KR20130039697A - Color composition for color filter and color filter - Google Patents

Abstract

PURPOSE: A coloring composition is provided to improve the loss of contrast ratio by using a colorant, thereby manufacturing a color filter with high brightness and high contrast ratio. CONSTITUTION: A coloring composition for a color filter includes a colorant, an organic compound denoted by chemical formula 1: P-Lm, and a binder resin. In the chemical formula 1: P is an organic pigment skeleton or an amino benzene skeleton; L is a functional group Lp which has a basic functional group Lb, an acid functional group La, or a phthalimide skeleton; and m is an integer from 1-4, and means a number of a functional group. A color filter includes a filter segment which is formed of the coloring composition.

Description

COLOR COMPOSITION FOR COLOR FILTER AND COLOR FILTER

This invention relates to the color composition for color filters used for manufacture of the color filter used for a color liquid crystal display device, a color image tube element, etc., and the color filter provided with the filter segment formed using this coloring composition.

A color liquid crystal display device is a display device which displays by controlling the state of the polarization which the liquid crystal layer interposed between two polarizing plates passed through the 1st polarizing plate, and controlling the quantity of light which passes through the 2nd polarizing plate. As a color liquid crystal display device, the type using the twisted nematic (TN) system is becoming mainstream. The liquid crystal display device enables color display by providing a color filter between two polarizing plates. Liquid crystal display devices capable of color display are widely used in televisions and PC monitors.

As another typical liquid crystal display system, an in-plane switching (IPS) method in which a pair of electrodes are provided on one substrate and an electric field is applied in a direction parallel to the substrate, and a nematic liquid crystal having negative dielectric anisotropy is vertically aligned. There are a vertically aligned (VA) system to be made, an optically compensated band (OCB) system which performs optical compensation by orthogonalizing the optical axes of a uniaxial retardation film, and the like, and each has been put to practical use.

In general, the color filter is composed of a red (R), green (G) and blue (B) filter layer formed on the surface of a transparent substrate such as glass, or cyan (C), respectively corresponding to the complementary colors of red, green and blue. ), A fine strip (stripe) shaped filter segment (pixel) composed of a magenta (M) and a yellow (Y) filter layer, which is arranged in parallel or in an intersecting manner, or the fine filter segments are vertically and horizontally arranged. It consists of placed. The filter segments are fine from several microns to several hundred microns, and are arranged in a predetermined arrangement for each color.

On the color filter used for a color liquid crystal display device, generally, the transparent electrode for driving a liquid crystal is formed by vapor deposition or sputtering, and the alignment film for orientating a liquid crystal in a fixed direction is formed on it. In order to fully acquire the performance of these transparent electrodes and an oriented film, the formation process generally needs to be performed at 200 degreeC or more, Preferably it is 230 degreeC or more.

The quality items required for the color filters include brightness and contrast ratio. When using a color filter that can not achieve a high contrast ratio, when the color filter disturbs the state of polarization controlled by the liquid crystal, light leaks or does not transmit light when the light must be blocked (OFF state). Since the transmitted light attenuates when it is not (ON state), the screen becomes blurred. Therefore, in order to realize a high quality liquid crystal display device, high contrast is indispensable.

In addition, when a low-brightness color filter is used, the light transmittance is low, so that a dark screen is obtained, and in order to obtain a bright screen, it is necessary to increase the number of backlights that are light sources. Therefore, from the standpoint of suppressing increase in power consumption, high brightness of color filters has become a trend. In addition, since the color liquid crystal display device is used for televisions, PC monitors, and the like as described above, the demand for high reliability is increased along with high brightness and high contrast for the color filter.

As a manufacturing method of a color filter, there exist a dyeing method using a dye and salt-forming dye as a coloring agent, the dye dispersion method, the pigment dispersion method using a pigment as a coloring agent, the printing method, the electrodeposition method, etc. Among these, the dyeing method and the dye dispersing method have a drawback in that the colorant is a dye, which is somewhat inferior in heat resistance and light resistance. Therefore, the pigment which is excellent in heat resistance and light resistance is used as a coloring agent of a color filter, and a pigment dispersion method is often used as a manufacturing method by the precision and stability of a formation method.

The pigment dispersion method forms a color resist by mixing and combining the photosensitive agent, an additive, etc. with what disperse | distributed the pigment particle which is a coloring agent in transparent resin, and forms this film resist on a board | substrate by coating apparatuses, such as a spin coater, It is a method of manufacturing a color filter by selectively exposing through a mask by a stepper etc., patterning by alkali image development and a thermosetting process, and repeating this operation.

In general, by producing a pigment dispersion in which the pigment particles are subjected to a micronization treatment and the micronized pigment is brought close to the primary particles to the limit, scattering of light by the pigment can be suppressed, thereby achieving high contrast. In addition, since the transparency of the dispersion is also improved, the spectral spectrum of the dispersion has a high transmittance and high brightness is realized. By using this dispersion for a color resist, the color filter which has high contrast and high brightness is obtained.

In recent years, attention is being paid to dye-based color materials in order to realize high contrast ratio and high brightness that cannot be achieved with pigments. Among them, xanthene-based dyes such as rhodamine dyes and eosin dyes, diarylmethane-based dyes such as diphenylmethane, and triarylmethane-based dyes such as triphenylmethane are superior in color characteristics, and thus materials that achieve high brightness. It is expected as.

However, dyes such as xanthene-based dyes and triarylmethane-based dyes have high solubility in solvents, so that scattering and the like, which are seen when only pigments are used, are not expected, resulting in a color filter having a high contrast ratio. Since it was a band (for example, refer patent document 6), there existed a problem that contrast ratio became low. Therefore, it was a phenomenon that the high brightness and high contrast ratio compatible color filter by fluorescent dye were not implemented.

Japanese Patent Laid-Open No. 6-75375 Japanese Patent Application Laid-Open No. 2001-81348 Japanese Patent Laid-Open No. 2005-292305 Japanese Patent Laid-Open No. 2009-265641 Japanese Patent Application Laid-Open No. 2010-32999 Japanese Laid-Open Patent Publication No. 2005-025175

The present inventors have intensively studied to solve the above problems, and as a result of the color filter coloring composition, a fluorescent dye (A), an organic pigment skeleton or an aminobenzene skeleton, an acidic functional group, a basic functional group or a phthalate By using the organic compound (B) which has a mid frame | skeleton, it is discovered that the fall of contrast ratio is improved and achievement of high brightness and high contrast ratio is realized, and this invention is made | formed based on this knowledge.

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

(Formula 1)

P-Lm

[In formula 1,

P is an organic pigment skeleton or an aminobenzene skeleton,

L consists of a basic functional group Lb, an acidic functional group La or a functional group Lp having a phthalimide backbone,

m is an integer of 1-4 and shows the number of functional groups.]

