TWI480602B - Coloring composition for color filter, and color filter - Google Patents

Description

Coloring composition and color filter for color filters

The present invention relates to a coloring composition for a color filter and a color filter including a filter segment formed using the coloring composition, and the coloring composition for the color filter is used for color production. A color filter used for liquid crystal display devices and color image sensor elements.

The liquid crystal display device is a display device that controls the degree of polarization of light passing through the first polarizing plate and controls the amount of light passing through the second polarizing plate to display the liquid crystal layer sandwiched between the two polarizing plates. The mainstream of the display device utilizes the type of twisted nematic (TN) mode. The liquid crystal display device can perform color display by providing a color filter between two polarizing plates. Liquid crystal display devices that can perform color display are widely used in televisions or personal computer monitors.

Other representative liquid crystal display methods include: providing a pair of electrodes on one substrate, and applying an electric field to the parallel direction (IPS) of the substrate; and making the nematic liquid crystal having negative dielectric anisotropy vertically aligned. The vertical alignment (VA) method or the optical compensation bending (OCB) method in which the optical axes of the uniaxial retardation films are orthogonal to each other, and each method has been put into practical use.

In general, a color filter is formed on a surface of a transparent substrate such as glass, and red (R), green (G), and blue (B) filter layers are arranged in parallel or intersecting, or are equivalent to red or green. , a complementary color of blue, that is, a thin band (striped) filter segment (pixel) composed of cyan (C), magenta (M), and yellow (Y) filter layers, or arranged in a vertical and horizontal direction It is composed of a fine filter section. The filter segments are a few micrometers to hundreds of micrometers, are very fine, and are arranged neatly in a specific arrangement for each hue.

For use in a color filter of a color liquid crystal display device, a transparent electrode for driving a 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. In order to sufficiently obtain the properties of the transparent electrode and the alignment film, the formation step is generally carried out at a high temperature of 200 ° C, more preferably 230 ° C or higher.

For the quality items required for color filters, the contrast ratio and brightness can be cited. If a color filter that cannot achieve a high contrast ratio is used, the polarization state controlled by the liquid crystal may be disordered, when light is blocked (closed state), or when light is required to be transmitted (on state) The transmitted light is attenuated, so the color filter becomes blurred. Therefore, in order to realize a high-quality liquid crystal display device, a high contrast system is indispensable.

Further, when a color filter having a low luminance is used, since the transmittance of light is low, the screen is dim, and in order to make the screen bright, the number of backlights as a light source must be increased. Therefore, from the viewpoint of suppressing an increase in power consumption, high luminance of color filters has been a trend. Further, as described above, since the color liquid crystal device is used for a television or a personal computer monitor or the like, the color filter is required to have high luminance and high contrast, and the demand for high reliability is also increased.

The color filter manufacturing method includes using a dye, a halogenated dye as a coloring A dyeing method of a dye, a dye dispersion method, or a pigment dispersion method using a pigment as a colorant, a printing method, a plating method, or the like. Among these methods, since the coloring agent of the dyeing method or the dyeing dispersion method is a dye, it has a disadvantage that heat resistance or light resistance is slightly inferior. Therefore, most of the color filter coloring agents utilize pigments having good heat resistance or light resistance, and are considered from the precision or stability of the formation method, and the production method mostly uses a pigment dispersion method.

In the pigment dispersion method, a pigment particle as a coloring agent is dispersed in a resin, and a sensitizer or an additive is mixed and mixed to form a color resist, and a coating device such as a spin coater is applied to the substrate. The color resist is formed into a coating film, and is selectively exposed by a photomask by an alignment machine, a stepper, or the like, and subjected to alkali development and heat hardening treatment to be patterned, and the operation is repeated. The method of making a color filter.

In general, the pigment particles are subjected to a refining treatment to produce a pigment dispersion in which the finely pigmented pigment has reached the limit of the primary particles, thereby suppressing light scattering by the pigment, thereby achieving high contrast. Further, since the transparency of the dispersion is also improved, the spectral spectrum of the dispersion has a high transmittance and high luminance can be achieved. By using the dispersion for a color resist, a color filter having high contrast and high brightness can be obtained.

In recent years, dye-based color materials have attracted attention in order to achieve high contrast ratios and high brightness in which only pigments can be achieved. Among them, xanthene pigments such as rose red pigment and ruthenium pigment, diarylmethane dyes such as diphenylmethane, and triarylmethane dyes such as triphenylmethane are preferable because of their superior color characteristics. The material is expected to be.

However, dyes such as xanthene-based pigments and triarylmethane-based dyes have high solubility in a solvent, and thus do not cause scattering or the like as seen when only a pigment is used, and it is expected that a color filter having a high contrast ratio can be obtained. However, since fluorescence is present (refer to, for example, Patent Document 6), There is a problem that the contrast ratio becomes lower. Therefore, it has not been realized in the current state that a color filter which can be simultaneously formed by high-luminance and high contrast ratio can be realized by a fluorescent dye.

Advanced technical literature

Patent Document 1: Japanese Patent Laid-Open No. Hei 6-75375

Patent Document 2: Japanese Laid-Open Patent Publication No. 2001-81348

Patent Document 3: Japanese Laid-Open Patent Publication No. 2005-292305

Patent Document 4: Japanese Laid-Open Patent Publication No. 2009-265641

Patent Document 5: Japanese Laid-Open Patent Publication No. 2010-32999

Patent Document 6: Japanese Laid-Open Patent Publication No. 2005-025175

The inventors of the present invention have earnestly accumulated research in order to solve the above problems, and as a result, have found that by using a fluorescent pigment (A), having an organic pigment skeleton or an aniline skeleton, and having an acidic functional group, a basic functional group or an anthracene. The organic compound (B) of the quinone imine skeleton can improve the contrast ratio and achieve high brightness and high contrast ratio, and the present invention has been completed based on this discretion.

That is, according to one aspect of the present invention, there is provided a coloring composition for a color filter comprising a fluorescent pigment (A), an organic compound (B) represented by the general formula (1), and Resin binder (C).

General formula (1): P-Lm [In general formula (1), P is an organic pigment skeleton or an aniline skeleton, and L is a basic functional group Lb, an acidic functional group La or a functional group Lp having a quinone imine skeleton , m is an integer from 1 to 4, indicating the number of functional groups.

Further, according to another aspect of the present invention, a color filter is provided, characterized in that a filter segment is provided on a substrate, and the filter segment is as claimed in claims 1 to 8 of the patent application. One color filter is formed using a colored composition.

The fluorescent pigment (A) is derived from a triphenylmethane dye, a diphenylmethane dye, a quinoline dye, a thiazine dye, a thiazole dye, a xanthene dye, and a diketopyrrolopyrrole dye. Any of the selected groups may also be selected.

The organic pigment skeleton is derived from a phthalocyanine pigment, a benzimidazolone pigment, a dioxazine pigment, an azo pigment, an anthraquinone pigment, a diterpene pigment, a diketopyrrolopyrrole pigment, a thiazine. Any one of the groups consisting of indigo pigments and quinophthalone pigments may also be selected.

The basic functional group Lb has a basic functional group represented by the general formula (2) or (5), and the acidic functional group La has an acidic functional group represented by the general formula (3) or (5) and has a quinone imine skeleton. The functional group Lp may have a functional group represented by the general formula (4) or (5).

General formula (4):

[In the general formulas (2) to (4), X ¹ is -SO ₂ -, -CO-, -CH ₂ -, -NH-, -O-, an alkenyl group having 2 to 36 carbon atoms, and a carbon number of 1 ~20 alkylene, arylene having 1 to 20 carbon atoms, -CH ₂ NHCOCH ₂ -, -CH ₂ NHSO ₂ CH ₂ -, -CONHC ₆ H ₁₀ -, -CONHC ₆ H ₄ CO-, -OCH ₂ CH ₂ - or directly combined; in the general formulas (2), (4), Y ¹ is -NH-, -O- or directly bonded, n is an integer from 0 to 10; in the general formula (2), R ¹ and R ² are as follows: 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 hydrogen atom at the terminal, -NR ⁴ R ⁵ or -NR ⁴ R ⁵ H ⁺ U ^- alkanediyl having 1 to 30 carbon atoms; or R ¹ and R ² being integrated to form a heterocyclic ring which may further contain a nitrogen, oxygen or sulfur atom; the alkanediyl group may be contained by -O-substitution -CH ₂ -, U ^- represents an anion which represents a halide, BF ₄ ^- , PF ₆ ^- , ClO ₄ ^- , R ⁶ -CO ₂ ^- , R ⁷ -SO ₃ ^- [R ⁶ , R ⁷ contains aromatic a monovalent organic group of the group]; R ³ is a ring-substituted group when R ¹ and R ^{2 are} integrated, o is a number thereof, and when o is 2 or more, R ³ may have another structure, and each of them is a hydrogen atom or a carbon. Alkyl groups of 1 to 20, alkenyl groups having 2 to 20 carbons or carbon 6 to 20. The arylene; general formula (3), G-based _{^{-COO -, -SO 3 -, -PO}} 3 2-, -OPO 3 2-, benzoic acid-terminated (-Ph-COO ^-), Any of the end of the salicylic acid (-Ph(OH)-COO ^- ), the end of the benzenesulfonic acid (-Ph-SO ₃ ^- ), and the end of the phosphate (-Ph-PO ₃ ^2- ), the M system includes the G, etc. a cation of a hydrogen cation (Ph is a phenyl group); in the general formula (4), R ⁸ is a hydrogen atom, a halogen atom, -NO ₂ , -NH ₂ or -SO ₃ H, and p is 1 to 4 In the general formula (5), R ⁹ is a functional group represented by the general formulae (2) to (4); Q ¹ is a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, or a general formula ( 2) to (4) functional groups; X ² -SO ₂ -, -CO-, -CH ₂ -, -NH-, -O-, 2 to 36 carbons, carbon number 1~ 20 alkylene, arylene having 1 to 20 carbon atoms, -CH ₂ NHCOCH ₂ -, -CH ₂ NHSO ₂ CH ₂ -, -CONHC ₆ H ₁₀ -, -OCH ₂ CH ₂ -, -NHCOCH (COCR ¹⁰ ) or direct combination; Y ² -NH-, -NR ¹¹ -Z-NR ¹² -, -SO ₂ -Z-NR ¹³ -, -N=N- or direct combination, R ¹¹ ~R ¹³ are separately It is 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; a Z-alkylene group having 1 to 20 carbon atoms or an Atomatic number having 1 to 20 carbon atoms; ; T independently each line having a substituent of a carbon atom or a carbon atom also. ]

Further, the present invention relates to the coloring composition for a color filter, characterized in that the anion M of the general formula (3) is a hydrogen ion, an alkali metal ion, an alkaline earth metal ion, a rare earth metal ion, a transition metal ion, and a general Any of the anions represented by the formula (8).

[In the general formula (6), R ¹⁴ to R ¹⁷ represent a hydrogen atom or an alkyl group having 1 to 30 carbon atoms (but not all hydrogen atoms). ]

The fluorescent pigment (A) may be a fluorescent acid dye halide and/or a fluorescent acid dye sulfonate amide compound.

The weight ratio of the organic compound (B) to the fluorescent pigment (A) may be 0.05 to 2.0.

The coloring composition for a color filter may further contain an organic pigment (D).

According to the present invention, it is possible to provide a coloring composition which can improve the contrast ratio of a problem in the case of using a fluorescent pigment, and to produce a color filter having a high luminance and a high contrast ratio.

The invention is described in detail below.

Furthermore, in the scope of this specification and the patent application, it is indicated as "(meth)acrylonitrile", "(meth)acrylyl", "(meth)acrylic acid", "(meth)acrylate" or " In the case of (meth)acrylamide, unless otherwise specified, "acrylonitrile and/or methacryl", "acryl" and/or methacryl", "acrylic acid and/or methacrylic acid" are respectively indicated. "Acrylate and / or methacrylate" or "acrylamide and / or methacrylamide".

Further, "C.I." described below means a color index (C.I.).

The coloring composition for a color filter according to an aspect of the present invention is characterized by comprising a fluorescent pigment (A), an organic compound (B) and a resin binder (C), and the aforementioned organic compound (B) has an organic A pigment skeleton or an aniline skeleton, and an acidic functional group, a basic functional group or a quinone imine skeleton.

"Colorant"

The colored filter coloring composition contains a fluorescent pigment (A) as a coloring agent. It is also advisable to use a fluorescent pigment (A) and a non-luminescent organic pigment (D).

<Fluorescent Pigment (A)>

The fluorescent pigment (A) is not particularly limited as long as it is a fluorescent pigment. That is, if it is a fluorescent dye or a fluorescent pigment, it can be used. For example, triphenylmethane dye, triphenylmethane lake pigment, diphenylmethane dye, diphenylmethane lake pigment, quinoline dye, quinoline pigment, thiazine dye, thiazole dye, xanthene It is a dye, a xanthene lake pigment, a diketopyrrolopyrrole pigment, and the like.

Among these, it is preferable to use a xanthene dye, a xanthene pigment of a xanthene lake pigment, a quinoline dye, a quinoline dye of a quinoline pigment, a triphenylmethane dye, and a triphenylmethane. A diphenylmethane-based dye, a diphenylmethane-based dye, a diphenylmethane-based pigment of a diphenylmethane-based lake pigment, and a diketopyrrolopyrrole-based dye of a diketopyrrolopyrrole-based pigment.

In particular, when a pigment which emits fluorescence in the visible light region is used, the effect of producing a color filter having a high contrast ratio is very good.

When the fluorescent pigment (A) is in the form of a dye, it is preferred to have any of various dyes such as an oil-soluble dye, an acid dye, a direct dye, a basic dye, a mordant dye, and an acid mordant dye.

Further, examples of the pigment form include a pigment which is fluorescent or a lake pigment which is subjected to laked dyeing.

When the dye (A) is a dye, it is preferable to use an oil-soluble dye, an acid dye, a direct dye, or a basic dye because the hue is good.

Oil-soluble dyes include dyes classified as CI Solvent according to the classification of color index. Basic dyes include dyes classified as CI Basic (CIBasic), and acid dyes include the same classification as CI acid (CIAcid). Dyes, direct dyes include dyes classified as CI Direct. Here, the direct dye is a substance having a sulfonic acid group (-SO ₃ H, -SO ₃ Na) in the structure, and thus the direct dye is regarded herein as an acid dye.

The preferred fluorescent dye (A) will be specifically described below.

(xanthene dye: xanthene dye, its lake pigment)

In the case of a xanthene dye, the transmittance in the 650 nm region is preferably 90% or more in the penetration spectrum, and the transmittance in the 600 nm region is preferably 75% or more, and the transmittance in the region of 500 to 550 nm. It is preferably 5% or less, and the transmittance in the 400 nm region is preferably 70% or more. More preferably, the transmittance in the 650 nm region is above 95%, and the transmittance in the 600 nm region is above 80% at 500. The transmittance in the ~550 nm region is below 10%, and the transmittance in the 400 nm region is above 75%. Among them, the spectroscopic characteristics of the xanthene-based basic dyes and the xanthene-based acid dyes are highly penetrating at 400 to 450 nm.

Further, among the xanthene-based pigments, the rosin-based pigment is particularly preferable because it has particularly good color developability and tolerance.

(The form of the xanthene dye as an oil-soluble dye)

The xanthene-based oil-soluble dye may specifically be CI solvent red 35, CI solvent red 36, CI solvent red 42, CI solvent red 43, CI solvent red 44, CI solvent red 45, CI solvent red 46, CI solvent red 47, CI Solvent Red 48, CI Solvent Red 49, CI Solvent Red 72, CI 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, etc.

Among them, rose red oil-soluble dye CI solvent red 35, CI solvent red 36, CI solvent red 49, CI solvent red 109, CI solvent red 237, CI solvent red 246, CI solvent violet 2 are suitable for high color rendering. .

