were confirmed.

  In the heat resistance test, when a rhodamine salt forming compound or a rhodamine sulfonic acid amide compound is used among xanthene dyes, a xanthene salt forming dye (Example 26) is used or a fine pigment (C.I. It was confirmed that the heat resistance is superior to that of CI Pigment Violet 23). On the other hand, in Examples 17 to 19 and Examples 22 and 54, good results were obtained in the heat resistance test. This is presumably because the curability of the coating film was improved by using an active energy ray curable resin having an ethylenically unsaturated double bond in the resin solution.

From these results, it has been clarified that the resist material using the colored composition of the present invention can provide excellent quality having all of color characteristics (brightness), contrast ratio, and heat resistance.
[Examples 27-41, 55, 56, Comparative Examples 9-12]
A color filter was produced using the obtained resist material.
(Example 27: Color filter (CF-1))
A black matrix is patterned on a glass substrate, and a red resist material is applied on the substrate with a spin coater in a C light source (hereinafter also used for green and blue) to a thickness of x = 0.640 and colored. A film was formed. The film was irradiated with ultraviolet rays of 300 mJ / cm ² through a photomask using an ultrahigh pressure mercury lamp. Next, spray development was performed with an alkaline developer composed of a 0.2% by weight aqueous sodium carbonate solution to remove unexposed portions, followed by washing with ion-exchanged water. The substrate was heated at 230 ° C. for 20 minutes to obtain a red filter segment. Formed. In the same manner, the green resist material is applied to a thickness such that y = 0.600, and the blue resist material (R-1) is applied to a thickness such that y = 0.06. A blue filter segment was formed to obtain a color filter (CF-1).
(Production of liquid crystal display device)
A transparent ITO electrode layer was formed on the obtained color filter, and a polyimide alignment layer was formed thereon. A polarizing plate was formed on the other surface of this glass substrate. On the other hand, a TFT array and a pixel electrode were formed on one surface of another (second) glass substrate, and a polarizing plate was formed on the other surface. The two glass substrates prepared in this way are arranged facing each other so that the electrode layers face each other, and are aligned using spacer beads while keeping the distance between the two substrates constant, and an opening for injecting a liquid crystal composition The periphery was sealed with a sealant so as to leave After injecting the liquid crystal composition from the opening, the opening was sealed. The liquid crystal display device thus produced was combined with a backlight unit to obtain a liquid crystal panel.
(Examples 28-41, 55, 56, Comparative Examples 9-12: Color filters (CF-2-19, 21, 22))
Hereinafter, primary color filters (CF-2 to 19, 21, 22) and a liquid crystal display device were produced in the same manner as the color filter (CF-1) except that the resist material was changed to the resist material shown in Table 6. . The red resist material and the green resist material were fixed conditions. The emission spectrum of the backlight used is shown in FIG.
[Evaluation of color filters (CF-1 to 19, 21, 22)]
Thereafter, in the obtained liquid crystal display device, a light source is emitted to display a color image, and in the primary color filter, the brightness of the red, green, and blue filter segment portions is measured with a microspectrophotometer ("OSP-" manufactured by Olympus Optical Co., Ltd.). SP200 "), and the brightness of white display in the color filter was determined from the obtained brightness. The contrast ratio of the red, green and blue filter segment portions was also measured with a microspectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.). The contrast ratio was determined. Incidentally, the practical performance of the white display contrast ratio is required to be 7600 or more, and preferably a numerical value of 7600 or more. Table 6 shows the evaluation results of the color filter.
However, Examples 27 and 28 are reference examples.

  Examples 27 to 41, 55 and 56 are Comparative Examples 9 to 12 which do not contain the colorant (A) containing the blue pigment [A1] and the xanthene dye [A2] and the amine compound (C) of copper phthalocyanine. On the other hand, the contrast ratio of the white display was high and satisfied the practical performance. This was calculated because Comparative Examples 9 to 11 did not contain an amine compound (C) of copper phthalocyanine, and thus a fluorescent component due to xanthene dye was present as leakage light, and as a result, the cross luminance at the time of measuring the contrast ratio was increased. This is because the contrast ratio is low. Further, it was confirmed that the brightness was further lowered in Comparative Example 12 using a fine pigment (CI Pigment Violet 23) instead of rhodamine dye or xanthene dye.