Moreover, according to another aspect of this invention, the color filter provided with the filter segment formed from the said coloring composition for color filters on a board | substrate is provided.

The fluorescent dye (A) is selected from the group consisting of triphenylmethane dyes, diphenylmethane dyes, quinoline dyes, thiazine dyes, thiazole dyes, xanthene dyes, and diketopyrrolopyrrole dyes. Either one may be sufficient.

The organic pigment skeleton is a phthalocyanine pigment, a benzimidazolone pigment, a dioxazine pigment, an azo pigment, an anthraquinone pigment, a dianthraquinone pigment, a diketopyrrolopyrrole pigment, a thiazine indigo pigment, and a quinoph It may be any one selected from the group consisting of talon pigments.

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

(Formula 2)

(Formula 3)

(Formula 4)

(Formula 5)

[In formulas 2-4,

X ¹ is —SO ₂ —, —CO—, —CH ₂ —, —NH—, —O—, an alkenyl group having 2 to 36 carbon atoms, an alkylene group having 1 to 20 carbon atoms, an arylene group 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 a direct bond,

In Formulas 2 and 4,

Y ¹ is —NH—, —O—, or a direct bond, n is an integer from 0 to 10,

In Formula 2,

R ¹ and R ² are, each independently, a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, having a carbon number of 2 to 30 alkenyl group, or hydrogen atom, -NR ⁴ R ⁵ or -NR at the terminal of the ⁴ R ⁵ H ⁺ U ^- An alkanediyl group having 1 to 30 carbon atoms or a heterocyclic ring which may further include a nitrogen, oxygen, or sulfur atom formed by uniting R ¹ and R ² ,

Art alkanediyl group is -CH ₂ included - may be replaced by a -O-, U ^- denotes an anion, a halogen ^{_{ion, BF 4 -, PF 6 -}} , ClO 4 -, R 6 -CO 2 -, R ⁷ -SO ₃ ^- represents [R ⁶ , R ⁷ is a monovalent organic group containing an aromatic],

R ³ is a ring substituent when R ¹ and R ² are united, o is the number thereof, and when o is 2 or more, each of R ³ may have a different structure, and each independently, a hydrogen atom or carbon number 1 It is a C20 alkyl group, a C2-C20 alkenyl group, or a C6-C20 arylene group,

In Formula 3,

G is _{^{-COO -, - SO 3 -,}} - PO 3 2 -, - OPO 3 2 -, acid terminus (-Ph-COO ^-), salicylic acid terminus ^{(-Ph (OH) -COO -)} , benzenesulfonic acid terminus ( -Ph-SO ₃ ^-), a benzene phosphonic acid terminus (-Ph-PO ₃ ^{2 -} and any one of a), M is a cation including a hydrogen cation equivalent to G (Ph is phenylene group),

In Formula 4,

R ⁸ is a hydrogen atom, a halogen atom, —NO _2, —NH ₂ or —SO ₃ H,

p is an integer of 1 to 4,

In Formula 5,

R ⁹ is a functional group represented by Chemical Formulas 2 to 4,

Q ¹ is a hydrogen atom, a hydroxyl group, an alkoxyl group having 1 to 20 carbon atoms, or a functional group represented by Formulas 2 to 4,

X ² is -SO _2- , -CO-, -CH _2- , -NH-, -O-, an alkenyl group having 2 to 36 carbon atoms, an alkylene group having 1 to 20 carbon atoms, an arylene group 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 a direct bond,

Y ² is —NH—, —NR ¹¹ —Z—NR ¹² —, —SO ₂ —Z—NR ¹³ —, —N = N— or a direct bond, and R ¹¹ to R ¹³ are each independently a hydrogen atom; , An alkyl group having 1 to 36 carbon atoms, an alkenyl group having 2 to 36 carbon atoms, or a phenyl group,

Z is a C1-C20 alkylene group or a C1-C20 arylene group,

T are each independently a nitrogen atom or a carbon atom which may have a substituent.]

The present invention also relates to a coloring composition for a color filter, wherein the cation M of the 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 cation represented by the formula (8). .

(Formula 6)

[Formula 6,

R ¹⁴ to R ¹⁷ represent a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, but not all of them become hydrogen atoms.]

The fluorescent dye (A) may be a salt salt compound of a fluorescent acid dye and / or a sulfonic acid amide compound of a fluorescent acid dye.

0.05-2.0 may be sufficient as the weight ratio (B / A) of the organic compound (B) with respect to the fluorescent dye (A).

The coloring composition for color filters may further contain the organic pigment (D).

According to this invention, the fall of the contrast ratio which was the subject at the time of using a fluorescent dye can be improved, and the coloring composition which can manufacture the color filter which has high brightness and high contrast ratio can be provided.

Hereinafter, the present invention will be described in detail.

In addition, in this specification and a claim, it expresses as "(meth) acryloyl", "(meth) acryl", "(meth) acrylic acid", "(meth) acrylate", or "(meth) acrylamide" In one case, unless otherwise specified, "acryloyl and / or methacryloyl", "acrylic and / or methacrylic", "acrylic acid and / or methacrylic acid", "acrylate and / or Methacrylate "or" acrylamide and / or methacrylamide ".

In addition, "C. I. ”means a color index (C. I.).

The coloring composition for color filters which concerns on 1 aspect of this invention is an organic compound (B) which has a fluorescent pigment | dye (A) which is a coloring agent, an organic pigment skeleton, or an aminobenzene skeleton, and an acidic functional group, a basic functional group, or a phthalimide skeleton. And binder resin (C).

"coloring agent"

The coloring composition for color filters contains the fluorescent dye (A) as a coloring agent. It is also preferable to use together fluorescent dye (A) and organic pigment (D) which does not emit light.

<Fluorescent dye (A)>

As the fluorescent dye (A), any dye that emits fluorescent light is not limited. That is, it can be used if it is a fluorescent dye or a fluorescent pigment. For example, triphenylmethane dye, triphenylmethane lake pigment, diphenylmethane dye, diphenylmethane lake pigment, quinoline dye, quinoline pigment, thiazine dye, thiazole dye, xanthene dye, Xanthene lake pigments, diketopyrrolopyrrole pigments and the like can be used.

Among these, xanthene dyes, xanthene dyes that are xanthene lake pigments, quinoline dyes, quinoline dyes that are quinoline pigments, triphenylmethane dyes, triphenylmethane dyes that are triphenylmethane lake pigments, and diketopyrrolo It is preferable to use diketopyrrolopyrrole pigment | dye which is a pyrrole pigment.

Especially when the pigment | dye which fluorescently emits in the visible light region is used, the effect which makes a high contrast ratio color filter excellent.

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

Moreover, as a form of a pigment, a fluorescent pigment and the lake pigment which lakeped the said dye are mentioned.

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 of excellent color.