(The form of the xanthene dye as an acid dye)

Acid dyes (xanthene acid dyes) of xanthene dyes should be CI Acid Red 51 (erythro red (food red 3)), CI acid red 52 (acid rose red), CI acid red 87 (blush G) (edible red 104)), CI acid red 92 (acid oleander red PB (food red 104)), CI acid red 289, CI acid red 388, tiger red B (food red 5), acid rose red G, CI Acid Violet 9.

Among them, from the aspect of heat resistance and light resistance, it is preferable to use xanthene acid dye C.I. acid red 87, C.I. acid red 92, C.I. acid red 388, or rose red acid dye C.I. Acid red 52 (acid rose red), C.I. acid red 289, acid rose red G, C.I. acid violet 9.

Among them, C.I. Acid Red 52 and C.I. Acid Red 289 are particularly preferably used from the viewpoints of color rendering property, heat resistance, and light resistance.

(The form of xanthene dye as a basic dye)

Examples of the xanthene-based basic dyes include C.I. Basic Red 1 (Rose Red 6GCP), 8 (Rose Red G), C.I. Basic Violet 10 (Rose Red B), and the like. Among them, in view of good color rendering, it is preferable to use C.I. Basic Red 1, C.I. Basic Violet 10.

(The form of xanthene dye as a lake pigment)

The metal lake pigment of the xanthene dye can be CI basic red 81, CI basic red 81:1, CI basic red 81:2, CI basic red 81:3, CI basic red 81:4, CI basic red 81: 5, CI basic red 169, CI basic purple 1, CI basic purple 1:1, CI basic purple 1:2, CI basic purple 2 and so on.

(Diphenyl and triphenylmethane dyes: triphenylmethane dyes, diphenylmethane dyes, and lake pigments thereof)

In the case of a diphenyl and triphenylmethane-based dye, the blue (blue) triarylmethane-based basic dye has a high spectral permeability at 400 to 440 nm.

(Diphenyl and triphenylmethane dyes are used as acid dyes)

Acid dyes for diphenyl and triphenylmethane dyes should be Edible Blue No. 101 (CI Acid Blue 1), Acid Pure Blue (CI Acid Blue 3), Lake Blue I (CI Acid Blue 5), Lake Blue II (CI) Acid Blue 7), Edible Blue No. 1 (CI Acid Blue 9), CI Acid Blue 22, CI Acid Blue 83, CI Acid Blue 90, CI Acid Blue 93, CI Acid Blue 100, CI Acid Blue 103, CI Acid Blue 104, CI Acid Blue 109.

(Diphenyl and triphenylmethane dyes are used as basic dyes)

The triphenylmethane-based basic dye and the diphenylmethane-based basic dye form a benzoquinone structure by oxidation with respect to the NH ₂ or OH group in the para position with respect to the central carbon, thereby developing color.

These dyes are classified into the following three types depending on the number of NH ₂ and OH groups, and in the form of a good blue, red, and green color, the form of the triamine triphenylmethane-based basic dye is should.

a) diamine triarylmethane basic dye

b) triamine triarylmethane basic dye

c) Rose acid basic dye with OH group

The triamine triarylmethane-based basic dye and the diamine-triarylmethane-based basic dye are more suitable in color tone and sunlight solidity than other dyes. Further, it is preferably a benzophenone basic dye and/or a triphenylmethane basic dye.

Specifically, CI basic blue 1 (basic cyanine 6G), CI basic blue 5 (basic cyanine EX), CI basic blue 7 (Victoria pure blue BO), CI basic blue 25 (basic blue GO), CI basic Blue 26 (Victoria Blue B conc.) and so on.

C.I. Basic Green 1 (Huanglu GX), C.I. Basic Green 4 (Peacock Green), and the like are mentioned.

C.I. Basic Violet 1 (methyl Violet), C.I. Basic Violet 3 (Crystal Violet), C.I. Basic Violet 14 (Magenta), and the like are mentioned.

(Diphenyl and triphenylmethane dyes as a form of lake pigment)

Specifically, the triarylmethane-based lake pigments include CI Pigment Blue 1, CI Pigment Blue 2, CI Pigment Blue 9, CI Pigment Blue 10, CI Pigment Blue 14, CI Pigment Blue 62, CI Pigment Violet 3, CI. Pigment Violet 27, CI Pigment Violet 39, and the like.

The following specifically indicates the preferred one.

C.I. Pigment Blue 1

C.I. Pigment Blue 26, C.I. Pigment Blue 7 by phosphotungsten ‧ molybdate

C.I. Pigment Violet 3

C.I. Pigment Violet 1 by phosphotungsten ‧ molybdate

C.I. Pigment Violet 39

C.I. Basic purple 3 (crystal violet) by phosphotungsten ‧ molybdate

Among them, it is preferable to use C.I. Pigment Blue 1.

(Quinoline-based dye: quinoline dye, quinoline pigment)

Examples of the quinoline dye include commercially available dyes such as Solvent Yellow 33, Solvent Yellow 98, Solvent Yellow 157, Disperse Yellow 54, Disperse Yellow 160, and Acid Yellow 3.

The quinoline-based pigment may, for example, be C.I. Pigment Yellow 138 (Paliotol Yellow K0961-HD manufactured by BASF Corporation).

(thiazine dye)

The thiazine-based dye may be a Lauth's Violet, methylene blue, methylene green, CI basic blue 9, 17, 24, 25 obtained by oxidizing P-aniline with FeCl ₂ in the presence of hydrogen sulfide. Solvent Blue 8, CI Basic Green 5, CI Direct Red 70, etc.

(thiazole dye)

The thiazole dye is a thiazole dye based on a dye having a thiazole ring, and specifically, CI basic yellow 1, CI basic violet 44, 46, CI basic blue 116, CI acid yellow 186, CI direct yellow 7, 8 , 9, 14, 17, 18, 22, 28, 29, 30, 54, 59, 165, CI straight Orange, C.I. Direct Red 11, etc.

(diketopyrrolopyrrole pigment)

The diketopyrrolopyrrole pigment is a red-orange pigment having a structure represented by the following general formula (7). Specific examples of the diketopyrrolopyrrole pigment represented by the following general formula (7) include C.I. Pigment Red 254, 255, 264, 272 and C.I. Pigment Orange 71, 73, and 81.

In the formula, X and Y each independently represent CN, C(CH ₃ ) ₃ , CH ₃ , Cl, C ₆ H ₅ or H.

Although the fluorescent pigment (A) has good spectral characteristics and good color rendering properties, it has problems in light resistance and heat resistance, and its characteristics are sometimes insufficient for use in color filters requiring high reliability. Image display device.

Therefore, in order to improve these disadvantages, in the case of a basic dye form, it is preferable to use it by halogenating with an organic acid or perchloric acid. The organic acid is preferably an organic sulfonic acid or an organic carboxylic acid. Among them, in terms of tolerance, it is particularly preferable to use naphthalenesulfonic acid or perchloric acid such as berbinoic acid.

Further, in the case of an acid dye or a direct dye form, it is preferable to use a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, a primary amine compound, etc. in terms of resistance, or it is preferable to use such a The resin component of the functional group is halogenated, used as a halide, or preferably sulfonated, and used as a sulfonate sulfonamide compound.

Among these, the acid dye halide and/or the acid dye sulfonate oxime compound are excellent in terms of resistance and use in combination with a pigment, and therefore it is preferable to use an acid dye as an antibacterial The ion functions as a compound which is halogenated using a quaternary ammonium salt compound of an anti-component.

The form of the fluorescent pigment (A) will be described in detail below.

(sulfonic acid guanamine compound of halide of acid dye and/or acid dye)

An acid dye-based quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, a primary amine compound, or the like, and a halogenated product of an acid dye by using a resin component having such a functional group, or a sulfonium halide Amination is carried out to form a sulfonium sulfonate compound, whereby high heat resistance, light resistance and solvent resistance can be imparted, which is preferable.

The primary amine compound may, for example, be methylamine, ethylamine, propylamine, isopropylamine, butylamine, amineamine, hexylamine, heptylamine, octylamine, decylamine, decylamine, Undecylamine, dodecylamine (laurylamine), tridodecylamine, myristylamine, pentaamine, hexadecylamine, stearylamine, oleylamine, cocoalkylamine, An aliphatic unsaturated primary amine such as tallow alkylamine, hardened tallow alkylamine or allylamine, aniline, benzylamine or the like.

The secondary amine compound may be an aliphatic unsaturated grade 2 such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamineamine or diallylamine. Amine, methylaniline, ethylaniline, dibenzylamine, diphenylamine, dicoalkylamine, dihardened tallow alkylamine, distearylamine, and the like.

The tertiary amine compound may, for example, be trimethylamine, triethylamine, tripropylamine, tributylamine, triamineamine, dimethylaniline, diethylaniline or tribenzylamine.

The fluorescent pigment (A) is especially suitable for the use of quaternary ammonium salts to impart acid dyes Halogenation or use of an acid dye for sulfonylation. The two forms are detailed below.

[halide composed of acid dye and quaternary ammonium salt compound]

From the viewpoint of heat resistance, light resistance, and solvent resistance, the fluorescent dye (A) is preferably used as a halide composed of the acid dye and the quaternary ammonium salt compound.

‧Quaternary ammonium salt compound

The quaternary ammonium salt compound has a counter ion which has an amine group and a cationic portion thereof which is a xanthene acid dye.

The preferred form of the quaternary ammonium salt compound which is the anti-component of the halogenated compound is colorless or white. Here, the colorless or white color means a so-called transparent state, and is defined as a state in which the transmittance is 95% or more, and more preferably 98% or more in the entire wavelength range of 400 to 700 nm in the visible light region. That is, it is required to prevent color development of the dye component and cause no color change.

The molecular weight of the cationic portion of the quaternary ammonium salt compound as the counter ion is preferably in the range of from 190 to 900. Here, the cation moiety corresponds to the (NR ¹ R ² R ³ R ⁴ ) moiety in the general formula (4) below. When the molecular weight is less than 190, the light resistance and heat resistance are lowered, and the solubility in a solvent may be lowered. Further, when the molecular weight is more than 900, the ratio of the coloring component in the molecule is lowered, so that the color rendering property may be lowered and the brightness may be lowered. The molecular weight of the cationic moiety is preferably in the range of 240 to 850, particularly preferably in the range of 350 to 800.

Here, the molecular weight is calculated according to the structural formula, and the atomic weight of C is 12, the atomic weight of H is 1, and the atomic weight of N is 14.

Further, as the quaternary ammonium salt compound, a compound represented by the following general formula (8) can be used.

General formula (8): [In the general formula (8), R ¹⁰¹ to R ¹⁰⁴ each independently represent an alkyl group having 1 to 20 carbon atoms or a benzyl group, and the number of at least two or more C groups of R ¹⁰¹ , R ¹⁰² , R ¹⁰³ or R ¹⁰⁴ is 5~20. Y represents an inorganic or organic anion. ]

The number of Cs of at least two or more side chains of R ¹⁰¹ to R ¹⁰⁴ is 5 to 20, and the solubility in a solvent is good. When there are three or more alkyl groups having a C number of less than 5 in R ¹⁰¹ to R ¹⁰⁴ , the solubility in a solvent is deteriorated, and a coating film foreign matter is likely to occur. Further, if an alkyl group having a C number exceeding 20 in the side chain is present, the color developability of the halide is impaired.

The Y ^- component constituting the anion of the quaternary ammonium salt compound may be an inorganic or organic anion, but is preferably a halogen, and is generally chlorine.

Specifically, such a quaternary ammonium salt compound is preferably tetramethylammonium chloride (the molecular weight of the cationic moiety is 74), tetraethylammonium chloride (the molecular weight of the cationic moiety is 122), and monostearylmethyl chloride. Ammonium (the molecular weight of the cationic moiety is 312), distearyl hydrazine methyl ammonium chloride (the molecular weight of the cationic moiety is 550), tristearic acid monomethyl ammonium chloride (the molecular weight of the cationic moiety is 788), sixteen Trimethylammonium chloride (molecular weight of the cationic moiety is 284), trioctylmethylammonium chloride (molecular weight of the cationic moiety is 368), dioctylmethylammonium chloride (molecular weight of the cationic moiety is 270), single Lauryl methyl ammonium chloride (having a molecular weight of 228 for the cationic moiety), dilauryl methyl ammonium chloride (the molecular weight of the cationic moiety is 382), and trilauryl methyl ammonium chloride (the molecular weight of the cationic moiety is 536), Triaminobenzylammonium chloride (molecular weight of the cationic moiety is 318), trihexylbenzylammonium chloride (yang) The molecular weight of the ionic moiety is 360), trioctylbenzylammonium chloride (molecular weight of the cationic moiety is 444), trilaurylbenzylammonium chloride (molecular weight of the cationic moiety is 612), benzyldimethyl stearin Ammonium chloride (molecular weight of the cationic moiety is 388), and benzyldimethyloctyl ammonium chloride (the molecular weight of the cationic moiety is 248), and dialkyl (alkyl is C14-C18) dimethylammonium chloride ( Hardened tallow) (the molecular weight of the cationic moiety is 438 to 550).

The products include QUARTAMIN 24P, QUARTAMIN 86P CONC, QUARTAMIN 60W, QUARTAMIN 86W, QUARTAMIN D86P, SANISOL C, SANISOL B-50, etc., ARQUAD 210-80E, 2C-75, 2HT-75 manufactured by LION Corporation. 2HT FLAKE, 2O-75I, 2HP-75, 2HP FLAKE, etc., especially QUARTAMIN D86P (distearate dimethylammonium chloride), ARQUAD 2HT-75 (dialkyl (alkyl is C14~C18) Methyl ammonium chloride is preferred.

The quaternary ammonium salt compound may also be in the form of a resin having a cationic group in a side chain, particularly having an amine group or an ammonium group, which can be reacted with a xanthene-based acid dye to be halogenated to form a quaternary ammonium salt structure. ‧How to make halides

The halide of the acid dye and the quaternary ammonium salt compound can be produced by a conventional method. A specific method is disclosed in Japanese Laid-Open Patent Publication No. Hei 11-72969.

For example, after dissolving an acid dye in water, a quaternary ammonium salt compound is added and halogenated while stirring. Here, a halide of a sulfonic acid group (-SO ₃ H), a sodium sulfonate (-SO ₃ Na) moiety in an acid dye, and an ammonium group (NH ₄ ⁺ ) moiety of a quaternary ammonium salt compound can be obtained. . Further, in place of water, methanol and ethanol are also solvents which can be used for halogenation.

As a halide, especially by using a fluorescent dye in the form of a fluorescent dye (A) (CI acid red 289 or CI acid red 52, etc.), and a halide of a quaternary ammonium salt compound having a molecular weight of 350 to 800 as a cationic portion of a counter ion, the solvent solubility is improved, and the pigment described later When used in combination, heat resistance, light resistance, and solubility resistance are further improved. Further, the halide and the pigment are used in combination, and it is presumed that the film is adsorbed to the pigment by being dissolved and dispersed in a solvent. At this time, the primary particle diameter of the pigment is suitably 20 to 100 nm.

The coloring composition is preferably in the form of a blue coloring composition containing a blue pigment, a red coloring composition containing a red pigment, a yellow coloring composition containing a yellow pigment, or a green coloring composition, as will be described later.

[Sulfonate oxime compound of acid dye]

The sulfonium sulfonamide compound which can be suitably used as the acid dye of the fluorescent pigment (A) can be chlorinated by an acid dye having -SO ₃ H or -SO ₃ Na by a general method, so that -SO ₃ H is -SO ₂ Cl, and the compound is produced by reacting with an amine having -NH ₂ .

Further, specifically, the amine compound used in the sulfonation of the sulfonic acid is preferably 2-ethylalkylamine, dodecylamine, 3-methoxypropylamine, 3-(2-ethylalkoxy). Base) propylamine, 3-ethoxypropylamine, cyclohexylamine, and the like.

For example, when CI Acid Red 289 is denatured using 3-(2-ethylalkoxy)propylamine to obtain a sulfonate decylamine compound, CI Acid Red 289 is chlorinated by a sulfonic acid group, The methane can be reacted with a theoretical equivalent of 3-(2-ethylalkoxy)propylamine to obtain a sulfonic acid guanamine compound of CI Acid Red 289.