From the above, by using the colorant (A) containing the blue pigment [A1] and the xanthene dye [A2] together with the amine compound (C) of copper phthalocyanine, color characteristics (lightness) and heat resistance, It has become possible to obtain a blue coloring composition for color filters and a color filter having an excellent contrast ratio.

Claims (6)

Look-containing blue pigment [A1] and xanthene dyes [A2] and colorant comprising a (A), the resin (B), the general formula (1) an amine compound of phthalocyanine having a structure represented by the (C) A blue coloring composition for a color filter , wherein the weight ratio (C / [A2]) between the xanthene dye [A2] and the compound (C) is 0.3 to 1.5 .
General formula (1)
P-Lm
[In General Formula (1), P is an m-valent phthalocyanine pigment residue, m is an integer of 1 to 4, and L is General Formula (2), (3), or (4) Any of the substituents selected from the group shown. ]
General formula (2):

General formula (3):

General formula (4):

[In the general formulas (2) to (4), X represents —SO ₂ —, —CH ₂ NHSO ₂ CH ₂ —,
Y ⁰ is —NH—, —O—, or a direct bond;
n is an integer of 1 to 10,
Y ¹ is —NH—, —NR ⁹ —Z—NR ¹⁰ —, or a direct bond;
R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 36 carbon atoms, an alkenyl group having 2 to 36 carbon atoms, or a phenyl group,
Z represents an alkylene group having 1 to 20 carbon atoms or an arylene group having 1 to 20 carbon atoms.
R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or a combination of R ¹ and R ² with further nitrogen, oxygen Or a heterocycle containing a sulfur atom,
R ³ , R ⁴ , R ⁵ , and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms. ,
R ⁷ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms,
R ⁸ is a substituent represented by the general formula (2) or a substituent represented by the general formula (3),
Q represents a hydroxyl group, an alkoxyl group having 1 to 20 carbon atoms, a substituent represented by the general formula (2), or a substituent represented by the general formula (3). ]   The blue coloring composition for a color filter according to claim 1, wherein the blue pigment [A1] is a copper phthalocyanine pigment.   The blue coloring composition for a color filter according to claim 1 or 2, wherein the xanthene dye [A2] is a salt forming compound of a xanthene acid dye and / or a sulfonic acid amide compound of a xanthene acid dye. .   The blue coloring composition for a color filter according to any one of claims 1 to 3, wherein the xanthene dye [A2] is a rhodamine dye.   A color filter comprising a filter segment formed from the blue coloring composition for a color filter according to any one of claims 1 to 4 on a substrate. A pigment dispersion containing a colorant (A) containing a blue pigment [A1] and a resin (B), a xanthene dye [A2], and an amine compound of phthalocyanine having a structure represented by the general formula (1) (C) is added, The manufacturing method of the blue coloring composition for color filters characterized by the above-mentioned.

General formula (1)
P-Lm
[In General Formula (1), P is an m-valent phthalocyanine pigment residue, m is an integer of 1 to 4, and L is General Formula (2), (3), or (4) Any of the substituents selected from the group shown. ]
General formula (2):

General formula (3):

General formula (4):

[In the general formulas (2) to (4), X represents —SO ₂ —, —CO—, —CH ₂ —,
_{-CH 2 NHCOCH 2 -, - CH} 2 NHSO 2 CH 2 -, or a direct bond,
Y ⁰ is —NH—, —O—, or a direct bond;
n is an integer of 1 to 10,
Y ¹ is —NH—, —NR ⁹ —Z—NR ¹⁰ —, or a direct bond;
R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 36 carbon atoms, an alkenyl group having 2 to 36 carbon atoms, or a phenyl group,
Z represents an alkylene group having 1 to 20 carbon atoms or an arylene group having 1 to 20 carbon atoms.
R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or a combination of R ¹ and R ² with further nitrogen, oxygen Or a heterocycle containing a sulfur atom,
R ³ , R ⁴ , R ⁵ , and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms. ,
R ⁷ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms,
R ⁸ is a substituent represented by the general formula (2) or a substituent represented by the general formula (3),
Q represents a hydroxyl group, an alkoxyl group having 1 to 20 carbon atoms, a substituent represented by the general formula (2), or a substituent represented by the general formula (3). ]

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