Oil-soluble dyes are classified as CI solvents classified by color index, basic dyes are classified as CI base type, acid dyes are classified as copper CI acid, and direct dyes are classified as copper CI direct. . Here, the direct dye has a sulfonic acid group (-SO ₃ H, -SO ₃ Na) in the structure, where the direct dye is regarded as an acid dye.

Hereinafter, the preferable fluorescent dye (A) will be described in detail.

(Xanthene Dye: Xanthene Dye, Its Lake Pigment)

In the case of xanthene-based dyes, the transmittance is 90% or more in the region of 650 nm in the transmission spectrum, the transmittance is 75% or more in the region of 600 nm, the transmittance is 5% or less in the region of 500 to 550 nm, and the transmittance in the region of 400 nm. It is preferable that it is 70% or more. More preferably, the transmittance is 95% or more in the region of 650 nm, the transmittance is 80% or more in the region of 600 nm, the transmittance is 10% or less in the region of 500 to 550 nm, and the transmittance is 75% or more in the region of 400 nm. Among them, xanthene basic dyes and xanthene acid dyes have spectroscopic characteristics having high transmittance at 400 to 450 nm.

Among the xanthene dyes, rhodamine dyes are preferred because of their excellent color development and resistance.

(Forms as Oil Soluble Dyes of Xanthene Dyes)

As xanthene oil-soluble dye, specifically, 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. are mentioned.

Among them, C. I. Solvent Red 35, C. I. Solvent Red 36, C. I. Solvent Red 49, C. I. Solvent Red 109, C. I. Solvent Red 237, C. I. Solvent Red 246, and C. I. Solvent Violet 2 are preferred.

(Form as Acid Dye of Xanthene Dye)

As acid dyes (xanthene acid dyes) of xanthene dyes, CI acid red 51 (erythrosine (edible red No. 3)), CI acid red 52 (acid rhodamine), CI acid red 87 (eosin G ( Edible Red No. 103)), CI Acid Red 92 (Acid Phloxine PB (Edible Red No. 104)), CI Acid Red 289, CI Acid Red 388, Rose Bengal B (Edible Red No. 5), Acid Preference is given to using rhodamine G, CI acid violet 9.

Among them, CI acid red 87 (CI acid red 92), CI acid red 92, CI acid red 388, or rhodamine acid dyes, CI acid red 52 (acid rhodamine). ), CI acid red 289, acid rhodamine G, CI acid violet 9 are more preferred.

Among these, it is most preferable to use C. I. acid red 52 and C. I. acid red 289 which are rhodamine type | system | group dyes from a point of color development, heat resistance, and light resistance.

(Form as Basic Dye of Xanthene Dye)

Examples of the xanthene basic dyes include C. I. basic red 1 (rhodamine 6GCP), 8 (rhodamine G), and C. I. basic violet 10 (rhodamine B). Especially, since it is excellent in color development, it is preferable to use C. I. basic red 1 and C. I. basic violet 10.

(Form as Xanthene Dye Lake Pigment)

As a metal lake pigment of xanthene dye, CI Pigment Red 81, CI Pigment Red 81: 1, CI Pigment Red 81: 2, CI Pigment Red 81: 3, CI Pigment Red 81: 4, CI Pigment Red 81: 5, CI Pigment Red 169, CI Pigment Violet 1, CI Pigment Violet 1: 1, CI Pigment Violet 1: 2, CI Pigment Violet 2, and the like.

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

In the case of diphenyl and triphenylmethane dyes, the blue (blue) triaryl methane-based basic dyes have spectral characteristics having a high transmittance at 400 to 440 nm.

(Forms as Acid Dyes of Diphenyl and Triphenylmethane Dyes)

Acid dyes of diphenyl and triphenylmethane dyes include edible blue No. 101 (CI acid blue 1), acid pure blue (CI acid blue 3), lake blue I (CI acid blue 5), and 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 Preference is given to using acid blue 103, CI acid blue 104, CI acid blue 109.

(Forms of basic dyes of diphenyl and triphenylmethane dyes)

Triphenylmethane-based basic dyes and diphenylmethane-based basic dyes develop by taking a quinone structure by oxidation of NH ₂ or OH groups in the position of para with respect to the central carbon.

These are divided into the following three forms by the number of NH ₂ and OH groups, and among them, the form of triaminotriphenylmethane-based basic dyes is preferable in terms of good blue, red and green color development.

a) a diaminotriphenylmethane-based basic dye

b) Triaminotriphenylmethane-based basic dyes

c) rosolic acid basic dyes having an OH group

Triamino triphenylmethane-based basic dyes and diamino triphenylmethane-based basic dyes are preferable because they have a clear color tone and excellent light fastness than others. Also preferred are diphenylnaphthylmethane basic dyes and / or triphenylmethane basic dyes.

Specifically, CI Basic Blue 1 (Basic Cyanine 6G), Copper 5 (Basic Cyanine EX), Copper 7 (Victoria Pure Blue BO), Copper 25 (Basic Blue GO), Copper 26 (Victoria Blue B conc.) Etc. can be mentioned.

C. I. basic green 1 (brilliant green GX), copper 4 (malachite green), etc. are mentioned.

C. I. Basic violet 1 (methyl violet), copper 3 (crystal violet), copper 14 (Magenta), etc. are mentioned.

(Forms as Diphenyl and Triphenylmethane Dye Lake Pigments)

Specific examples of 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, and CI Pigment. And cement violet 3, CI pigment violet 27, and CI pigment violet 39.

More preferable ones are specifically shown below.

C. I. Pigment Blue 1

C. I. basic blue 26, C. I. basic blue 7 laked with phosphotungsten molybdate

C. I. Pigment Violet 3

C. I. Lake Violet 1 was lysed with phosphotungsten molybdate

C. I. Pigment Violet 39

C. I. Lake Violet 3 (Crystal Violet) rakes with phosphotungsten molybdate

Especially, it is preferable to use C. I. pigment blue 1.

(Quinoline dyes: quinoline dyes, quinoline pigments)

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

Examples of the quinoline pigment include C. I. Pigment Yellow 138 (Palitolol Yellow K0961-HD manufactured by BASF).

(Thiazine dye)

As the thiazine dye, Lauth's Violet, methylene blue, methylene green B, CI basic blue 9, 17, 24, 25, solvent blue 8, CI basic green obtained by oxidizing P-phenylenediamine in the presence of hydrogen sulfide under FeCl ₂ 5, CI direct red 70, etc. are mentioned.

(Thiazole dye)

As the thiazole dye, a dye having a thiazole ring is used as a thiazole dye. Specifically, CI basic yellow 1, CI basic violet 44, 46, CI basic blue 116, CI acid yellow 186, copper direct yellow 7, 8, 9, 14, 17, 18, 22, 28, 29, 30, 54, 59, 165, CI direct orange 18, CI direct red 11, etc. are mentioned.