Further, when CI Acid Red 52 is denatured using 3-(2-ethylalkoxy)propylamine to obtain a sulfonate decylamine compound, CI Acid Red 52 is chlorinated by a sulfonic acid group, and then is dissolved in dioxane. , which is reacted with a theoretical equivalent of 3-(2-ethylalkoxy)propylamine to obtain a sulfonic acid hydrazine of CI Acid Red 52. The amine compound can be used.

[halide composed of a basic dye and a compound of an organic acid or an inorganic acid]

The basic dye is more resistant to light and heat, and its characteristics are insufficient for use in an image display device using a color filter requiring high reliability. Therefore, in order to improve the disadvantages of the dyes, it is preferred to use an organic acid or an inorganic acid to halogenate the basic dye. The organic acid is preferably an organic sulfonic acid or an organic carboxylic acid, and among them, naphthalenesulfonic acid is particularly preferably used. It is especially suitable to be a suitable acid. Perchloric acid is particularly preferred as the inorganic acid.

<Other colorants>

The color filter coloring composition may further use the organic pigment (D) as another coloring agent. Other colorants are, for example, dyes that do not emit fluorescence or organic pigments that do not emit fluorescence.

When used in combination with other colorants, the use of organic pigment (D) is suitable for adjusting the hue and increasing the tolerance. When the fluorescent pigment (A) and the organic pigment (D) are used together, the ratio of the fluorescent pigment (A) to the organic pigment (D) is a fluorescent pigment (A) relative to the organic pigment (D). 100 parts by weight should be 1 to 80 parts by weight. More preferably 5 to 60 parts by weight. When the amount of the fluorescent pigment (A) is in this range, a composition having a good hue and a reproducible chromaticity region can be obtained.

For the filter segments of the respective colors, the following pigments can be used as the pigment to be used in combination.

(Used in the red filter section of the pigment)

The red pigment used in the red filter section may be exemplified by a red pigment or a red dye as described below.

Red pigments can use CI Pigment Red 7, 14, 41, 48:1, 48:2, 48:3, 48:4, 57:1, 81, 81:1, 81:2, 81:3 81:4, 122, 146, 149, 166, 168, 169, 176, 177, 178, 179, 184, 185, 187, 200, 202, 208, 210, 221, 242, 246, 254, 255, 264, 270, 272, 273, 274, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286 or 287, and the like. Among them, C.I. Pigment Red 177, 179, and 254 are particularly used.

Here, C.I. Pigment Red 254 and 255 also function as the fluorescent dye (A).

A yellow or orange pigment may also be used in combination to form a red filter segment. The yellow or orange pigment may, for example, be a yellow pigment, an orange pigment or the like as described below.

Yellow pigments can be used for 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 221, and the like.

As the orange pigment, C.I. Pigment Orange 38, 43, 71 or 73 can be used.

These pigments may be used singly or in combination of two or more kinds in any ratio as needed.

As a coloring agent for the red filter segment, when the organic pigment (D) and the pigment (A) are used together, the organic pigment (D) is preferably a red pigment or from the viewpoint of color reproducibility and tolerance. Orange pigment. In this case, from the viewpoint of brightness and contrast ratio, the red pigment or the orange pigment is particularly preferably CI Pigment Red 254, 177, 242 or CI Pigment Orange 38, and the fluorescent pigment (A) is preferably Rose Red. A pigment or a diketopyrrolopyrrole dye. By using these organic pigments (D) in combination with the fluorescent pigment (A), it is possible to provide a red colored composition having a good brightness and a good ratio.

(Used in the blue filter section of the pigment)

The pigment used in the blue filter section may, for example, be CI Pigment Blue 1, 1:2, 1:3, 2, 2:1, 2:2, 3, 8, 9, 10, 10:1. 11, 12, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 18, 19, 22, 24, 24:1, 53, 56, 56:1, 57, Blue pigments such as 58, 59, 60, 61, 62, 64, etc., purple pigments such as CI Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42 and 50, and combinations thereof.

As a coloring agent for the blue filter segment, when the organic pigment (D) is used in combination with the pigment (A), the organic pigment (D) is preferably a blue pigment from the viewpoint of color reproducibility and tolerance. . In this case, from the viewpoint of brightness and contrast ratio, the blue pigment is particularly preferably CI Pigment Blue 15:1, 15:6, and the fluorescent pigment (A) is preferably rose red pigment or triphenyl. Methane pigment. By combining these pigments (A), it is possible to provide a blue coloring composition having a good brightness, a ratio of ‧ and a good tolerance.

(Used in the green filter section of the pigment)

The pigment used in the green filter section may be a green pigment such as C.I. Pigment Green 7, 10, 36, 37, 58 or the like. Among them, it is preferable to use C.I. Pigment Green 36, 58.

Further, in the case of the green coloring composition, CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34 can be used. , 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, 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, A yellow pigment such as 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220 or 221 is used in combination with the pigment (A).

Among these, it is preferable to use C.I. Pigment Yellow 138, 150 and the like.

When the organic pigment (D) and the pigment (A) are used in combination as a coloring agent for the green filter segment, the organic pigment (D) is preferably a green pigment from the viewpoint of color reproducibility and resistance. In this case, from the viewpoint of brightness and contrast ratio, the green pigment is particularly preferably CI Pigment Green 36, 58. Further, the fluorescent pigment (A) is preferably a yellow dye, and particularly preferably a quinoline dye. . By combining these pigments (A), it is possible to provide a green coloring composition having a good brightness, a ratio of ‧ and a good tolerance.

In the coloring composition for a color filter, the concentration of the coloring agent relative to the total nonvolatile component is preferably from 10 to 90% by weight, more preferably from 15 to 85% by weight, from the viewpoint of sufficient color reproducibility. Most preferably 20 to 80% by weight. When the concentration of the colorant component is less than 10% by weight, sufficient color reproducibility may not be obtained, and when it exceeds 90% by weight, the concentration of the colorant carrier such as a resin binder may be lowered, and the stability of the coloring composition may sometimes be Getting worse.

(pigment refinement)

The organic pigment (D) should be used in a fine manner. The method of refining is not particularly limited, and any method such as wet grinding, dry grinding, and dissolution precipitation may be employed. For example, it can be refined by salt grinding treatment or the like by one of wet grinding. From the viewpoint of being well dispersed in the colorant carrier, the primary particle diameter of the pigment is preferably 20 nm or more. Also, in order to form In the filter section having a high contrast ratio, the primary particle diameter of the pigment is preferably 100 nm or less. A particularly suitable range is in the range of 25 nm to 85 nm. Further, the primary particle diameter of the pigment is carried out by directly measuring the particle size by means of an electron microscope photograph of a TEM (transmission electron microscope) of the pigment. Specifically, the minor axis diameter and the major axis diameter of the primary particles of each pigment are measured, and the average is used as the particle diameter of the pigment particles.

Salt grinding treatment refers to the use of a batch or continuous mixing mixer such as a kneader, a 2-roll mill, a 3-roll mill, a ball mill, an attritor, a sand mill, a planetary mixer, etc. The mixture of the inorganic salt and the water-soluble organic solvent is heated, and after mechanically mixing and stirring, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt functions as a pulverization aid, and when salt milling, the pigment is pulverized by the high hardness of the inorganic salt. By optimizing the conditions for the polishing treatment of the pigment, it is possible to obtain a pigment having a very fine primary particle diameter and a narrow distribution range and a clear particle size distribution.

As the water-soluble inorganic salt, sodium chloride, cesium chloride, potassium chloride or sodium sulfate can be used, and sodium chloride (salt) is preferably used from the viewpoint of price. From the viewpoints of processing efficiency and production efficiency, the water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by weight, and preferably 300 to 1000 parts by weight, based on 100 parts by weight of the total weight of the pigment.

The water-soluble organic solvent functions as a wet pigment and a water-soluble inorganic salt, and is not particularly limited as long as it is dissolved (mixed) in water and substantially does not dissolve the inorganic salt. However, in the salt milling treatment, the temperature rises and the solvent is in a state of easy evaporation. Therefore, from the viewpoint of safety, it is preferably a high boiling point solvent having a boiling point of 120 ° C or higher. For example, 2-methoxyethane, 2-butoxyethane, 2-(isopropoxy)ethane, 2-(hexyloxy)ethane, diethylene glycol, diethylene glycol can be used. Ethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propane, 1-ethoxy-2-propane, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether or liquid polypropylene glycol. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by weight, and most preferably 50 to 500 parts by weight, based on 100 parts by weight of the total weight of the pigment.

When the pigment is subjected to salt milling, the resin may be added as needed. The type of the resin to be used is not particularly limited, and a natural resin, a modified natural resin, a synthetic resin, or a synthetic resin modified with a natural resin can be used. The resin to be used is preferably solid at room temperature and insoluble in water, and more preferably partially soluble in the above organic solvent. The amount of the resin used is preferably from 5 to 200 parts by weight based on 100 parts by weight of the total weight of the pigment.

When the pigment is subjected to salt grinding treatment (fine refinement), it is also preferable to add a fluorescent pigment (A). A good color former can be produced by adding the pigment together.

Organic Compound (B)

When a dye is used as the fluorescent pigment (A), a color filter having high brightness can be obtained from a dye characteristic or even a high solubility of a dye, but it is due to the pigment itself. Fluorescence occurs, which has a problem of a decrease in the contrast ratio. This main cause is due to the presence of fluorescence in the light leakage during the comparative measurement, and the brightness on the staggered side becomes high.

The inventors of the present invention reviewed the problem of the reduction in the contrast ratio caused by the fluorescence emission, and as a result, found that it has an organic pigment skeleton or an aniline skeleton, and an acidic functional group, a basic functional group or a quinone imine. The organic compound (B) of the skeleton is used in combination with the fluorescent pigment (A), and the pigment (A) does not fluoresce, and the brightness on the staggered side can be lowered, and high contrast can be achieved.

When these substances are used, the reason for suppressing the fluorescence-removing effect of fluorescence is remarkable, and it is judged that it may have an organic pigment skeleton or an aniline skeleton, and an acidic functional group, a basic functional group or a quinone imine skeleton. The organic compound (B) is compatible with the fluorescent pigment (A) Since the fluorescence is highly efficient, the fluorescence removal efficiency is high, and since it is easy to form a charge shifting complex with the fluorescent pigment (A), the fluorescent light itself is remarkably suppressed, and the fluorescence is remarkably eliminated.

The organic compound (B) having an organic pigment skeleton or an aniline skeleton, and an acidic functional group, a basic functional group or a quinone imine skeleton is preferably a compound represented by the following general formula (1).

General formula (1): P-Lm [In general formula (1), P is an organic pigment skeleton or an aniline skeleton, and L is a basic functional group Lb, an acidic functional group La or a functional group having a quinone imine skeleton. The composition of Lp, m is an integer from 1 to 4, indicating the number of functional groups. ]

The organic pigment skeleton (P) of the organic compound (B) may, for example, be a diketopyrrolopyrrole pigment; an azo pigment such as azo, disazo or polyazo; an amine onion, a diamine and an onion , pyridoxine, xanthone, indolinone, standard reduced blue, furanone, anthrone purple dye, etc.; quinacridone pigment; anthraquinone pigment; anthraquinone pigment; thioindigo pigment; Azinium blue pigment; isoindane pigment; isoindolinone pigment; quinophthalone pigment; durene pigment; phthalocyanine pigment; benzimidazolidone pigment; dithiazine pigment; And organic pigments such as metal-missing pigments.

The organic compound (B) has both an organic pigment skeleton and an aniline skeleton.

Among these, from the viewpoint of hue and contrast ratio, it is preferably an organic pigment skeleton, and more preferably selected from the group consisting of a phthalocyanine pigment, a benzimidazolidinone pigment, a dithiazine pigment, and an azo system. Pigments, onion pigments, scallions pigments, diketopyrrolopyrrole pigments and quinolin Any of the organic pigment skeletons in the group consisting of an anthrone-based pigment. In this case, since the organic compound (B) having the organic pigment skeleton has high affinity with the fluorescent pigment (A), the fluorescence eliminating effect is increased.

When the blue coloring composition is used, the organic pigment skeleton is particularly preferably a skeleton of a phthalocyanine pigment or a dithiazine pigment. Further, when such a red colored composition is used, the organic pigment skeleton is particularly preferably a skeleton of a benzimidazolidinone pigment, a dicamba pigment, or a diketopyrrolopyrrole pigment. Further, since aniline is colorless, it can be suitably used in either blue or red.

The functional group (L) is a basic functional group Lb, an acidic functional group La or a functional group Lp having a quinone imine skeleton, and has a structure represented by the following general formulas (2) to (5). This is because the above functional group has a certain steric hindrance site, and in addition to the good fluorescence elimination effect, it also contributes to ensuring the viscosity stability of the dye solution.

The basic functional group Lb is represented, for example, by the general formula (2) or (5), the acidic functional group La is represented by the general formula (3) or (5), and the functional group having the quinone imine skeleton is represented by, for example, General formula (4) or (5).

The basic component used for forming the substituent represented by the general formula (2) or (5) may, for example, be dimethylamino, diethylamino, N,N-ethylisopropylamine or N,N-B. Propylamine, N,N-methylbutylamine, N,N-methylisobutylamine, N,N-butylethylamine, N,N-tert-butylethylamine, diisobutylamine, dipropylamine, N,N-second butyl propylamine, dibutylamine, di-second butylamine, diisobutylamine, diisobutylamine, N,N-isobutyl second butylamine, diamylamine, diisoamylamine , dihexylamine, bis(2-ethylhexyl)amine, dioctylamine, N,N-methyloctadecylamine, diamine, diarylamine, N,N-methyl-1,2-dimethyl Propylamine, N,N-methylhexylamine, dioleylamine, distearylamine, N,N-dimethylamine methylamine, N,N- Dimethylamine, N,N-dimethylamine methylamine, N,N-dimethylamine, N,N-diethylamine ethylamine, N,N-diethylamine propylamine, N,N-di Ethylamine, N,N-diethylamine butylamine, N,N-diethylamine pentylamine, N,N-dipropylamine butylamine, N,N-dibutylamine propylamine, N,N-dibutylamine Ethylamine, N,N-dibutylamine butylamine, N,N-diisobutylamine pentylamine, N,N-methyl-lauramide, N,N-ethyl-hexylamine ethylamine, N, N-distearylamine ethylamine, N,N-dioleylamine, N,N-distearate butylamine, piperidine, 2-methylpiperidine, 4-methylpiperidine, 2,4 - dimethyl piperidine, 2,6-dimethyl piperidine, 3,5-dimethyl piperidine, 3-piperidinyl methanol, methyl piperidic acid, isopiperidinecarboxylic acid, isopiperidinecarboxylic acid methyl , isopiperidinic acid ethyl, 2-piperidinemethanol, pyrrole, 3-hydroxypyrrole, N-amine ethylpiperidine, N-amineethyl-4-methylpiperidine, N-amine ethylmorpholine, N-aminopropyl piperidine, N-aminopropyl-2-methylpipecolic acid, N-aminopropyl-4-methylpipecolic acid, N-aminopropylmorpholine, N- Methylpiperazine, N-butylpiperazine, N-methylhomopiperazine, 1-cyclopentylpiperazine, 1-amino-4-methylpiperazine or 1-cyclopentylpiperazine.

The organic compound (B) can be synthesized by using the various synthetic routes described above. For example, after introducing a substituent represented by the following formula (11) to formula (15) to an organic pigment skeleton or an aniline skeleton, the above-mentioned substituent is reacted to form a substituent represented by the formula (2) or (5). An amine component such as N,N-dimethylaminopropylamino, N-methylpiperidine, diethylamino or 4-[4-hydroxy-6-[3(dibutylamino)propylamino]-1, It is obtained by a reaction such as 3,5-triazin-2-amine]aniline.

Formula (11)-SO ₂ Cl

Formula (12)-COCl

Formula (13)-CH ₂ NHSO ₂ CH ₂ Cl

Formula (14)-CH ₂ NHCOCH ₂ Cl

Formula (15)-CH ₂ Cl

When the substituent of the formula (11) to the formula (15) is reacted with the above amine component, it is mixed Some of the formulae (11) to (15) may be hydrolyzed, and chlorine may be substituted with a hydroxyl group. In this case, the formula (11) and the formula (12) are each a decanoic acid group and a carboxylic acid group, but both may maintain a free acid or a salt of a valence of 1 to 3 or a salt of the above monoamine.

Among the organic compounds (B), the substituents represented by the general formula (5) can be synthesized by various synthetic routes. For example, by using cyanogen chloride as a starting material and at least one chlorine of cyanogen chloride, an amine component forming a substituent represented by the general formula (2), such as N,N-dimethylamine propylamine or N- The reaction such as methylpiperidine is carried out by reacting residual chlorine of cyanogen chloride with various amines or alcohols.

One of the best forms among the organic compounds (B) is a form of a sulfonic acid oxime compound having an organic pigment skeleton having a sulfonate decylamine structure.

The sulfonate sulfonamide compound refers to the above-mentioned organic compound (B), in the general formula (2) or (5), for example, X ¹ -SO ₂ - of the general formula (2), Y ¹ is a direct bond, and n is 0. .

Further, regardless of the presence or absence of the sulfonate oxime structure, the compound having a good fluorescence-eliminating property is a triazine-based compound having a triazine skeleton as shown in the general formula (5).

In other words, when the basic skeleton of the organic compound (B) has a triazine skeleton or a sulfonate oxime skeleton, the fluorescence elimination property is good, which is particularly preferable.

In the acidic derivative having the acidic functional group La, the acidic group having a dye derivative may, for example, be a sulfonic acid group, a carboxylic acid group or a phosphonic acid group. A pigment derivative having a sulfonic acid group can be produced by an organic pigment and allowing sulfuric acid to act. The sulfonic acid group may also be a metal atom having a valence of 1 to 3 such as lithium, potassium, sodium, calcium, magnesium, barium or aluminum, a transition metal such as Fe, Co, Ni or Cu, a monoalkyl group such as ethylamine or butylamine. An amine such as a dialkylamine such as an amine, dimethylamine or diethylamine; a trialkylamine such as trimethylamine or triethylamine; an organic amine such as an alcoholamine such as monoethanolamine, diethanolamine or triethanolamine; or ammonia; salt.

Among them, the use of a transition metal to form a salt can show the good effect of fluorescence elimination. More suitable.

Further, in order to make the counter metal ion of the acidic derivative into a transition metal ion such as Fe, Co, Ni or Cu, the derivative having an acidic functional group terminal may be dissolved in an alkaline aqueous solution such as sodium hydroxide or ammonia, or dissolved. After adding an equivalent amount of each metal salt to an organic solvent such as methanol, ethylene glycol, acetone, pyridine, DMF or DMSO, the mixture is heated and stirred to obtain a precipitate.

The following is an example in which an acid group is introduced into a pigment skeleton and halogenated by an organic amine. Here, an example of a quinoline halide is given.

A xanthene-based dye composed of a quinone-based yellow pigment C.I. Pigment Yellow 138 deuterated pigment derivative and distearyl dimethyl ammonium chloride (QUARTAMIN D86P) (having a molecular weight of 550 in a cationic portion) was prepared. Further, 30 parts of a quinophthalone-based yellow pigment C.I. Pigment Yellow 138 ("Paliotol K0960-HD" manufactured by BASF Corporation) was dissolved in 300 parts of 101% sulfuric acid, and stirred at 70 ° C for 8 hours to carry out a deuteration reaction. The spectroscopic spectrum of the sulfuric acid solution was measured, and the end point of the reaction was obtained when no spectral change was observed. Next, the reaction solution was poured into 3000 parts of ice water, and the precipitated deuterated pigment derivative was filtered and washed, and washed with water to obtain a paste of the deuterated pigment derivative.

LC-MASS analysis was performed on the obtained deuterated pigment derivative. HPLC (column: "ODS-100S" manufactured by Tosoh Corporation), the molecular weight of the main peak of 80% of the area ratio is MW = 774 (electric discharge mode, negative mode), and the mono-derivative derivative of CI Pigment Yellow 138 The molecular weight is the same. Further, the deuterated dye derivative having the following structure was determined by 1H-NMR.

The organic compound (B) can be synthesized by a conventionally known method. Japanese Patent Publication No. Sho 63-305173, Japanese Patent No. Sho 57-15620, Japanese Patent No. 59-40172, Japanese Patent No. Sho 63-17102, Japanese Patent Publication No. 5-9469, and Japanese Patent Laid-Open A specific method is described in Japanese Laid-Open Patent Publication No. SHO-61-246261, and the like.

Further, as a method of introducing a functional group Lp having a quinone imine skeleton to an organic pigment skeleton or an aniline skeleton, a conventional method of reacting with hydroxymethyl quinone imine in sulfuric acid can be used, for example, by Japan. The method described in JP-A-55-108466 is incorporated.

The organic compound (B) having an organic pigment skeleton, an aniline skeleton, an acidic functional group, a basic functional group or a quinone imine skeleton may be used singly, or may be used in combination of two or more.

In the coloring composition, the compounding amount of the organic compound (B) is preferably 0.05 to 2 by weight (B/A) based on the fluorescent pigment (A). When it is less than 0.05, since the fluorescence suppression and the dispersibility of the organic compound (B) are insufficient, the contrast ratio becomes low, and if it is more than 2, the color characteristics are affected, and the luminance is lowered. A better weight ratio (B/A) is 0.2 to 2, and an optimum weight ratio (B/A) is 0.5 to 1.5.

Resin

The coloring composition for a color filter is characterized by comprising a resin binder (C). Further, in addition to the above-mentioned main resin binder (C), other resins such as rosin grease may be contained as an auxiliary resin. That is, the resin is composed of a main resin binder (C) and an auxiliary resin as an option.

<Resin Adhesive (C)>

The resin binder (C) is a coloring agent such as a pigment or a pigment, in particular, a pigment (A) which is fluorescent, or a pigment (A) which is fluorescent, is dyed and infiltrated, and a thermoplastic resin or heat is mentioned. Curable resin, etc.

The resin binder (C) is preferably a resin having a spectral transmittance of 80% or more, more preferably 95% or more in the entire wavelength range of 400 to 700 nm in the visible light region. Further, when it is used in the form of an alkali-developable coloring resist material, an alkali-soluble vinyl-based resin obtained by copolymerizing an ethylenically unsaturated monomer having an acidic group is preferably used.

Further, in order to further enhance the light sensitivity, an energy ray-curable resin having a double bond of ethylenically unsaturated activity may also be used.

In order to disperse and infiltrate the coloring agent composed of the fluorescent pigment (A) and the optional organic pigment (D), the weight average molecular weight (Mw) of the resin binder (C) is preferably in the range of 5,000 to 80,000. More preferably in the range of 7,000 to 50,000. Further, the number average molecular weight (Mn) is preferably in the range of 2,500 to 40,000, and the Mw/Mn value is preferably 10 or less.

Here, the resin molecular weight is obtained by using HLC-8220GPC (manufactured by Tosoh Co., Ltd.) as a device, and two rows of TSK-GEL SUPER HZM-N are connected as a column, and the molecular weight converted to polystyrene is measured using THF as a solvent. .

The resin binder (C) is used as a photosensitive coloring group for a color filter to be described later In the case of a product (resist material), a coloring agent adsorbing group and a carboxyl group acting as an alkali-soluble group during development, a colorant carrier, and an aliphatic group and an aromatic group functioning as an affinity group for a solvent The balance is important for the dispersibility, permeability, and developability of the pigment, and further, 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 developer is not good, and it is difficult to form a fine pattern. If it exceeds 300 mgKOH/g, a fine pattern is not left at the time of development.

The resin binder (C) is preferably 30 parts by weight or more based on 100 parts by weight of the colorant, and exhibits good color characteristics because of a high concentration of the colorant component. It is preferably used in an amount of 500% by weight or less based on 100 parts by weight of the colorant.

(thermoplastic resin)

The thermoplastic resin may, for example, be an acrylic resin, a butyral resin, a styrene-maleic acid copolymer, a chlorinated polyethylene, a chlorinated polypropylene, a polyvinyl chloride, a vinyl chloride-vinyl acetate copolymer, or a polyvinyl acetate. , polyurethane resin, polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, cellulose, polyethylene (HDPE, LDPE), poly Butadiene and polyimine resin.

The vinyl base-soluble resin to which the ethylenic unsaturated monomer having an acidic group is copolymerized may, for example, be a resin having an acidic group such as a carboxyl group or a sulfo group. Specifically, the alkali-soluble resin may, for example, be an acrylic resin having an acidic group, an α-olefin-(anhydride) maleic acid copolymer, a styrene/styrenesulfonic acid copolymer, or a styrene/(meth)acrylic acid. Copolymer or isobutylene / (anhydride) maleic acid copolymer, and the like. Among them, at least one resin selected from the group consisting of an acrylic resin having an acidic group and a styrene/styrenesulfonic acid copolymer, particularly an acrylic resin having an acidic group is heat resistant It is suitable for use because of its high transparency and transparency.

The active energy ray-curable resin having a double bond of ethylenic unsaturation may, for example, be a resin in which an unsaturated ethylenic double bond is introduced by the following method (i) or (ii).

[method (i)]

As the method (i), for example, by copolymerizing an ethylenically unsaturated ethylenic monomer having an epoxy group with one or more other monomers, the side chain epoxy group of the obtained copolymer is rendered unsaturated. The ethylenic double-bonded unsaturated carboxyl group of the monovalent acid is subjected to an additional reaction, and the polyhydroxy acid anhydride is reacted with the generated hydroxyl group to introduce an unsaturated ethylenic double bond and a carboxyl group.

Examples of the unsaturated ethylenic monomer having an epoxy group include a glycidyl (meth) acrylate, a methyl epoxypropyl (meth) acrylate, and a 2-epoxypropoxy group (A). Acrylate, 3,4 epoxybutyl (meth) acrylate and 3,4 epoxy cyclohexyl (meth) acrylate. These may be used alone or in combination of two or more. From the standpoint of reactivity with an unsaturated monovalent acid in the next step, it is preferably a propylenepropyl (meth) acrylate.

Examples of the unsaturated monovalent acid include (meth)acrylic acid, crotonic acid, o-, m- or p-vinylbenzoic acid, and α-halogenane, alkoxy, halogen, and nitrate of (meth)acrylic acid. And a monocarboxylic acid such as a cyanide substituent. These may be used alone or in combination of two or more.

Examples of the polyvalent acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride. These may be used alone or in combination of two or more. If necessary, the number of carboxyl groups and the like may be increased, and a tricarboxylic acid anhydride such as trimellitic anhydride may be used, or a tetracarboxylic dianhydride such as pyromellitic dianhydride may be used, or the residual anhydride group may be hydrolyzed or the like. also, As the polyvalent acid anhydride, if tetrahydrophthalic anhydride or maleic anhydride having an unsaturated ethylenic double bond is used, the unsaturated ethylenic double bond can be further increased.

A similar method of the method (i) includes, for example, a part of a side chain carboxyl group of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having a carboxyl group with one or more other monomers, and having an epoxy group. The ethylenically unsaturated monomer is subjected to an additional reaction to introduce an ethylenically unsaturated double bond and a carboxyl group.

[method (ii)]

As the method (ii), comprising using an ethylenically unsaturated monomer having a hydroxyl group, copolymerizing with another unsaturated monovalent acid having a carboxyl group or another monomer, and having a side chain hydroxyl group of the obtained copolymer, having an isocyanate A method in which an isocyanate group of an ethylenically unsaturated monomer is reacted.

Examples of the ethylenically unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxy butyl A hydroxyalkyl (meth) acrylate such as a (meth) acrylate, a glycerol (meth) acrylate or a cyclohexane dimethanol mono (meth) acrylate. These may be used alone or in combination of two or more. Further, it can also be used in the above-mentioned hydroxyalkyl (meth) acrylate, and polyether mono(meth)acrylic acid obtained by additionally polymerizing an ethylene peroxide, a propylene peroxide, and/or a butyl peroxide. An ester or a (poly)ester mono(meth)acrylate to which (poly)γ-valerolactone, (poly)ε-caprolactone, and/or (poly)12-hydroxystearic acid are added. From the viewpoint of suppressing the coating film foreign matter, it is preferably 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate.

Examples of the ethylenically unsaturated monomer having an isocyanate group include 2-(meth)acryloyloxyethyl isocyanate or 1,1-bis[(meth)acryloxime]ethyl isocyanate, but are not limited thereto. These may also be used in combination of two or more types.

(thermosetting resin)

Examples of the thermosetting resin include an epoxy resin, a benzoamide resin, a melamine resin, a phenol resin, and the like.

<Other resins>

In addition to the resin binder (C), the coloring composition may contain other resins such as rosin for the purpose of improving the resistance of the fluorescent pigment (A) and improving the dispersibility of the organic pigment (D). .

Rosin fat is a rosin, tall rosin, wood rosin, and uneven rosin, rosin, wood rosin, which are mainly composed of rosin acid, neo-rosin acid, levo-sea rosin acid, peroxy abietic acid, tyrosine acid, and dextran rosin acid. An ester of polyvalent alcohols of rosin, hydrogenated rosin, partially heterogeneous rosin, butylated rosin and mixtures thereof and polyvalent alcohols thereof (glycerides, pentaerythritol esters, diethylene glycol esters, etc.) Especially suitable for neopentyl ester).

Rosin is obtained by the following method.

A refined rosin such as refined gum rosin, refined wood rosin, refined polymerized rosin, refined uneven rosin or refined tall oil rosin is used as a starting material, and esterified with an alcohol to obtain a rosin ester. In the esterification reaction, general conditions can be directly used, for example, under an inert gas flow, generally, the refined rosin is reacted with an alcohol such as the following under heating of 150 to 300 ° C to remove the produced water to the outside of the system. can.

The alcohol component to be used for the esterification is not particularly limited, and examples thereof include n-octanol, 2-ethylhexanol, decyl alcohol or lauryl alcohol, and ethylene glycol, diethylene glycol, propylene glycol, and new a divalent alcohol such as pentaerythritol or cyclohexane dimethanol; a trivalent alcohol such as glycerin, trimethylolethane or trimethylolpropane; And a tetravalent alcohol such as pentaerythritol or diglycerin. Among them, it is preferable to use a trivalent or tetravalent polyvalent alcohol. These may be used alone or in combination of two or more.

Further, an esterification catalyst or an oxidation inhibitor may be used as needed. The esterification catalyst may, for example, be an acid catalyst such as acetic acid or p-toluenesulfonic acid, a hydroxide of an alkali metal such as potassium hydride, or a metal oxide such as potassium oxide or magnesium oxide.

Hereinafter, rosin esters of specific commercially available products which can be used are exemplified.

Rosin grease can be made by Ashinawa Chemical Industry Co., Ltd. PENSEL A, AZ, Ester Gum AAG, AAL, A, AAV, 105, HS, AT, etc., Neomatall G2, 101K, NT-15, 125HK, manufactured by Harima Chemicals. Hariester TF, NL, S, P, C, DS-70L, DS-90, DS-130, etc.

Further, the polymerized rosin is exemplified by PENSEL D-125, D-135, D-160, etc. manufactured by Arakawa Chemical Industry Co., Ltd., and Harareer KT-2 manufactured by Harima Chemicals Co., Ltd., and the like.

Further, the uneven rosin is exemplified by Super Ester A-75, A-100, A-115, A-125, T-125 and the like manufactured by Arakawa Chemical Industry Co., Ltd.

Further, rosin-modified maleic acid resin and rosin modified fumaric acid resin are MALKYD NO. 1, 2, 5, 6, 8, 30A, 31, 32 manufactured by Arakawa Chemical Industry Co., Ltd. , 33, 34, 3002, etc., HARIMACK T-80, R-100, M-453, M-130A, 135GN, 145P, R-120AH, etc. manufactured by Harima Chemicals.