(Diketopyrrolopyrrole Pigment)

Diketopyrrolopyrrole pigments are red to orange pigments of the structure represented by the formula (7). If the specific example of the diketopyrrolopyrrole pigment represented by the following formula (7), C. I. Pigment Red 254, 255, 264, 272 and C. I. Pigment Orange 71, 73, 81.

(Formula 7)

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

Fluorescent dye (A) has good spectral characteristics and is excellent in color development, but is problematic in light resistance and heat resistance, and its characteristics are sufficient for use in an image display device using a color filter requiring high reliability. You may not do it.

Therefore, in order to improve these drawbacks, in the case of the form of basic dye, it is preferable to use it salt-proof using organic acid or perchloric acid. As the organic acid, it is preferable to use an organic sulfonic acid or an organic carboxylic acid. Among them, it is preferable to use naphthalenesulfonic acid such as tobic acid or perchloric acid in terms of resistance.

In the case of acid dyes and direct dyes, quaternary ammonium salt compounds, tertiary amine compounds, secondary amine compounds, primary amine compounds and the like and salts are formed using resin components having these functional groups to be used as salt forming compounds. Or sulfonamide and used as a sulfonamide compound is preferable in view of resistance.

Among these, the quaternary ammonium salt which is a counter component which is preferable since it is excellent from the viewpoint of resistance and combined use with a pigment is a salt salt compound of an acid dye, and / or a sulfonic acid amide compound of an acid dye especially. More preferred are compounds which have been salted using the compound.

Hereinafter, the form of the fluorescent dye (A) will be described in detail.

(Salt salt compounds of acid dyes and / or sulfonamide compounds of acid dyes)

An acid dye is salt-formed using the quaternary ammonium salt compound, the tertiary amine compound, the secondary amine compound, the primary amine compound, etc., and the resin component which has these functional groups, and it is set as the salt compound of an acid dye. Or it is preferable because it can provide high heat resistance, light resistance, and solvent resistance by making sulfonamide into a sulfonamide compound.

Primary amine compounds include methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine (laurylamine ), Aliphatic unsaturations such as tridodecylamine, tetradecylamine (myristylamine), pentadecylamine, cetylamine, stearylamine, oleylamine, cocoalkylamine, Uji alkylamine, hardened Uji alkylamine, allylamine, etc. Primary amine, aniline, benzylamine, and the like.

As the secondary amine compound, aliphatic unsaturated secondary amines such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine, diarylamine, methylaniline, ethylaniline, dibenzylamine, Diphenylamine, dicoalkylalkylamine, dicured tallow alkylamine, distearylamine, and the like.

Examples of the tertiary amine compound include trimethylamine, triethylamine, tripropylamine, tributylamine, triamylamine, dimethylaniline, diethylaniline, tribenzylamine, and the like.

Fluorescent dye (A) is particularly preferably used by salting an acidic dye with a quaternary ammonium salt or by sulfonating an acidic dye. These two forms are demonstrated in detail below.

[Basic salt compound consisting of an acid dye and a quaternary ammonium salt compound]

The fluorescent dye (A) is most preferably used from the viewpoint of heat resistance, light resistance and solvent resistance, as a salt forming compound composed of the above-mentioned acidic dye and quaternary ammonium salt compound.

Quaternary ammonium salt compounds

The quaternary ammonium salt compound has an amino group so that the cation moiety becomes a counter of the xanthene acid dye.

The preferred form of the quaternary ammonium salt compound which is the counter component of the salt forming compound is colorless or white. Here, colorless or white means what is called a transparent state, and is defined as the state in which the transmittance | permeability becomes 95% or more, Preferably it is 98% or more in the 400-700 nm full-wavelength region of visible region. That is, it is necessary to be a thing which does not cause a color change which does not inhibit the color development of a dye component.

It is preferable that the molecular weight of the cation part used as the counter of a quaternary ammonium salt compound is the range of 190-900. Here, the cation portion is to correspond to the portion of the of the general formula ^{4 (NR 1 R 2 R 3} R 4) +. When molecular weight is smaller than 190, light resistance and heat resistance may fall, and solubility to a solvent may fall. Moreover, when molecular weight becomes larger than 900, since the ratio of the color development component in a molecule | numerator falls, color development property may fall and brightness may also fall. More preferably, the molecular weight of the cationic moiety is in the range of 240 to 850, particularly preferably in the range of 350 to 800.

The molecular weight was calculated based on the structural formula, and the atomic weight of C was 12, the atomic weight of H was 1, and the atomic weight of N was 14.

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

(Formula 8)

In formula (8), R <^101> -R <^104> respectively independently represents a C1-C20 alkyl group or benzyl group, and at least 2 or more of R <^101> , R <^102> , R <^103> or R <^104> has 5-C number. 20. Y represents an inorganic or organic anion.]

Solubility to a solvent becomes favorable by setting the number of C of at least 2 or more side chains of R <^101> -R <^104> to 5-20. ~ R ¹⁰¹ R when the three or more than the number of small groups 5 of C of ¹⁰⁴ to poor solubility in a solvent, resulting coating film tends to have foreign substances occurs. Moreover, when the alkyl group which the number of C exceeds 20 exists in a side chain, the coloring property of a salt-forming compound may be impaired.

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

Specific examples of such quaternary ammonium salt compounds include tetramethylammonium chloride (the molecular weight of the cation moiety is 74), tetraethylammonium chloride (the molecular weight of the cation moiety is 122), and monostearyltrimethylammonium chloride (the molecular weight of the cation moiety is 312. ), Distearyldimethylammonium chloride (molecular weight of cation moiety 550), tristearyl monomethylammonium chloride (molecular weight of cation moiety 788), cetyltrimethylammonium chloride (molecular weight of cation moiety 284), trioctylmethylammonium Chloride (molecular weight of cation moiety 368), dioctyldimethylammonium chloride (molecular weight of cation moiety 270), monolauryltrimethylammonium chloride (molecular weight of cation moiety 228), dilauryldimethylammonium chloride (molecular weight of cation moiety 382), trilaurylmethylammonium chloride (cationic mole molecular weight of 5 36), triamylbenzylammonium chloride (molecular weight of cation moiety is 318), trihexylbenzylammonium chloride (molecular weight of cation moiety is 360), trioctylbenzylammonium chloride (molecular weight of cation moiety is 444), trilaurylbenzylammonium Chloride (molecular weight of cation moiety 612), benzyldimethylstearylammonium chloride (cation moiety 388), and benzyldimethyloctylammonium chloride (cationic moiety 248), or dialkyl (alkyl is C14-C18) It is preferable to use dimethyl ammonium chloride (cured tallow) (molecular weight of cation part is 438-550).