Further, examples of the hydrogenated rosin are Ester Gum H, HP, HD, and the like manufactured by Arakawa Chemical Industry Co., Ltd.

Among them, it is especially suitable to use polymerized rosin, uneven rosin, rosin to improve Acetyic acid resin (including rosin modified fumaric acid resin).

The acid value of the rosin is preferably 100 mgKOH/g or less. More preferably, it is 40 mgKOH/g or less. A particularly suitable range is in the range of 5 to 40 mgKOH/g, and if it is in this range, the performance of the xanthene-based dye (A) is effectively maintained.

Further, in consideration of compatibility with the resin binder (C), storage stability, and productivity, the softening point of the rosin gum 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, the coloring composition is likely to be coagulated, and if it exceeds 150 ° C, the adhesion of the color filter may be lowered.

The addition amount of the rosin is preferably 0.3 to 5 parts by weight with respect to 100 parts by weight of the resin binder (C). When the amount of the rosin is less than 0.3 parts by weight, it is difficult to obtain an effect, and if it is more than 5 parts by weight, the performance of the resin binder (C) may be hindered.

"Organic solvents"

The coloring composition may contain a solvent to cause the fluorescent component (A) of the coloring agent component to further sufficiently disperse and penetrate the organic pigment (D) or the like into a coloring agent carrier such as a resin binder (C). On a substrate such as a glass substrate, the coating film has a dry film thickness of 0.2 to 5 μ to form a filter segment.

The solvent may, for example, be benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butanediol, 1,3-butanediol diacetate, 1,4 - Dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,3,5-trimethyl-2-cyclohexen-1-one, 3,5,5 trimethylcyclo Hexanone, ethyl 3-ethoxypropionate, butyl 3-methoxy-3-methylacetate, 3-methoxybutanol, 3-methoxyacetic acid butyl ester, 4-heptanone, Xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, n-butylbenzene, propyl orthoacetate, N-pyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene O-dichlorobenzene, pair Chlorotoluene, p-diethylbenzene, secondary butylbenzene, tertiary butylbenzene, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol single third Ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, diisobutyl ketone, cyclohexanol acetate, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monobutyl ether, diacetone Alcohol, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, phenyl alcohol, methyl isobutyl ketone Methylcyclohexanol, n-aminoacetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, divalent acid ester, lactic acid butyl, and the like.

Among them, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate are preferably used from the viewpoint of dispersibility, solubility, and permeability of the fluorescent pigment (A) and the organic pigment (D). An alcohol such as an ester, an ethylene glycol monomethyl ether acetate or an ethylene glycol monoethyl ether acetate; an aromatic alcohol such as benzyl alcohol; or a ketone such as cyclohexanone. Among them, alcohol acetates, ketones, propylene glycol monomethyl ether acetate, and cyclohexanone are particularly preferably used.

The organic solvent may be used singly or in combination of two or more. Further, since the solvent can adjust the coloring composition to an appropriate viscosity to form a desired filter segment having a uniform film thickness, it is preferably in an amount of 800 to 4000% by weight based on 100% by weight of the total weight of the colorant component. To use.

Photopolymerizable monomer

Further, a photopolymerizable monomer may be added to the colored composition. A preferred photopolymerizable monomer is a monomer or oligomer which is cured by ultraviolet light or heat to form a transparent resin.

A monomer or oligomer which forms a transparent resin by curing by ultraviolet rays or heat For example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (A Acrylate, β-carboxy (meth) acrylate, polyethylene glycol mono (meth) acrylate, 1,6-hexane dimethylene (meth) acrylate, triethylene glycol di (methyl) ) acrylate and tripropylene glycol di(meth) acrylate, trimethylolpropane (meth) acrylate, neopentyl alcohol (meth) acrylate, neopentyl alcohol tetra (meth) acrylate, Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa(meth) acrylate, 1,6-butanediol diglycidyl ether, bisphenol A diglycidyl ether, neopentyl Various acrylates and methacrylates such as diol glyceryl ether and methylolated melamine, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, and neopentyl Alcohol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinyl methamine, acrylonitrile, etc., but are not necessarily limited thereto.

These photopolymerizable compounds may be used singly or in combination of two or more kinds at any ratio as needed.

The amount of the photopolymerizable monomer is preferably from 5 to 400 parts by weight based on 100 parts by weight of the colorant, and more preferably from 10 to 300 parts by weight from the viewpoint of photocurability and developability.

Photopolymerization initiator

In the colored composition, in order to cure the composition by ultraviolet irradiation, a filter segment is formed by photolithography, a photopolymerization initiator or the like may be added, and a solvent development type or an alkali development type photosensitive coloring may be added. The form of the composition is modulated.

As the photopolymerization initiator, for example, 4-phenoxydichloroacetophenone, 4-t-butyldichloroacetophenone, diethoxyacetophenone, 1-(4-isopropyl group can be used. Phenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl benzophenone, 2-benzyldimethylamine-1-(4-morpholinylphenyl)-butane-1 - An acetophenone compound such as a ketone; a benzo compound such as benzo, benzoxyl ether, benzoether, benzoisopropyl ether or benzyldimethylketal; benzophenone, benzoquinone benzoic acid, benzene Benzoic acid methyl, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoquinone-4'-methyldiphenyl sulfide, 3,3', a benzophenone compound such as 4,4'-tetrakis(t-butylperoxycarboxy)benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthiophene a thioxanthone compound such as ketone, 2,4-diisopropylthioxanthone or 2,4-diethylthioxanthone; 2,4,6-trichloro-o-triazine, 2-phenyl- 4,6-bis(trichloromethyl)-o-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-o-triazine, 2-(p-tolyl) -4,6-bis(trichloromethyl)-o-triazine, 2-piperidin-4,6-bis(trichloromethyl)-o-triazine, 2,4-bis(trichloromethyl)- 6-styryl-o-triazine, 2-(naphtho-1-yl)-4,6-bis(trichloromethyl)-o-triazine, 2-(4-methoxynaphtho-1- -4,6-bis(trichloromethyl)-o-triazine, 2,4-trichloromethyl-(piperidyl)-6-triazine, 2,4-trichloromethyl (4'- Methoxystyrene a triazine-based compound such as -6-triazine; 1,2-octanedione, 1-[4-(phenylthio)-, 2(O-benzopyrene)], O-(acetyl)-N An oxime ester compound such as -(1-phenyl-2-carbonyl-2-(4'-methoxy-naphthyl)ethylidene)hydroxylamine; bis(2,4,6-trimethylbenzo) ring a phosphine compound such as oxyphenylphosphine or 2,4,6-trimethylbenzoepoxyphenylphosphine; an anthraquinone compound such as 9,10-phenanthrenequinone, camphorquinone or ethylhydrazine; a borate ester compound; An azole compound; or an imidazole compound.

These photopolymerization initiators may be used singly or in combination of two or more kinds at any ratio as needed.

The content of the photopolymerization initiator is preferably from 2 to 200% by weight based on 100 parts by weight of the colorant, and is preferably from 3 to 150 parts by weight from the viewpoint of photocurability and developability.

Sensitizer

The coloring composition may further contain a sensitizer.

The sensitizer may, for example, be an unsaturated ketone represented by a flavonoid derivative or dibenzylideneacetone, a 1,2-diketone derivative represented by benzyl or camphorquinone, a benzo derivative or a hydrazine derivative. , naphthoquinone derivatives, anthracene derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, coumarin derivatives a polymethine pigment such as a cyanine derivative, a merocyanine derivative, or a cyanine derivative, an acridine derivative, an azabenzene derivative, a diene terpene derivative, an oxazine derivative, or a porphyrin derivative. , anthracene derivative, sulfonium salt derivative, squaraine ylide derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative, tetrapyrazine porphyrin derivative , phthalocyanine derivative, tetrazoporphyrin derivative, tetraquinoxaline porphyrin derivative, naphthalocyanine derivative, phthalocyanine derivative, pyridinium salt derivative, thiopyridinium salt derivative, Tetraporphyrin derivative, olefin derivative, spiropyran derivative, spirooxazine derivative, thiospirol derivative, metal aromatic hydrocarbon Complex, organic hydrazine complex, methyl ketone derivative, α-decyloxy ether, decyl phosphide hydroxide, tolyl glyoxylic acid, benzyl-9,10-phenanthrene Camphor, ethyl hydrazine, 4,4'-diethyl phenol ketone, 3,3' or 4,4'-tetrakis (tertiary butylperoxycarboxy) benzophenone, 4,4'- Dimethylamine benzophenone and the like.

These sensitizers may be used singly or in combination of two or more kinds at any ratio as needed.

Specifically, the "Pigment Handbook" (1986, Kodansha), and the "Chemistry of Functional Pigments" (1981, CMC) and Chisen-Sang Sanlang, etc., edited by Ohara Shinto et al. The sensitizers described in "Special Functional Materials" (1986, CMC) are not limited to these. Further, it may contain a sensitizer which exhibits absorption of light from the ultraviolet to the near-infrared region.

The content of the sensitizer is relative to the photopolymerization initiation contained in the coloring composition. The weight of the agent is preferably from 3 to 60% by weight, and is preferably from 5 to 50 parts by weight from the viewpoint of photocurability and developability.

Polyfunctional thiophenol

The coloring composition for a color filter may contain a polyfunctional thiophenol which functions as a chain shifting agent.

The polyfunctional thiophenol may have a compound having two or more thiophenol groups, and examples thereof include hexathiophenol, decyl phenol, 1,4-butanediol dithiopropionic acid, and 1,4-butanediol. Dithioacetic acid, ethylene glycol dithioacetic acid, ethylene glycol dithiopropionic acid, trimethylolpropane trithioacetic acid, trimethylolpropane trithiopropionic acid, trimethylolpropane tri 3-thiol butyric acid), pentaerythritol tetrathioacetic acid, pentaerythritol tetrathiopropionic acid, trithiol propionic acid tris(2-hydroxyethyl)isocyanate, 1,4-dimethylthiol benzene, 2 , 4,6-trithiol-secondary triazine, 2-(N,N-dibutylamine)-4,6-dithiol-secondary triazine, and the like.

These polyfunctional thiophenols may be used singly or in combination of two or more kinds at any ratio as needed.

The content of the polyfunctional thiophenol is preferably from 0.1 to 30% by weight, more preferably from 1 to 20% by weight, based on the total weight of the total solid content of the coloring composition for the color filter, more preferably from 1 to 20% by weight. When the content of the functional thiophenol is less than 0.1% by weight, the effect of adding the polyfunctional thiophenol is insufficient, and if it exceeds 30% by weight, the sensitivity is too high, and the resolution is rather lowered.

Antioxidant

The coloring composition for a color filter may contain an oxidation inhibitor. Since the oxidation preventing agent prevents the photopolymerization initiator or the thermosetting compound contained in the coloring composition for the color filter from being oxidized and yellowed by a thermal process during thermal curing or ITO annealing, the penetration of the coating film can be improved. rate. Therefore, by containing the oxidation preventing agent, yellowing caused by oxidation at the heating step can be prevented, and high coating film transmittance can be obtained.

The "oxidation inhibitor" may be a compound having an ultraviolet absorbing function, a radical replenishing function, or a peroxide decomposition function, and specific examples of the oxidation preventing agent include a hindered phenol system, a hindered amine system, a phosphine system, and a phosphite. A benzotriazole type, a benzophenone type, a hydroxylamine type, an oxalate type, and a triazine type compound can be used, and a conventional ultraviolet absorber, oxidation inhibitor, etc. can be used.

Among the above-mentioned oxidation inhibitors, from the viewpoint of the penetration rate and the sensitivity of the coating film, a preferred oxidation inhibitor is a hindered phenol oxidation inhibitor, a hindered amine oxidation inhibitor, and a phosphine oxidation prevention. Agent or phosphite system oxidation inhibitor. Further, it is more preferably a hindered phenol-based oxidation preventing agent, a hindered amine-based oxidation preventing agent or a phosphine-based oxidation preventing agent.

These oxidation inhibitors may be used singly or in combination of two or more kinds at any ratio as needed.

The content of the oxidation inhibitor is preferably based on the weight of the total solid content of the coloring composition for a color filter (100% by weight). When the content is 0.5 to 5.0% by weight, the brightness and sensitivity are good.

Uniform dye

In the colored composition, in order to improve the leveling property of the composition on the transparent substrate, it is preferred to add a leveling agent. The leveling agent is preferably a dimethyl siloxane having a polyether structure or a polyester structure in the main chain. Specific examples of the dimethyl siloxane having a polyether structure in the main chain include FZ-2122 manufactured by TORAY‧Dow Corning Co., Ltd. and BYK-333 manufactured by BYK Corporation. Specific examples of the dimethyl methoxy olefin having a polyester structure in the main chain include, for example, BYK Corporation. BYK-310 and BYK-370, etc. It is also possible to use dimethyl methoxyoxane having a polyether structure in the main chain and dimethyl methoxy oxane having a polyester structure in the main chain. The content of the leveling agent is generally 0.003 to 0.5% by weight based on the total weight of the coloring composition (100% by weight).

A particularly suitable leveling agent is a compound having a hydrophobic group and a hydrophilic group in the molecule, which is a kind of a so-called surfactant, which has hydrophilicity and low solubility in water, and is added to a red colored composition. The feature that the surface tension reducing ability is low, and even if the surface tension reducing ability is low, it is useful for a material having good lubricity of a glass plate, and it is preferably used in an amount of coating film defects caused by no foaming. It suppresses the chargeability. It is preferred to use a dimethyl siloxane having a polyalkylene oxide unit as a leveling agent having such suitable characteristics. The polyalkylene oxide unit includes a polyethylene oxide unit and a polyoxypropylene unit; the dimethyloxane may also have both a polyethylene oxide unit and a polypropylene oxide unit.

Further, the combination of the polyalkylene oxide unit and the dimethyloxane may be any of the following types: a pendant type in which a polyalkylene oxide unit is combined in a repeating unit of dimethyloxane; a polyepoxy a terminal unit modified with an alkane unit bonded to a terminal end of dimethyloxane; and a linear block copolymer type in which a polyalkylene oxide unit is repeatedly and repeatedly bonded to dimethyloxane. A dimethyl methoxy olefin having a polyalkylene oxide unit is commercially available from TORAY‧Dow Corning Co., Ltd., and examples thereof include FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, and FZ-2203. FZ-2207, but is not limited to these.

Anionic, cationic, nonionic or amphoteric surfactants may also be added to the leveling agent. It is also possible to use two or more kinds of surfactants in combination.

Examples of the anionic surfactant which is auxiliaryly added to the leveling agent include polyethylene oxide ether sulfate, sodium dodecylbenzenesulfonate, and styrene-acrylic acid copolymer acrylate. Sodium alkylnaphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, ethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, ethanolamine stearate, ammonium stearate, sodium lauryl sulfate, styrene - Monoethanolamine and polyethylene oxide ether phosphate ether of an acrylic copolymer.

The cationic surfactant of the auxiliary leveling agent may, for example, be an alkyl 4-grade ammonium salt or the like. Examples of the nonionic surfactant that is auxiliaryly added to the leveling agent include polyethylene oxide oleyl ether, polyethylene oxide lauryl ether, polyepoxy decyl phenyl ether, and polyethylene oxide ether phosphate. Bismuth of alkyl quaternary ammonium carboxylate and alkyl imidazoline, such as polyethylene oxide sorbitan glyceryl stearate, polyethylene glycol monolauryl ester, alkyl dimethylamine acetate quaternary ammonium carboxylate inner salt A surfactant, and a fluorine- or sulfhydryl surfactant.

"hardener, hardening accelerator"

Moreover, in order to assist the hardening of the thermosetting resin, a hardener, a hardening accelerator, etc. may be contained in this coloring composition as needed. The hardening agent to be used is a phenol resin, an amine compound, an acid anhydride, an active ester, a carboxylic acid compound, a sulfonic acid compound, etc., but is not particularly limited thereto, and may be used in a reaction with a thermosetting resin. Any hardener can be used. These may be used alone or in combination of two or more. The content of the hardening accelerator is preferably 0.01 to 15% by weight based on the total amount of the thermosetting resin.

<Other additive ingredients>

In the colored composition, a storage stabilizer may be contained in order to stabilize the viscosity of the composition over time. Further, in order to improve the adhesion to the transparent substrate, a adhesion promoter such as a decane coupling agent may be contained.

Examples of the storage stabilizer include 4-grade ammonium chlorides such as benzyltrimethyl chloride and dimethylhydroxylamine; organic acids such as lactic acid and oxalic acid, and ethyl ether; tertiary butyl pyrocatechol; An organic phosphine such as ethyl phosphine or tetraphenylphosphine; and a phosphite. The storage stabilizer is preferably used in an amount of 0.1 to 10% by weight based on the coloring agent component in the colored composition (100% by weight).

Examples of the adhesion promoter include the following decane coupling agents: ethylene decane such as ethylene tris(β-methoxy oxy) decane, ethylene ethoxy decane, and ethylene trimethoxy decane; γ-methyl propylene oxy propylene; (meth)acrylic acid decane such as trimethoxydecane; β-(3,4-epoxycycloalkyl)ethyltrimethoxydecane, β-(3,4-epoxycycloalkyl)methyltrimethoxy Pyrantane, β-(3,4-epoxycycloalkyl)ethyltriethoxydecane, β-(3,4-epoxycycloalkyl)methyltriethoxydecane, γ-glycidyl Epoxy decanes such as oxypropyltrimethoxydecane and γ-glycidoxypropyltriethoxydecane; N-β(aminoethyl)γ-aminopropyltrimethoxydecane, N-β (Amineethyl) γ-aminopropyltriethoxydecane, N-β(aminoethyl)γ-aminopropylmethyldiethoxydecane, γ-aminopropyltriethoxydecane, γ- Amino decane such as aminopropyltrimethoxydecane, N-phenyl-γ-aminopropyltrimethoxydecane, N-phenyl-γ-aminopropyltriethoxydecane; and γ-mercaptopropyltrimethyl A thiononane such as oxydecane or γ-mercaptopropyltrimethylethyl decane. The adhesion improving agent can be used in an amount of 0.01 to 10% by weight, and more preferably 0.05 to 5% by weight, based on the total amount of the coloring agent in the coloring composition (100% by weight).

"Manufacturing method of coloring composition"

The coloring composition for the color filter may be variously dispersed using a kneader, a 2-roll mill, a 3-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, a planetary mixer, or an attritor. By the method, the fluorescent pigment (A) is finely dispersed in a coloring agent carrier composed of a resin binder (C) and/or an organic solvent, and is preferably produced by finely dispersing together with a dispersing aid. Further, when the solubility of the colorant is high, the solubility in the solvent to be used is specifically high, if It is a state which melt|dissolved by stirring, and the state of a foreign material is not confirmed, and it is not necessarily the fine-

Further, when the organic pigment (D) is contained as a coloring agent, the fluorescent pigment (A), the organic pigment (D), other coloring agents, and the like are mixed, dispersed, or individually dissolved or dispersed in the colorant carrier. It can be mixed and manufactured.

When used as a photosensitive coloring composition (resist material) for a color filter, it can prepare as a solvent-developing type or an alkali-developing type coloring composition. The solvent-developing type or the alkali-developing type coloring composition may be a mixture of a resin solution containing the above-mentioned fluorescent pigment (A), a photopolymerizable monomer and/or a photopolymerization initiator, and a solvent mixture and a dispersion aid if necessary. Adjust with additives and the like. The organic compound (B) can also be added at the stage of preparing the coloring composition, and later added to the prepared coloring composition, and the same effect can be obtained.

(dispersion aid)

When the colorant is dispersed in the colorant carrier, a dispersing aid such as a resin type dispersant or a surfactant may be suitably used. The dispersing aid has a good ability to disperse the coloring agent, and the effect of preventing the re-coagulation of the dispersing coloring agent is great. Therefore, when a coloring composition obtained by dispersing a coloring agent in a coloring agent carrier by using a dispersing aid is used, a color filter having a high spectral transmittance can be obtained.

[Resin type dispersant]

The resin type dispersant has a pigment affinity site having a property of adsorbing on a pigment and a site compatible with a pigment carrier, and has a function of adsorbing to a colorant to stabilize the dispersion of the colorant with respect to the pigment carrier. As the specific resin type dispersant, for example, a polycarboxylate such as polyurethane or polyacrylate, an unsaturated polyamine, a polycarboxylic acid, a polycarboxylic acid (partial) amine salt, or a polycarboxylic acid can be used. Ammonium salt, polycarboxylic acid alkylamine salt, polyoxyalkylene oxide, long chain polyamine guanamine phosphate, hydrocarbon group-containing polycarboxylate or the like, by having a polymerization (lower alkylenimine) An oily dispersant such as guanamine or a salt thereof formed by reacting a polyester having a free carboxyl group, (meth)acrylic acid-(meth)acrylate copolymer, styrene-maleic acid copolymer, polyethylene A water-soluble resin such as an alcohol or polyvinylpyrrolidone, a water-soluble polymer compound, a polyester-based dispersant, a modified polyacrylate-based dispersant, an ethylene oxide/propylene oxide-addition compound, and a phthalate-based dispersant. These may be used alone or in combination of two or more. The resin type dispersant is not necessarily limited to these.

Commercially available resin type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166 manufactured by BYK-Chemie. 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164, Or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, 21116, 21324, or Lactimon, Lactimom-WS or Bykumen, etc., SOLSPERSE 3000, 9000, 13000, 13240 manufactured by Lubrizol, Japan. , 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000 , 76500, etc., EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, manufactured by Chiba Corporation, Japan. , 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 75 00, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., AJISPER-PA111, PB711, PB821, PB822, PB824, etc., manufactured by Ajinomoto Fine-Techno.

[Surfactant]

The surfactant may, for example, be sodium lauryl sulfate, polyethylene oxide ether sulfate, sodium dodecylbenzenesulfonate, an acrylate of a styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate or an alkyl group. Sodium phenyl ether disulfonate, ethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, ethanolamine stearate, ammonium stearate, sodium lauryl sulfate, ethanolamine of styrene-acrylic acid copolymer, polyepoxy An anionic surfactant such as an ethane ether phosphate; an alkyl surfactant such as an alkyl 4- toluene salt or an ethylene oxide additive thereof; an alkyl group such as an alkyl dimethylamine acetate quaternary ammonium carboxylate a quaternary ammonium carboxylate inner salt; and an amphoteric surfactant such as an alkyl imidazoline. These may be used singly or in combination of two or more, but it is not necessarily limited to these.

When a resin type dispersant or a surfactant is added, it is preferably 0.1 to 55 parts by weight, and more preferably 0.1 to 45 parts by weight, based on 100 parts by weight of the coloring agent. When the amount of the resin-type dispersant or the surfactant is less than 0.1 part by weight, it is difficult to obtain an effect of addition, and when the amount is more than 55 parts by weight, excessive dispersant may affect dispersion.

"Removing coarse particles"

The coloring composition for a color filter is preferably a coarse particle of 5 μm or more, more preferably a coarse particle of 1 μm or more, and more preferably a coarse particle of 0.5 μm or more, by a mechanism such as a centrifugal separation, a sintered filter or a membrane filter. Removal of particles and mixed dust. As described above, it is preferable that the coloring composition for a color filter does not contain particles of 0.5 μm or more. All particles are preferably substantially 0.3 μm or less. Here, the measurement was carried out using a particle size distribution measuring apparatus "Nano-S (Sysmex Co., Ltd.)" using a dynamic light scattering method.

Color Filter

The color filter of this aspect has at least one red filter segment, at least 1 The green filter segments and the at least one blue filter segment are formed by using the color filter composition for the at least one filter segment. Among them, the red filter segment and the blue filter segment are preferably formed using the above colored composition.

"Manufacturing method of color filter"

The color filter can be manufactured by a printing method or photolithography.

When the filter segment is formed by the printing method, only the printing and drying of the blue coloring composition prepared as the printing ink are repeated, and the patterning can be completed. Therefore, the color filter is manufactured at a low cost. Good mass production. Further, by the development of printing technology, it is possible to perform printing of a fine pattern having high dimensional accuracy and smoothness. When printing, it is preferable that the ink does not dry and solidify on the printing plate or on the felt cloth. Moreover, the control of the fluidity of the ink on the printing press is also very important, and the viscosity of the ink can be adjusted by a dispersing agent or an extender pigment.

When the filter segment is formed by the photolithography method, the coating is used as the solvent developing type or the alkali developing type by a coating method such as spray coating or spin coating, slit coating or roll coating on a transparent substrate. The photosensitive coloring composition of the blue coloring composition prepared by the resist material was applied to have a dry film thickness of 0.2 to 5 μm. The film which is dried as needed is subjected to ultraviolet light exposure through a mask having a specific pattern which is provided in contact with or non-contact with the film. Thereafter, the solution is immersed in a solvent or an alkali developer, or the developer is sprayed by a sprayer or the like to remove the uncured portion, and a desired pattern is formed, and then the same operation is repeated for other colors to produce a color filter. Further, in order to promote polymerization of the colored resist material, heating may be applied as needed. If the photolithography method is used, a color filter having a higher precision than the above printing method can be manufactured.

At the time of development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as the alkali developing solution, and an organic base such as dimethylbenzylamine or triethanolamine can also be used. Also, in the developer An antifoaming agent or a surfactant may be added.

Further, in order to increase the ultraviolet exposure sensitivity, after drying and drying the coloring resist, a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin may be applied to form a film which prevents oxygen from inhibiting polymerization. , UV exposure.

In addition to the above methods, the color filter can also be produced by an electrodeposition method, a transfer method, or the like, and the coloring composition can be used in any method. Furthermore, the electrodeposition method is formed by using a transparent conductive film formed on a substrate, and performing electrophoretic deposition of each color filter segment on the transparent conductive film by electrophoresis of colloidal particles, thereby fabricating a color filter. The method. Further, the transfer method is a method in which a filter segment is formed in advance on the surface of the transferable transfer substrate, and the filter segment is transferred to a desired substrate.

A black matrix may be formed in advance before forming the color filter segments on the transparent substrate or the reflective substrate. The black matrix is a multilayer film of chromium or chromium/chromium oxide, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed, but is not limited thereto. Further, 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. Further, a film, a transparent conductive film, or the like may be formed on the color filter as needed.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. Further, in the examples, "part" and "%" indicate "weight portion" and "weight%", respectively.

Further, the method for measuring the weight average molecular weight (Mw) of the resin and the contrast ratio of the coating film is as follows.

(weight average molecular weight (Mw) of resin

The weight average molecular weight (Mw) molecular weight of the resin is connected to the 2 rows of TSK-GEL using HLC-8220GPC (manufactured by TOSOH Co., Ltd.) as a device. SUPER HZM-N was used as a column and the molecular weight converted to polystyrene was measured using THF as a solvent.

(measurement method of contrast ratio)

The light emitted from the backlight unit for liquid crystal display is polarized by the polarizing plate, and reaches the polarizing plate by the dried coating film of the colored composition applied on the glass substrate. If the polarizing plate is parallel to the polarizing plate, the light will penetrate the polarizing plate, but when the polarizing surface is orthogonal, the light will be blocked by the polarizing plate. However, when the light which is polarized by the polarizing plate passes through the dried coating film of the coloring composition, if scattering due to the pigment particles occurs, a deviation occurs in one of the polarizing surfaces, and when the polarizing plates are parallel, the amount of light penetrating the polarizing plate is reduced. When the polarizing plates are orthogonal, a part of the light penetrates the polarizing plate. The transmitted light was measured as the luminance on the polarizing plate, and the luminance ratio (contrast ratio) between the luminance when the polarizing plates were parallel and the orthogonal direction was calculated.

(contrast ratio) = (brightness in parallel) / (brightness in orthogonal)

Therefore, if scattering occurs due to the pigment in the coating film, the brightness in parallel is lowered, and the brightness in the orthogonal direction is increased, so that the contrast ratio is lowered.

In addition, a color luminance meter ("BM-5A" manufactured by TOPCON Co., Ltd.) was used as a luminance meter, and a polarizing plate ("NPF-G1220DUN" manufactured by Nitto Denko Corporation) was used as a polarizing plate. Further, in order to block unnecessary light during measurement, a black mask having a 1 cm square hole was placed in alignment with the measurement portion.

First, a method for producing a resin binder (C) solution, a method for preparing a resin-based dispersant solution, a fluorescent pigment (A), a method for producing the same, and a general formula (1) will be described. The organic compound (B), the method for producing a pigment dispersion, and the method for producing a photosensitive coloring composition.

<Method for Producing Resin Adhesive (C) Solution> (modulation of acrylic resin solution)

Into the reaction vessel, 800 parts of cyclohexanone was placed, and while the container was filled with nitrogen gas, the mixture was heated to 100 ° C, and at the same temperature, 80.0 parts of styrene, 40.0 parts of methacrylic acid, and 85.0 parts of methyl methacrylate were dropped over 1 hour. A mixture of 95.0 parts of n-butyl methacrylate and 10.0 parts of azobisisobutyronitrile was subjected to polymerization.

After the dropwise addition, the mixture was further reacted at 100 ° C for 3 hours, and then 2.0 parts of azobisisobutyronitrile was dissolved in 50 parts of cyclohexanone, and the reaction was further continued at 100 ° C for 1 hour to obtain a weight average molecular weight of about 30,000 and an acid value. 87 mg KOH / g of a cyclohexanone solution of an acrylic resin.

After cooling to room temperature, the resin solution was sampled to about 2 g, and dried by heating at 180 ° C for 20 minutes, and the non-volatile component was measured. In the previously synthesized resin solution, ethylene glycol monomethyl ether ethyl ester was added to make the non-volatile component 20% by weight, prepared into an acrylic resin solution.

<Modulation method of resin type dispersant solution>

A commercially available resin type dispersant EFKA 4300 manufactured by BASF Corporation and ethylene glycol monomethyl ether ethyl ester were used to prepare a 40% by weight solution of a nonvolatile component, and used as a resin type dispersant solution.

<Method for producing fluorescent pigment (A)> (xanthene dye (A-1); rose red halide)

The following procedure was used to prepare a xanthene system consisting of CI Acid Red 52 and dialkyl (alkyl C14-C18) dimethylammonium chloride (Arquad 2HT-75) (molecular weight of the cationic moiety 438-550). Dye (A-1).

In the 7~15 mol% sodium hydroxide solution, the C.I. acid red is dissolved and charged. Mix and mix, stir, heat to 70-90 ° C, and then drop Arquad 2HT-75. Further, Arquad 2HT-75 may be dissolved in water and used as an aqueous solution. After dropping Arquad 2HT-75, the mixture was stirred at 70 to 90 ° C for 60 minutes to sufficiently carry out the reaction. The end point of the reaction was confirmed to be that the reaction liquid was dropped on the filter paper, and the end point was not bleed, and it was judged that the halide was obtained. After being allowed to cool to room temperature while stirring, suction filtration is carried out, and after washing with water, the halide remaining on the filter paper is removed by a dryer and dried to obtain CI acid red 52 and a dialkyl group (alkyl group is C14 to C18). A xanthene dye (A-1) of a halide of dimethyl ammonium chloride.

(xanthene dye (A-2); rose red halide)

The xanthene dye (A-2) consisting of C.I. Acid Red 52 and distearyl dimethylammonium chloride (QUARTAMIN D86P) (having a molecular weight of 550 in the cationic portion) was prepared by the following procedure.