As a product, it is made from the Co., Ltd. 24P, cotamine 86P conk, cotamine 60W, cotamine 86W, cotamine D86P, sanisol C, sanisol B-5 0 light, Lion Corporation Arquad 210-80E, 2C- 75, 2HT-75, 2HT fragment, 2O-75I, 2HP-75, or 2HP flake, and the like, and among them, cotamine D86P (distearyldimethylammonium chloride) or arquad 2HT-75 (dialkyl ( Alkyl is C14-C18) dimethylammonium chloride).

The quaternary ammonium salt compound may be in the form of a resin having a cationic group, particularly an amino group, and an ammonium group in the side chain, and capable of reacting and salting with a xanthene acid dye to form a quaternary ammonium salt structure.

Preparation method of salt salt compound

The salt forming compound of an acidic dye and a quaternary ammonium salt compound can be manufactured by the method known conventionally. Japanese Patent Laid-Open No. 11-72969 discloses a specific technique.

For example, after dissolving an acidic dye in water, it is good to perform a roughening process, adding and stirring a quaternary ammonium salt compound. Here, the salt forming compound is a part of sulfonic acid groups in the acidic dye (-SO ₃ H), an ammonium group and a quaternary ammonium salt compound of a portion of the sulfonate groups _{(-SO 3 Na) (NH 4} +) combined is obtained. In addition, instead of water, methanol and ethanol are also solvents usable at the time of salting.

Examples of the salt forming compound include a fluorescent dye (A) (such as CI acid red 289 or CI acid red 52) in the form of an acid dye, and a quaternary ammonium salt compound having a molecular weight of 350 to 800 of the cation moiety used as a counter. By using a salt-forming compound, it is excellent in solvent solubility, and when used together with the pigment mentioned later, it becomes more excellent in heat resistance, light resistance, and solvent resistance. Moreover, it is guessed that what becomes favorable by using a salt-forming compound together with a pigment is because it adsorb | sucks to a pigment, melt | dissolving and disperse | distributing in a solvent. At this time, it is suitable that the primary particle diameter of a pigment is 20-100 nm.

Although this coloring composition is mentioned later, it is preferable that it is a form of the blue coloring composition containing a blue pigment, the red coloring composition containing a red pigment further, the yellow coloring composition containing a yellow pigment, or the green coloring composition further.

[Sulfonic Acid Amide Compounds of Acid Dyes]

The sulfonic acid amide compound of the acidic dye which can be preferably used for the fluorescent dye (A) can be chlorolated by an ordinary method of an acidic dye having -SO ₃ H, -SO ₃ Na, and -SO ₃ H It may be prepared by -SO ₂ Cl and reacting this compound with an amine having a -NH ₂ group.

Moreover, as an amine compound used for sulfonation, specifically, 2-ethylhexylamine, dodecylamine, 3-decyloxypropylamine, 3- (2-ethylhexyloxy) propylamine, 3-ethoxypropyl Preference is given to using amines, cyclohexylamines and the like.

For example, when obtaining the sulfonic acid amide compound which modified CI acid red 289 using 3- (2-ethylhexyloxy) propylamine, after CI acid red 289 was sulfonyl chloride, What is necessary is just to react with theoretical equivalent of 3- (2-ethylhexyloxy) propylamine in oxane, and to obtain the sulfonic acid amide compound of CI acid red 289.

In addition, in the case of obtaining a sulfonamide compound obtained by modifying CI acid red 52 using 3- (2-ethylhexyloxy) propylamine, the theory was found in dioxane after sulfonyl chloride CI acid red 52 was used. It is sufficient to react with an equivalent of 3- (2-ethylhexyloxy) propylamine to give the sulfonic acid amide compound of CI acid red 52.

[Basic salt compound consisting of a compound of a basic dye, an organic acid and an inorganic acid]

The basic dye is not sufficient in order to be used in an image display device using a color filter which is further deficient in light resistance and heat resistance and which requires high reliability. Therefore, in order to improve the fault in these dyes, it is preferable to salt-basic a basic dye using an organic acid and an inorganic acid. It is preferable to use organic sulfonic acid and organic carboxylic acid as an organic acid, and it is preferable to use naphthalene sulfonic acid especially. In particular, tobias acid is preferable. Moreover, it is especially preferable to use perchloric acid as an inorganic acid.

<Other colorants>

The coloring composition for color filters may further use an organic pigment (D) as another coloring agent. Other colorants are, for example, dyes which do not fluoresce or organic pigments which do not fluoresce.

In the case of using together with other colorants, it is preferable to use an organic pigment (D) for adjustment of color and improvement of resistance. When using a fluorescent dye (A) and an organic pigment (D) together, the use ratio of the fluorescent dye (A) and the organic pigment (D) is fluorescent with respect to 100 parts by weight of the organic pigment (D). It is preferable that dye (A) is 1-80 weight part. More preferably, it is 5-60 weight part. When the addition amount of the fluorescent dye (A) is in this range, the composition can also be excellent in color and reproducible chromaticity region.

As a pigment to be used together, the following are used for each filter segment of each color.

(Pigment used for red filter segment)

As a red pigment used for a red filter segment, the red pigment or red dye mentioned below is mentioned.

As a red pigment, 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, 287, or the like. Among them, it is preferable to use C. I. Pigment Red 177, 179, 254.

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

In order to form a red filter segment, you may use together a yellow or orange pigment.

As a yellow or orange pigment, the yellow pigment, orange pigment, etc. which are described below are mentioned.

As yellow pigment, CI 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 is used.

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

These pigments can be used individually or in mixture of 2 or more types in arbitrary ratios as needed.

When using together organic pigment (D) with a pigment (A) as a coloring agent of a red filter segment, it is preferable that an organic pigment (D) is a red pigment or an orange pigment from a viewpoint of a color reproduction area | region and resistance. In this case, as a red pigment or an orange pigment, CI pigment red 254, 177, 242, or CI pigment orange 38 is especially preferable from a viewpoint of lightness and contrast ratio. As a fluorescent pigment | dye (A), it is a rhodamine type | system | group. It is preferable to use a dye and a diketopyrrolopyrrole dye. By using together these organic pigment (D) and fluorescent pigment | dye (A), provision of the red coloring composition excellent in both brightness, contrast ratio, and resistance is attained.

(Pigment used for blue filter segment)

As a pigment used for a blue filter segment, CI pigment blue 1, 1: 2, 1: 3, 2, 2: 1, 2: 2, 3, 8, 9, 10, 10: 1, 11, for example. , 12, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 18, 19, 22, 24, 24: 1, 53, 56, 56: 1, 57, 58 Blue pigments such as, 59, 60, 61, 62, 64, violet pigments such as CI pigment violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50, and combinations thereof Can be mentioned.

When using together organic pigment (D) with a pigment (A) as a coloring agent of a blue filter segment, it is preferable that an organic pigment (D) is a blue pigment from a viewpoint of a color reproduction area | region, resistance, etc. In this case, CI pigment blue 15: 1 and 15: 6 are especially preferable as a blue pigment from a viewpoint of lightness and contrast ratio, As a fluorescent pigment | dye (A), a rhodamine pigment | dye and a triphenylmethane pigment | dye are mentioned. It is preferable to use. By combining these dyes (A), it becomes possible to provide a blue colored composition excellent in brightness, contrast ratio and resistance.