In 7~15 mol% sodium hydroxide solution, dissolve C.I. Acid Red 52, mix thoroughly, stir, heat to 70-90 °C, and then drop QUARTAMIN D86P several times. Further, Arquad 2HT-75 may be dissolved in water and used as an aqueous solution. After dropping Arquad 2HT-75, the mixture was stirred at 70 to 90 ° C for 60 minutes to sufficiently carry out the reaction. The end point of the reaction was confirmed to be that the reaction liquid was dropped on the filter paper, and the end point was not bleed, and it was judged that the halide was obtained. After being cooled to room temperature while stirring, suction filtration is carried out, and after washing with water, the halide remaining on the filter paper is removed by a dryer and dried to obtain CI Acid Red 52 and distearyl dimethyl ammonium chloride. Halogenated xanthene dye (A-2).

(xanthene dye (A-3); rose red sulfonate sulfonamide compound)

According to the description of JP-A-6-194828, CI acid red 52 is chlorinated by a sulfonic acid group, and then reacted with a theoretical equivalent of 2-ethylalkylamine in dioxane. Further, a xanthene dye (A-3) of a sulfonic acid guanamine compound of CI Acid Red 52 was obtained.

(xanthene dye (A-4); rose red halide)

The xanthene dye (A-4) consisting of C.I. Basic Red 1 and 2-Amine-1-naphthalenesulfonic acid (prodosic acid) (molecular weight 223) was prepared by the following procedure.

2-Amino-1-naphthalenesulfonic acid (proteroic acid) (molecular weight 223) was dissolved in a 9 mol% sodium hydroxide solution, and the mixture was sufficiently stirred and stirred to obtain a sodium salt. After heating the aqueous solution of the 2-amino-1-naphthalenesulfonic acid (prefibeic acid) sodium salt to 85 ° C, the rose red 6GCP dye (C.I. Basic Red 1) was added dropwise one by one. Further, rose red 6GCP is dissolved in water and used as an aqueous solution. After the rose red 6GCP was dropped, the mixture was stirred at 85 ° C for 55 minutes to sufficiently carry out the reaction. The end point of the reaction was confirmed to be that the reaction liquid was dropped on the filter paper, and the end point was not bleed, and it was judged that the halide was obtained. After being allowed to cool to room temperature while stirring, suction filtration is carried out, and after washing with water, the halide remaining on the filter paper is removed by a dryer and dried to obtain Rose Bengal 6GCP and 2-amine-1-naphthalenesulfonic acid. A xanthene dye (A-4) of a halide of an acid.

(triphenylmethane dye (A-5); triphenylmethane halide)

A triphenylmethane dye (A-5) consisting of C.I. Basic Blue 7 and 2-Amine-1-naphthalenesulfonic acid (prodosic acid) (molecular weight 223) was produced by the following procedure.

2-Amino-1-naphthalenesulfonic acid (proteroic acid) (molecular weight 223) was dissolved in a 9 mol% sodium hydroxide solution, and the mixture was sufficiently stirred and stirred to obtain a sodium salt. After heating the aqueous solution of the 2-amino-1-naphthalenesulfonic acid (proteroic acid) (molecular weight 223) sodium salt to 85 ° C, the Victoria blue dye (C.I. Basic Blue 7) was successively dropped. Further, the Victoria blue dye may be dissolved in water and used as an aqueous solution. After the Victoria blue dye was dropped, the mixture was stirred at 85 ° C for 55 minutes to sufficiently carry out the reaction. The end point of the reaction was confirmed to be that the reaction liquid was dropped on the filter paper, and the end point was not bleed, and it was judged that the halide was obtained. After being allowed to cool to room temperature while stirring, suction filtration is carried out, and after washing with water, the dryer remains in the dryer. The halide on the filter paper was dehydrated and dried to obtain a xanthene dye (A-5) of a Victoria blue dye and a halide of 2-amine-1-naphthalenesulfonic acid (topoic acid).

(triphenylmethane dye (A-6); triphenylmethane halide)

The triphenylmethane dye (A-6) consisting of C.I. Basic Blue 7 and perchloric acid (molecular weight 100.5) was prepared by the following procedure.

Perchloric acid (molecular weight 100.5) was dissolved in a 9 mol% sodium hydroxide solution, and the mixture was thoroughly stirred and stirred to obtain a sodium salt. After heating the aqueous solution of sodium perchlorate to 85 ° C, the Victoria Blue dye (C.I. Basic Blue 7) was added dropwise one by one. Further, the Victoria blue dye may be dissolved in water and used as an aqueous solution. After the Victoria blue dye was dropped, the mixture was stirred at 85 ° C for 55 minutes to sufficiently carry out the reaction. The end point of the reaction was confirmed to be that the reaction liquid was dropped on the filter paper, and the end point was not bleed, and it was judged that the halide was obtained. After being cooled to room temperature while stirring, suction filtration is carried out, and after washing with water, the halide remaining on the filter paper is removed by a dryer and dried to obtain a xanthene dye of Victoria blue dye and perchloric acid halide ( A-6).

(Quinoline dye (A-7))

The quinoline dye (A-7) was obtained by the following method.

[Method for producing quinoline dye (A-7)]

2.3 parts of 6-iso-propyl-2-methylquinoline, 2.5 parts of naphthalene dicarboxylic anhydride, and 30 parts of benzoic acid were mixed, and stirred at 200 ° C for 7 hours. After allowing to cool, 100 parts of methanol was added and stirred for 1 hour. Then, the precipitated solid was collected by suction filtration. Further, the solid was placed in 200 portions of methanol, and after stirring for 1 hour, the solid was collected by suction filtration. The mixture was dried overnight in a vacuum dryer (40 ° C) to obtain a product of 3.1 parts. The yield was 67%. The resultant was subjected to the same method as a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics Co., Ltd.). m/z = 366 (molecular weight: 365.4), which was confirmed to be a target substance.

(Quinoline pigment (A-8))

As the quinoline pigment, C.I. Pigment Yellow 138 (Paliotol Yellow K0961-HD manufactured by BASF Corporation) was used.

(Benzene dye (A-9); triphenylmethane dye halide)

The triphenylmethane halide (A-9) obtained by the following method was used.

By blacing 106 g (1 mol) of benzaldehyde with 508 g (2 mol) of n-benzyl-n-butyl-m-toluidine, sulfonation was carried out by the method disclosed in the literature BIOS 1157, 53 to introduce a trisulfonate group by manganese dioxide ( After oxidizing it by MnO2), it reacted with p-aminophenylethyl ether to obtain 500 g of an anion component.

This 91 g (0.1 mol) was dissolved in water at a water temperature of 60 ° C to obtain a 3% aqueous solution. It was prepared to pH 7 and filtered. While stirring the filtrate, an aqueous solution of 22.5 g (0.12 mol) of an anionic component of 3-(2-ethylhexyloxy)propylamine was added dropwise over 40 minutes. After reacting at room temperature for 2 hours, it was adjusted to pH = 5 to 6, and heated to 40 ° C to be coarsely granulated. Thereafter, it was filtered, washed with water and dried to obtain 97 g of a blue halide.

(thiazine dye (A-10); thiazine halide)

The following procedure was used to prepare C.I. Basic Blue 9 and 2,8-Diamine-1-naphthyl-5,7- A thiazide dye (A-8) composed of disulfonic acid (molecular weight 334). 2,8-diamine-1-naphthyl-5,7-disulfonic acid (molecular weight 334) is dissolved in 7~15 mol% sodium hydroxide solution, fully mixed and stirred to obtain the sodium salt . After heating the aqueous solution of sodium 2,8-diamine-1-naphthyl-5,7-disulfonate to 70 to 90 ° C, the methylene blue FZ dye (C.I. Basic Blue 9) was added dropwise one by one. Further, the methylene blue FZ dye may be dissolved in water and used as an aqueous solution. After the methylene blue FZ dye was dropped, the mixture was stirred at 70 to 90 ° C for 40 to 60 minutes to sufficiently carry out the reaction. The end point of the reaction was confirmed to be that the reaction liquid was dropped on the filter paper, and the end point was not bleed, and it was judged that the halide was obtained. After being cooled to room temperature while stirring, suction filtration is carried out, and after washing with water, the halide remaining on the filter paper is removed by a dryer and dried to obtain methylene blue FZ dye and 2,8-diamine-1-naphthalene. A thiazide dye (A-10) of a halide of a base-5,7-disulfonic acid.

(thiazole dye (A-11); thiazole halide)

The thiazole dye (A-9) consisting of C.I. Direct Yellow 8 and distearyl dimethylammonium chloride (QUARTAMIN D86P) (molecular weight of the cationic moiety 550) was prepared by the following procedure.

In 7~15 mol% sodium hydroxide solution, dissolve C.I. Direct Yellow 8 and mix thoroughly. Stir and heat to 70-90 °C, then drop QUARTAMIN D86P several times. Further, QUARTAMIN D86P may be dissolved in water and used as an aqueous solution. After dropping QUARTAMIN D86P, stir at 70 to 90 ° C for 40 to 60 minutes to fully carry out the reaction. The end point of the reaction was confirmed to be that the reaction liquid was dropped on the filter paper, and the end point was not bleed, and it was judged that the halide was obtained. After being cooled to room temperature while stirring, suction filtration is carried out, and after washing with water, the halide remaining on the filter paper is removed by a dryer and dried to obtain CI Direct Yellow 8 and distearyl dimethyl ammonium chloride. Halide thiazole dye (A-11).

(diketopyrrolopyrrole pigment (A-12))

As the diketopyrrolopyrrole pigment, a diketopyrrolopyrrole-based red pigment C.I. Pigment Red 254 ("IRGAZIN RED 2030" manufactured by Chiba Corporation, Japan) was used.

<Organic compound (Bb) having an organic pigment skeleton or an aniline skeleton and a basic functional group>

The details of the organic compound (Bb) used in the examples are shown in Table 1.

<Organic compound (Ba) having an organic pigment skeleton or an aniline skeleton and an acidic functional group>

Table 2 shows the details of the organic compound (Ba) used in the examples.

<Organic compound (Bp) having an organic pigment skeleton or a functional group of an aniline skeleton and a quinone imine skeleton>

The details of the organic compound (Bp) used in the examples are shown in Table 3.

<Method for Producing Pigment Dispersion> (blue pigment dispersion (P-1))

11.0 parts of CI Pigment Blue 15:6 ("LIONOL BLUE ES" manufactured by Toyo Ink Co., Ltd.), 35.0 parts of acrylic resin solution, 5 parts of resin type dispersant solution, and 49 parts of ethylene glycol monomethyl ether acetate were used. After uniformly stirring and mixing, zirconia beads having a diameter of 0.5 mm were used, and dispersed by an IGER mill ("Mini Model M-250 MKII" manufactured by Iger Japan Co., Ltd.) for 3 hours, and then filtered through a 5.0 μm filter to prepare PB15:6. Blue pigment dispersion (P-1).

(Purple Pigment Dispersion (P-2))

The same procedure as for the blue pigment dispersion (P-1) was carried out except that CI Pigment Blue 15:6 was changed to CI Pigment Violet 23 (PV23) ("LIONOL VIOLET RL" manufactured by Toyo Ink Co., Ltd.). A violet pigment dispersion (P-2) of PV23 was produced.

(Red pigment dispersion (P-3))

The same procedure as for the blue pigment dispersion (P-1) was carried out except that CI Pigment Blue 15:6 was changed to CI Pigment Red 254 (PR254) ("IRGAPHOR RED B-CF" manufactured by Chiba Specialty Chemical Co., Ltd.). A red pigment dispersion (P-3) of PR254 was produced.

(Red pigment dispersion (P-4))

In addition to changing C.I. Pigment Blue 15:6 to C.I. Pigment Red 177 (PR177) (BASF A red pigment dispersion (P-4) of PR177 was produced in the same manner as the blue pigment dispersion (P-1) except for the "A2B" manufactured by the company.

(Green Pigment Dispersion (P-5))

In the same manner as the blue pigment dispersion (P-1), the same was produced except that CI Pigment Blue 15:6 was changed to CI Pigment Green 58 (PG58) ("A110" manufactured by Dainippon Ink Co., Ltd.). Green pigment dispersion of PG58 (P-5).

(Yellow Pigment Dispersion (P-6))

A yellow pigment of PY150 was produced by the same method as the blue pigment dispersion (P-1) except that CI Pigment Blue 15:6 was changed to CI Pigment Yellow 150 (PY150) ("E4GN" manufactured by LANXESS Co., Ltd.). Dispersion (P-5).

(Orange pigment dispersion (P-7))

An orange pigment of PY242 was produced by the same method as the blue pigment dispersion (P-1) except that CI Pigment Blue 15:6 was changed to CI Pigment Red 242 (PY242) ("Sandorin Scarlet 4RF" manufactured by Clariant Co., Ltd.). Dispersion (P-7).

(Blue pigment dispersion (P-8))

The same procedure was applied to the blue pigment dispersion (P-1) except that CI Pigment Blue 15:6 was changed to CI Pigment Blue 15:1 ("LIONOL BLUE 7120-V" manufactured by Toyo Ink Co., Ltd.). A blue pigment dispersion (P-8) of PB 15:1 was produced by the method.

(Green pigment dispersion (P-9))

The same procedure as for the blue pigment dispersion (P-1) was carried out except that CI Pigment Blue 15:6 was changed to CI Pigment Green 36 (PG36) ("LIONOL EGREEN 2YS" manufactured by Toyo Ink Co., Ltd.). A green pigment dispersion (P-9) of PG36 was produced.

[Example 1] (Dye containing resin solution (DA-1))

After the mixture was stirred and mixed to have a composition of the following composition, zirconia beads having a diameter of 0.5 mm were used, and dispersed by an IGER mill ("Mini Model M-250 MKII" manufactured by Iger Japan Co., Ltd.) for 2 hours, and further 5.0. A filter of μm was filtered to prepare a resin solution (DA-1) containing a dye.

Xanthene dye (A-1): 3.0

Acrylic resin solution: 57.5 parts

Organic Compound (Ba-19): 0.5

Cyclohexanone: 39.0

[Examples 2 to 36 and Comparative Examples 1 to 12] (Resin-containing resin solution (DA-2~48))

In the following, as shown in Table 2, a resin solution containing a dye (DA-2 to 48) was obtained in the same manner as the resin solution (DA-1) containing a dye, except that the composition and the amount of the mixture were changed. In addition, (A-8) was added as the dye (A), and when (A-12) was used, 0.8 parts of a commercially available resin type dispersant EFKA 4300 manufactured by BASF Corporation was added.

[Evaluation of coloring composition]

For the obtained dye-containing resin solution (DA-1 to 48), the following method was used to evaluate the contrast ratio. The results are shown in Table 5.

(contra rate)

The dye-containing resin solution (DA-1 to 48) is applied to a glass substrate of 100 mm × 100 mm and a thickness of 1.1 mm by a spin coater, and the film thickness of the dried coating film is applied. 1.2 μm was fired in an oven at 230 ° C for 20 minutes to prepare a coated substrate. The contrast ratio (CR) was measured using the obtained coated substrate.

The judgment criteria are as follows. Regarding the evaluation result, ○ indicates a good result, and Δ indicates a slight problem, but the level which does not constitute a problem in use, × corresponds to an unsuitable use.

○: 10000 or more

△: 7000 or more, less than 10000

×: less than 7000

a coloring composition comprising a fluorescent pigment (A), and an organic compound (B) having an organic pigment skeleton or an aniline skeleton, and an acidic functional group, a basic functional group or a quinone imine skeleton (B) It is very good, and it is said that this is an effect of suppressing the fluorescence of the fluorescent pigment (A) due to the organic compound (B).

[Example 37] (Blue photosensitive coloring composition (RB-1))

The mixture was uniformly stirred and mixed, and then filtered through a 1.0 μm filter to prepare a blue photosensitive coloring composition (RB-1).

Pigment dispersion (P-1): 40.0 parts

Dye-containing resin solution (DA-1): 10.0

Acrylic resin solution: 7.5

Photopolymerizable monomer: 2.0

(dipentaerythritol hexaacrylate)

Photopolymerization initiator: 1.5

2-methyl-1-[4-(methylthio)]-2-morpholinylpropan-1-one ("IRGACURE 907" manufactured by Chiba Special Chemical Co., Ltd.)

Organic solvent: 39.0

(ethylene glycol monomethyl ether acetate)

[Examples 38 to 46 and Comparative Examples 13 to 19] (Blue photosensitive coloring composition (RB-2~17))

A blue photosensitive coloring composition (RB-2 to 17) was produced in the same manner as in the blue photosensitive coloring composition (RB-1) except that the type of the dye-containing resin solution was changed as shown in Table 6. Here, the blending amount (weight portion) of the pigment dispersion and the dye-containing resin solution is selected at a temperature of 230 ° C when the coated substrate is formed, so as to conform to the C light source, x=0.150, y=0.060. Chroma. Further, the total content of the pigment dispersion and the dye-containing resin solution was 50.0 parts.

[Example 47] (Green photosensitive coloring composition (RG-1))

The mixture was uniformly stirred and mixed, and then filtered through a 1.0 μm filter to prepare a green photosensitive coloring composition (RG-1).

Pigment dispersion (P-5): 35.0 parts

Dye-containing resin solution (DA-19): 15.0 parts

Acrylic resin solution: 7.5

Photopolymerizable monomer: 2.0

(dipentaerythritol hexaacrylate)

Photopolymerization initiator: 1.5

2-methyl-1-[4-(methylthio)]-2-morpholinylpropan-1-one ("IRGACURE 907" manufactured by Chiba Special Chemical Co., Ltd.)

Organic solvent: 39.0

(ethylene glycol monomethyl ether acetate)

[Examples 47 to 52 and Comparative Examples 20 to 22] (Green photosensitive coloring composition (RG-2~9))

A green photosensitive coloring composition (RG-2 to 9) was produced in the same manner as the green photosensitive coloring composition (RG-1) except that the pigment dispersion and the dye-containing resin solution were changed as shown in Table 7. Here, the blending amount (weight portion) of the pigment dispersion and the dye-containing resin solution is selected at a temperature of 230 ° C when the coated substrate is produced, so as to conform to the C light source, x=0.290, y=0.600. Chroma. Further, the total content of the pigment dispersion and the dye-containing resin solution was 50.0 parts.

[Example 53] (Red photosensitive coloring composition (RR-1))

The mixture was uniformly stirred and mixed, and then filtered through a 1.0 μm filter to prepare a red photosensitive coloring composition (RR-1).

Pigment dispersion (P-3): 35.0 parts

Dye-containing resin solution (DA-3): 15.0 parts

Acrylic resin solution: 7.5

Photopolymerizable monomer: 2.0

(dipentaerythritol hexaacrylate)

Photopolymerization initiator: 1.5

2-methyl-1-[4-(methylthio)]-2-morpholinylpropan-1-one ("IRGACURE 907" manufactured by Chiba Special Chemical Co., Ltd.)

Organic solvent: 39.0

(ethylene glycol monomethyl ether acetate)

[Examples 54 to 59 and Comparative Examples 22 to 27] (Red photosensitive coloring composition (RR-2~13))

A red photosensitive coloring composition (RB-2 to 13) was produced in the same manner as the red photosensitive coloring composition (RR-1) except that the pigment dispersion and the dye-containing resin solution were changed as shown in Table 8. Here, the blending amount (weight portion) of the pigment dispersion and the dye-containing resin solution is selected at a temperature of 230 ° C when the coated substrate is formed, so as to conform to the C light source, x=0.645, y=0.323. Chroma. Further, the total content of the pigment dispersion and the dye-containing resin solution was 50.0 parts.

[Evaluation of photosensitive coloring composition]

For the obtained photosensitive coloring compositions (RB-1~17, RG-1~9, RR-1~13), the following methods were used to evaluate the brightness (spectral transmittance) and the contrast ratio (CR). . The results are shown in Tables 6-8.

(brightness (spray penetration rate))

Each of the photosensitive coloring compositions was applied onto a glass substrate of 100 mm × 100 mm and a thickness of 1.1 mm by a spin coater, and exposed to ultraviolet light at an exposure amount of 50 mJ/cm 2 to obtain 0.2% by weight of sodium carbonate at 23 ° C. The aqueous solution was spray-developed for 30 seconds, and baked in an oven at 230 ° C for 20 minutes to obtain a coated substrate of the obtained photosensitive colored composition. The measurement of the luminance (the spectral transmittance) was performed using the obtained coated substrate.

Further, the blue coating film formed of the blue photosensitive coloring composition was applied so as to have a chromaticity of x=0.150 and y=0.060 in accordance with the C light source after firing at 230 °C. Further, in the same manner, the green coating film formed of the green photosensitive coloring composition was applied at 230 ° C, and then applied in a color ratio of x=0.290 and y=0.600 in accordance with the C light source. The red coating film formed by the photosensitive coloring composition was applied at 230 ° C, and then applied in a chromaticity of x=0.645 and y=0.323 in accordance with the C light source.

Further, the measurement of the luminance (spectral transmittance) in the XYZ colorimetric chromaticity diagram was performed by using a spectrophotometer (OTSUKA LCF-1100M).

The judgment criteria are as follows. In terms of the evaluation results, ○ indicates a good result, and Δ indicates a slight problem, but does not constitute a problem level in use.

Blue photosensitive coloring composition

○: 11.8 or more

△: 11.5 or more and less than 11.8

×: less than 11.5

Green photosensitive coloring composition

○: 61 or more

△: 60 or more, less than 61

×: less than 60

Red photosensitive coloring composition

○: 20.4 or more

△: 20.0 or more and less than 20.4

×: less than 20.0

(contra rate)

The contrast ratio (CR) was measured using the same substrate as the coated substrate used for the luminance measurement.

The judgment criteria are as follows. In terms of the evaluation results, ○ indicates a good result, and Δ indicates a slight problem, but does not constitute a problem level in use.

Blue photosensitive coloring composition

○: 11,000 or more

△: 8000 or more, less than 11000

×: less than 8000

Green photosensitive coloring composition

○: 11,000 or more

△: 9000 or more, less than 11000

×: less than 9000

Red photosensitive coloring composition

○: 22000 or more

△: More than 20,000, less than 22,000

×: less than 20000

The coloring composition containing the fluorescent pigment (A) and the organic pigment skeleton or the aniline skeleton and the organic compound (B) having a basic functional group is very good in contrast ratio, and it is judged that this is due to the organic compound. (B) The effect of suppressing the fluorescence of the fluorescent pigment (A) is suppressed.

[Example 60] (Color Filter (CF-1))

On the glass substrate, the black matrix is patterned, on the substrate, The red photosensitive coloring composition (RR-13) was applied by a spin coater to form a colored film. In the film, an intermediate mask was used to irradiate ultraviolet rays of 150 mJ/cm 2 with an ultrahigh pressure mercury lamp. Next, spray development was carried out by an alkali developing solution composed of a 0.2% by weight aqueous sodium carbonate solution, and the unexposed portion was removed, and then washed with ion-exchanged water, and the substrate was heated at 220 ° C for 20 minutes to form a red filter. Section. Here, the red filter segment is subjected to heat treatment at 220 ° C, and conforms to the chromaticity of the C light source (hereinafter also used for green and blue), x=0.645, y=0.323. Moreover, by the same method, the green color filter section uses a green photosensitive coloring composition (RG-9), which conforms to the chromaticity of x=0.290 and y=0.600, and the blue filter section uses blue. The coloring composition (RB-1) satisfies the chromaticity of x=0.150 and y=0.060, and each of the filter segments is formed to obtain a color filter (CF-1).

[Examples 61 to 74 and Comparative Examples 28 to 34] (Color Filter (CF-2~22))

The color filter was obtained in the same manner as the color filter (CF-1) except that the red photosensitive coloring composition, the green photosensitive coloring composition, and the blue photosensitive coloring composition shown in Table 9 were changed. (CF-2~22).

[Evaluation of color filters]

For the obtained color filter, the following methods were used to evaluate the brightness (split transmittance) and the contrast ratio. The results are shown in Table 9.

(brightness (spray penetration rate))

The measurement of the luminance (spectral transmittance) in the XYZ colorimetric chromaticity diagram was carried out using a spectrophotometer (OTSUKA LCF-1100M).

The judgment criteria are as follows. In terms of the evaluation results, ○ indicates a good result, and Δ indicates a slight problem, but does not constitute a problem level in use.

○: 28.80 or more

△: 28.60 or more and less than 28.80

×: less than 28.60

(contra rate)

The judgment criteria are as follows. In terms of the evaluation results, ○ indicates a good result, and Δ indicates a slight problem, but does not constitute a problem level in use.

○: 18000 or more

△: 165000 or more and less than 18000

×: less than 165,000

[Example 75 and Comparative Example 35]

In order to confirm the effect of the organic compound B on the fluorescence elimination of the dye A, the following conditions were used to compare the fluorescence emission intensity of the coated substrate prepared in Example 20 with Comparative Example 7.

Measuring device: Japan spectrophotometer FP-750

Measurement conditions: excitation wavelength 420 nm (selected as visible wavelength in the visible region)

The measurement wavelength is 570 nm (the wavelength side longer than the excitation wavelength, which is selected in the maximum region of the fluorescence intensity distribution)

High light sensitivity condition

Measurement results: coated substrate of Example 20 (Example 74)----fluorescence intensity 10

Coating substrate of Comparative Example 7 (Comparative Example 35)----fluorescence intensity 28

The above "fluorescence intensity" is the intensity of light emitted from the fluorescent light emitted from the film surface when the film is irradiated with the excitation light, and the larger the number, the stronger the light emission intensity. The film having a higher fluorescence intensity is more likely to increase in the proportion of unpolarized light when the polarized light is transmitted, and it is judged that the CR value is lowered.

By the addition of the organic compound (B), there is a fluorescence-eliminating effect on the dye (A), and it is confirmed that the CR value-improving effect for Comparative Example 7 has been confirmed in Example 20.

Therefore, there is a fluorescence-eliminating effect of the organic compound (B) on the dye (A), which is confirmed to contribute to an increase in the CR value.

By using the colored composition for a color filter to suppress fluorescence emission by a fluorescent pigment, a color filter having high luminance and high contrast ratio can be produced.

The embodiments of the present invention have been described, but the embodiments are presented as examples and are not intended to limit the scope of the invention. The present invention can be implemented in various other forms, and various omissions, substitutions and changes can be made without departing from the scope of the invention. The embodiments and the modifications thereof are included in the scope of the invention and the scope of the invention as set forth in the appended claims.

Claims (8)

A coloring composition for a color filter, comprising a fluorescent pigment (A), an organic compound (B) represented by the general formula (1), and a resin binder (C); general formula (1) : P-Lm [In the general formula (1), P is an organic pigment skeleton or an aniline skeleton, and L is a basic functional group Lb, an acidic functional group La or a functional group Lp having a quinone imine skeleton, m is 1~ An integer of 4 representing the number of functional groups. The fluorescent pigment (A) is derived from a triphenylmethane dye, a diphenylmethane dye, a quinoline dye, a thiazine dye, a thiazole dye, a xanthene dye, and a diketopyrrolopyrrole. Any one of the groups consisting of a pigment. The coloring composition for a color filter according to the first aspect of the invention, wherein the organic pigment skeleton is a phthalocyanine pigment, a benzimidazolone pigment, a dioxazine pigment, an azo pigment, or an anthraquinone pigment. Any one selected from the group consisting of diterpene pigments, diketopyrrolopyrrole pigments, thiazinium blue pigments, and quinophthalone pigments. The coloring composition for a color filter according to the first aspect of the invention, wherein the basic functional group Lb has a basic functional group represented by the general formula (2) or (5), and the acidic functional group La has a general formula (3). Or the acidic functional group represented by (5), the functional group Lp having a quinone imine skeleton has a functional group represented by the general formula (4) or (5). General formula (2): [In the general formulas (2) to (4), X ¹ is -SO ₂ -, -CO-, -CH ₂ -, -NH-, -O-, an alkenyl group having 2 to 36 carbon atoms, and a carbon number of 1 ~20 alkylene, arylene having 1 to 20 carbon atoms, -CH ₂ NHCOCH ₂ -, -CH ₂ NHSO ₂ CH ₂ -, -CONHC ₆ H ₁₀ -, -CONHC ₆ H ₄ CO-, -OCH ₂ CH ₂ - or directly combined; in the general formulas (2), (4), Y ¹ is -NH-, -O- or directly bonded, n is an integer from 0 to 10; in the general formula (2), R ¹ and R ² are as follows: 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 hydrogen atom at the terminal, -NR ⁴ R ⁵ or -NR ⁴ R ⁵ H ⁺ U ^- alkanediyl having 1 to 30 carbon atoms; or R ¹ and R ² being integrated to form a heterocyclic ring which may further contain a nitrogen, oxygen or sulfur atom; the alkanediyl group may be contained by -O-substitution -CH ₂ -, U ^- represents an anion which represents a halide, BF ₄ ^- , PF ₆ ^- , ClO ₄ ^- , R ⁶ -CO ₂ ^- , R ⁷ -SO ₃ ^- [R ⁶ , R ⁷ contains aromatic a monovalent organic group of a group; R ³ is a ring-substituted group when R ¹ and R ^{2 are} integrated, o is a number thereof, and when o is 2 or more, R ³ may have another structure, and each is a hydrogen atom or a carbon alone. Alkyl groups of 1 to 20, alkenyl groups having 2 to 20 carbons or carbon 6 to 20. The arylene; general formula (3), G-based _{^{-COO -, -SO 3 -, -PO}} 3 2-, -OPO 3 2-, benzoic acid-terminated (-Ph-COO ^-), Any of the lysine end (-Ph(OH)-COO-), the benzenesulfonic acid end (-Ph-SO ₃ ^- ), and the phosphoric acid end (-Ph-PO ₃ ^2- ), the M system includes the G, etc. a cation of a hydrogen cation (Ph is a phenyl group); in the general formula (4), R ⁸ is a hydrogen atom, a halogen atom, -NO ₂ , -NH ₂ or -SO ₃ H, and p is 1 to 4 In the general formula (5), R ⁹ is a functional group represented by the general formulae (2) to (4); Q ¹ is a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, or a general formula ( 2) to (4) functional groups; X ² -SO ₂ -, -CO-, -CH ₂ -, -NH-, -O-, 2 to 36 carbons, carbon number 1~ 20 alkylene, arylene having 1 to 20 carbon atoms, -CH ₂ NHCOCH ₂ -, -CH ₂ NHSO ₂ CH ₂ -, -CONHC ₆ H ₁₀ -, -OCH ₂ CH ₂ -, -NHCOCH (COCR ¹⁰ ) or direct combination; Y ² -NH-, -NR ¹¹ -Z-NR ¹² -, -SO ₂ -Z-NR ¹³ -, -N=N- or direct combination, R ¹¹ ~R ¹³ are separately It is 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; a Z-alkylene group having 1 to 20 carbon atoms or an arylene group having 1 to 20 carbon atoms; T independently each line having a substituent of a carbon atom or a carbon atom also. ] The coloring composition for color filters according to item 3 of the patent application, wherein the anion M of the general formula (3) is a hydrogen ion, an alkali metal ion, an alkaline earth metal ion, a rare earth metal ion, a transition metal ion, and a general formula ( 8) Any of the anions shown. [In the general formula (6), R ¹⁴ to R ¹⁷ represent a hydrogen atom or an alkyl group having 1 to 30 carbon atoms (but not all hydrogen atoms). ] A coloring composition for a color filter according to item 1 of the patent application, wherein The fluorescent pigment (A) is a fluorescent acid dye halide and/or a fluorescent acid dye sulfonate guanamine compound. The coloring composition for a color filter according to the first aspect of the invention, wherein the weight ratio (B/A) to the organic compound (B) of the fluorescent pigment (A) is 0.05 to 2.0. A coloring composition for a color filter according to the first aspect of the invention, which further comprises an organic pigment (D). A color filter comprising: a filter segment on a substrate, wherein the filter segment is colored by a color filter according to any one of claims 1 to 7; The object is formed.