(Pigment used for green filter segment)

As a pigment used for a green filter segment, green pigments, such as C. I. pigment green 7, 10, 36, 37, 58, are mentioned. Especially, it is preferable to use C. I. pigment green 36, 58.

In addition, in green coloring composition, CI 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 , Yellow pigments such as 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, or 221 can be used in combination with the dye (A).

Among these, it is preferable to use C. I. pigment yellow 138, 150, etc.

When using together organic pigment (D) with a pigment (A) as a coloring agent of a green filter segment, it is preferable that an organic pigment (D) is a green pigment from a viewpoint of a color reproduction area | region, resistance, etc. In this case, CI pigment greens 36 and 58 are particularly preferable as the green pigment from the viewpoint of lightness and contrast ratio, and a yellowish dye is preferable as the fluorescent dye (A), and in particular a quinoline pigment It is preferable to use. By combining these dyes (A), it becomes possible to provide a green coloring composition excellent in brightness, contrast ratio and resistance.

In this color filter coloring composition, it is preferable that the coloring agent concentration with respect to all the non volatile components is 10 to 90 weight% from a viewpoint of obtaining sufficient color reproduction, More preferably, it is 15 to 85 weight%, Most preferably 20 to 80% by weight.

When the concentration of the colorant component is less than 10% by weight, sufficient color reproduction may not be obtained. When the concentration of the colorant component is more than 90% by weight, the concentration of colorant carriers such as binder resin may be lowered, resulting in poor stability of the coloring composition. .

(Fineness of pigment)

It is preferable to refine | miniaturize and use an organic pigment (D). The refinement | miniaturization method is not specifically limited, For example, it can be used for all of a wet grinding, a dry grinding, and a dissolution precipitation method. For example, it can refine | miniaturize by performing the salt milling process by the kneader method which is one type of wet grinding. It is preferable that the primary particle diameter of a pigment is 20 nm or more from the point which the dispersion | distribution in a coloring agent support is favorable. Moreover, since the primary particle diameter of a pigment can form the filter segment with a high contrast ratio, it is preferable that it is 100 nm or less. Especially preferable range is the range of 25-85 nm. In addition, the primary particle diameter of a pigment was performed by the method of measuring the size of a primary particle directly from the electron microscope photograph by a TEM (transmission electron microscope) of a pigment. Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment were measured, and the average was made into the particle diameter of the pigment particle. Salt milling treatment involves heating a mixture of pigments, water-soluble inorganic salts and water-soluble organic solvents using batch or continuous kneaders such as kneaders, two-roll mills, three-roll mills, ball mills, attritors, sand mills, planetary mixers, etc. After kneading with water, it is a process of removing water-soluble inorganic salt and water-soluble organic solvent by water washing. The water-soluble inorganic salt acts as a crushing aid, and the pigment is crushed using the high hardness of the inorganic salt during salt milling. By optimizing the conditions at the time of salt milling the pigment, it is possible to obtain a pigment having a very fine primary particle diameter, a narrow distribution width, and a sharp particle size distribution.

As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but it is preferable to use sodium chloride (salt) from the point of view of price. It is preferable to use 50-2000 weight part of water-soluble inorganic salts with respect to 100 weight part of total weight of a pigment from both surfaces of processing efficiency and productive efficiency, and it is most preferable to use 300-1000 weight part.

The water-soluble organic solvent acts to wet the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it is dissolved (mixed) in water and does not substantially dissolve the inorganic salt to be used. However, since a temperature rises at the time of salt milling and a solvent becomes easy to evaporate, the high boiling point solvent of 120 degreeC or more of boiling point is preferable at the point of safety. For example, there can be mentioned 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl Diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, diethylene glycol monomethyl ether, Monoethyl ether, and liquid polypropylene glycol. It is preferable to use 5-1000 weight part with respect to 100 weight part of total weight of a pigment, and, as for a water-soluble organic solvent, it is most preferable to use 50-500 weight part.

When salt milling a pigment, you may add resin as needed. The kind of resin which can be used is not specifically limited, A natural resin, a modified natural resin, a synthetic resin, the synthetic resin modified with the natural resin, etc. can be used. The resin used is solid at room temperature, preferably insoluble in water, and more preferably partially soluble in the organic solvent. It is preferable that the usage-amount of resin is the range of 5-200 weight part with respect to 100 weight part of total weight of a pigment.

It is also preferable to add the fluorescent dye (A) when salt milling (micronizing) the pigment. When refine | miniaturizing a pigment, it can be set as a favorable coloring agent by adding together.

<< organic compound (B) >>

In the case where a dye is used as the fluorescent dye (A), a high-brightness color filter is obtained with the high transparency derived from the characteristics of the dye and the high solubility of the dye, compared to the case of using a conventional pigment, whereas the dye itself Fluorescence was generated at, and the contrast ratio was lowered. This main reason is that fluorescence exists in the leakage light at the time of contrast measurement, and the luminance at the cross side is increased.

MEANS TO SOLVE THE PROBLEM As a result of this examination in order to solve the problem of the contrast ratio fall by this fluorescence, the organic compound (B) which has an organic pigment skeleton or an aminobenzene skeleton, and an acidic functional group, a basic functional group, or a phthalimide skeleton, By using together with the fluorescent dye (A), it has been found that the generation of fluorescence from the dye (A) can be eliminated and the luminance on the cross side can be lowered, thereby achieving high contrast.

The reason why the fluorescence quenching effect of suppressing fluorescence becomes remarkable when these substances are used is not clear, but the organic compound (B) having an organic pigment skeleton or an aminobenzene skeleton and a basic functional group, an acidic functional group and a phthalimide skeleton is Since the compatibility with the fluorescent dye (A) is high, the efficiency of fluorescence quenching is high, and since it is easy to form a fluorescent dye (A) and a charge transfer complex, fluorescence emission itself is remarkably suppressed, It is thought that fluorescence is extinct remarkably.

It is preferable that the organic compound (B) which has an organic pigment skeleton or an aminobenzene skeleton, and an acidic functional group, basic functional group, or phthalimide skeleton is a compound represented by following General formula (1).

(Formula 1)

P-Lm

[Formula 1,

P is an organic pigment skeleton or an aminobenzene skeleton,

L consists of a basic functional group Lb, an acidic functional group La or a functional group Lp having a phthalimide backbone,

m is an integer of 1-4 and shows the number of functional groups.]

Examples of the organic pigment skeleton (P) of the organic compound (B) include diketopyrrolopyrrole pigments, azo pigments such as azo, disazo and polyazo, aminoanthraquinones, diaminodianthraquinones, anthrapyrimidines, and flavantrons. Anthraquinone pigments such as anthrone, indanthrone, pyrantrone, and violatron, quinacridone pigments, perinone pigments, perylene pigments, thioindigo pigments, thiazine indigo pigments, isoindolin pigments, And organic pigments such as isoindolinone pigments, quinophthalone pigments, tren pigments, phthalocyanine pigments, benzimidazolone pigments, dioxazine pigments and metal complex pigments.

The organic compound (B) may have both an organic pigment skeleton and an aminobenzene skeleton.

Among these, an organic pigment skeleton is preferable from a viewpoint of a hue and contrast ratio, and also a phthalocyanine pigment, a benzimidazolone pigment, a dioxazine pigment, an azo pigment, an anthraquinone pigment, a dianthraquinone pigment, a dike Particularly preferred is an organic pigment skeleton which is any one selected from the group consisting of topyrrolopyrrole pigments and quinophthalone pigments. This is because the organic compound (B) having these organic pigment skeletons has a high affinity with the fluorescent dye (A), and thus the fluorescence quenching effect is increased.

When using these in a blue coloring composition, it is especially preferable that an organic pigment skeleton is a skeleton of a phthalocyanine pigment and a dioxazine pigment. Moreover, when using these in a red coloring composition, it is especially preferable that an organic pigment skeleton is a skeleton of a benzimidazolone pigment, a dianthraquinone pigment, and a diketopyrrolopyrrole pigment. Moreover, since aminobenzene is colorless, either blue or red can be used preferably.

The functional group (L) is a functional group Lp having a basic functional group Lb, an acidic functional group La or a phthalimide skeleton, and preferably has a structure represented by the following formulas (2) to (5). This is because having a constant steric hindrance site as the functional group contributes to securing the viscosity stability of the dye solution in addition to being excellent in the fluorescence quenching effect.

The basic functional group Lb is represented by, for example, Formula 2 or 5, the acidic functional group La is represented by, for example, Formula 3 or 5, and the functional group Lp having a phthalimide skeleton is, for example, Formula 4 Or five.

Examples of the basic component used to form the substituent represented by the formula (2) or (5) include dimethylamine, diethylamine, methylethylamine, N, N-ethylisopropylamine, N, N-ethylpropylamine, N, N-methylbutylamine, N, N-methylisobutylamine, N, N-butylethylamine, N, N-tert-butylethylamine, diisopropylamine, dipropylamine, N, N-sec- Butylpropylamine, dibutylamine, di-sec-butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine, diisoamylamine, dihexylamine, dicyclohexylamine, Di (2-ethylhexyl) amine, dioctylamine, N, N-methyloctadecylamine, didecylamine, diallylamine, N, N-ethyl-1,2-dimethylpropylamine, N, N-methylhexyl Amine, dioleylamine, distearylamine, N, N-dimethylaminomethylamine, N, N-dimethylaminoethylamine, N, N-dimethylaminoamylamine, N, N-dimethylaminobutylamine, N, N -Diethylaminoethyl Min, N, N-diethylaminopropylamine, N, N-diethylaminohexylamine, N, N-diethylaminobutylamine, N, N-diethylaminopentylamine, N, N-dipropylaminobutyl Amine, N, N-dibutylaminopropylamine, N, N-dibutylaminoethylamine, N, N-dibutylaminobutylamine, N, N-diisobutylaminopentylamine, N, N-methyllauryl Aminopropylamine, N, N-ethylhexylaminoethylamine, N, N-distearylaminoethylamine, N, N-dioleylaminoethylamine, N, N-distearylaminobutylamine, piperidine, 2-pipecoline, 3-pipecoline, 4-pipecoline, 2,4-ropetidine, 2,6-ropetidine, 3,5-ropetidine, 3-piperidinemethanol, pipecolinic acid, Isonifecotic acid, methyl isonifecotate, ethyl isonifecotate, 2-piperidineethanol, pyrrolidine, 3-hydroxypyrrolidine, N-aminoethylpiperidine, N-aminoethyl-4 -Pipecoline, N-aminoethyl morpholine, N-aminopropylpiperidine, N-amino Lofil-2-Pipecoline, N-aminopropyl-4-pipecoline, N-aminopropylmorpholine, N-methylpiperazine, N-butylpiperazine, N-methylhompiperazine, 1-cyclopentylpiperazine, 1-amino-4-methyl piperazine, 1-cyclopentyl piperazine, etc. are mentioned.

The organic compound (B) can be synthesized by the above various synthetic routes. For example, the said amine component which introduce | transduces the substituent represented by following formula (11)-(15) to an organic pigment skeleton or an aminobenzene skeleton, and reacts with the said substituent, and forms the substituent represented by Formula (2) or (5), For example, N, N-dimethylaminopropylamine, N-methylpiperazine, diethylamine, or 4- [4-hydroxy-6- [3- (dibutylamino) propylamino] -1,3, 5-triazin-2-ylamino] aniline etc. are obtained by making it react.

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

In the reaction of the substituents of the formulas (11) to (15) with the amine component, a part of the substituents of the formulas (11) to (15) may be hydrolyzed and chlorine may be substituted with a hydroxyl group. In that case, although formula (11) and formula (12) respectively become a sulfonic acid group and a carboxylic acid group, all may be free acid, and may be a monovalent trivalent metal or a salt with said monoamine.

In the organic compound (B), the substituent represented by the formula (5) can be synthesized by various synthetic routes. For example, an amine component, such as N, N-dimethylaminopropylamine or N-methylpipe, which is made of cyanuric chloride as a starting material and forms a substituent represented by the formula (2) in at least one chlorine of cyanuric chloride. It is obtained by reacting a razine or the like and then reacting the remaining chlorine of cyanuric chloride with various amines or alcohols.

One of the most preferable forms among organic compounds (B) is the form of the sulfonic acid amide compound which has group of the structure of sulfonic acid amide in an organic pigment skeleton.

In the organic compound (B), the sulfonic acid amide compound means, in formula (2) or (5), for example, X ¹ in formula (2) is -SO _2- , Y ¹ is a direct bond, and n is 0. to be.

Regardless of the presence or absence of the structure of sulfonic acid amide, excellent fluorescence quenching properties are triazine compounds having a triazine skeleton represented by the formula (5).

That is, the basic skeleton of the organic compound (B) having a triazine skeleton and a skeleton of sulfonic acid amide is particularly preferable because of its excellent characteristic of fluorescence quenching.

In the acidic derivative having an acidic functional group La, examples of the acidic group of the pigment derivative include a sulfonic acid group, a carboxylic acid group, and a phosphonic acid group. The pigment derivative having a sulfonic acid group can be produced by reacting sulfuric acid with an organic pigment. The sulfonic acid group includes monovalent trivalent metal atoms such as lithium, potassium, sodium, calcium, magnesium, strontium, and aluminum, transition metals such as Fe, Co, Ni, and Cu, monoalkylamines such as ethylamine, and butylamine, dimethylamine, You may form salts with organic amines, such as alkynamine, such as dialkylamines, such as diethylamine, trialkylamines, such as trimethylamine, and triethylamine, monoethanolamine, diethanolamine, and triethanolamine.

Especially, it is preferable to use a transition metal as a salt because the effect of fluorescence quenching is favorable. In order to convert the metal ions of the counter of the acidic derivative into transition metal ions such as Fe, Co, Ni and Cu, the derivative having an acidic functional group terminal may be a basic aqueous solution such as sodium hydroxide or ammonia, or methanol, ethylene glycol, acetone or pyridine. After dissolving in organic solvents, such as DMF and DMSO, it can obtain as a precipitate by adding the equivalent metal salt and stirring by heating.

An example which introduce | transduces an acidic group into a pigment skeleton and salts with an organic amine is shown below. Here, an example of quinoline salt forming compound is shown.

A sulfonated dye derivative of quinophthalone-based yellow pigment C. I. pigment yellow 138 and distearyldimethylammonium chloride (cotamine D86P) (molecular weight of cation moiety is 550), to prepare a xanthene dye

Also,

30 parts of quinophthalone type yellow pigment C.I. pigment yellow 138 ("Palitolol yellow K0960-HD" by BASF Corporation) was dissolved in 300 parts of 101% sulfuric acid, and stirred at 70 ° C for 8 hours to perform sulfonation reaction. The end point of reaction measured the spectral spectrum of a sulfuric acid solution, and made it the point that a change of a spectrum is not seen. Subsequently, this reaction solution was poured into 3000 parts of ice water, and the sulfonated dye derivative which precipitated was separated by filtration and washed with water to obtain a paste of sulfonated dye derivative.

LC-MASS analysis was performed on the obtained sulfonated dye derivative. In HPLC (Column: "ODS-100S" manufactured by Tosoh Corporation), the molecular weight of the main peak, which occupies 80% of the area ratio, was MW = 774 (electron spray method, negative mode), and the molecular weight of the monosulfonated derivative of CI Pigment Yellow 138. Matched. In addition, 1 H-NMR identified the sulfonated dye derivative having the following structure.

An organic compound (B) can be synthesize | combined by the method known conventionally. JP 63-305173, JP 57-15620, JP 59-40172, JP 63-17102, JP 5-9469, JP 49-46 Specific techniques are described in Japanese Patent Laid-Open No. 59136 and Japanese Patent Laid-Open No. 61-246261.

As a method of introducing a functional group Lp having a phthalimide skeleton into an organic pigment skeleton or an aminobenzene skeleton, a known method of reacting with hydroxymethylphthalimide in sulfuric acid, for example, Japanese Patent Application Laid-Open No. 55-108466 It can introduce | transduce by the method as described in a publication.

Although the organic compound (B) which has an organic pigment skeleton or an aminobenzene skeleton, and an acidic functional group, basic functional group, or phthalimide skeleton can be used individually, you may use it in combination of 2 or more types.

In this coloring composition, it is preferable that the weight ratio (B / A) of the compounding quantity of an organic compound (B) with respect to the fluorescent dye (A) is 0.05-2. If it is less than 0.05, the contrast ratio is low because the suppression of fluorescence and the dispersibility of the organic compound (B) are insufficient. If the value is more than 2, the color characteristics are affected, resulting in low brightness. More preferable weight ratio (B / A) is 0.2-2, and most preferable weight ratio (B / A) is 0.5-1.5.

"Suzy"

This color filter coloring composition is characterized by containing binder resin (C). In addition to the main binder resin (C), other resins such as rosin ester may be included as auxiliary resins. That is, resin consists of main binder resin (C) and auxiliary resin as an option.

<Binder Resin (C)>

Binder resin (C) disperse | distributes coloring agents, such as a pigment and a pigment, especially a fluorescent pigment | dye (A), or dyeing and penetrating a fluorescent pigment | dye (A), and a thermoplastic resin, a thermosetting resin, etc. Can be mentioned.

As the binder resin (C), the spectral transmittance is preferably 80% or more, more preferably 95% or more, in the entire wavelength range of 400 to 700 nm in the visible light region. Moreover, when using in the form of alkali developing type coloring resist material, it is preferable to use alkali-soluble vinyl resin which copolymerized the acidic group containing ethylenically unsaturated monomer.

Moreover, in order to further improve light sensitivity, you may use energy ray curable resin which has an ethylenically unsaturated active double bond.

In order to disperse | distribute and penetrate the coloring agent which consists of a fluorescent dye (A) and an organic pigment (D) as an option preferably, the weight average molecular weight (Mw) of binder resin (C) has the preferable range of 5,000-80,000, More preferably, it is the range of 7,000-50,000. Moreover, the range of 2,500-40,000 is preferable, and, as for number average molecular weight (Mn), it is preferable that the value of Mw / Mn is 10 or less.

Here, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are used as an apparatus using HLC-8220GPC (manufactured by Tosoh Corp.), and TSK-GEL SUPER HZM-N is used by connecting two columns in a column. And polystyrene reduced molecular weight measured using THF as a solvent.

When using binder resin (C) as the photosensitive coloring composition (resist material) for color filters mentioned later, it acts as a carboxyl group which acts as a colorant adsorption group and the alkali soluble group at the time of image development, a colorant carrier, and an affinity group to a solvent. The balance of aliphatic groups and aromatic groups is important for dispersibility, permeability, developability, and durability of the colorant, and it is preferable to use a resin having an acid value of 20 to 300 mgKOH / g. If the acid value is less than 20 mgKOH / g, solubility in a developer is poor, and it is difficult to form a fine pattern. If it exceeds 300 mgKOH / g, no micro pattern remains in development.

The binder resin (C) is preferably 30 parts by weight or more with respect to 100 parts by weight of the colorant in consideration of film forming properties and various resistances, and has a high concentration of the colorant component and can express good color characteristics. It is preferable to use it in the quantity of 500 weight% or less with respect to.

(Thermoplastic)

As the thermoplastic resin, for example, acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, poly Ester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, cellulose, polyethylene (HDPE, LDPE), polybutadiene, polyimide resin and the like.

As vinyl alkali-soluble resin which copolymerized the acidic group containing ethylenically unsaturated monomer, resin which has acidic groups, such as a carboxyl group and a sulfone group, is mentioned, for example. Specifically as alkali-soluble resin, acrylic resin which has an acidic group, (alpha) -olefin / (maleic anhydride) copolymer, a styrene / styrene sulfonic acid copolymer, ethylene / (meth) acrylic acid copolymer, or isobutylene / (anhydride) male Acid copolymers and the like. Especially, the acrylic resin which has an acidic group, and at least 1 sort (s) of resin chosen from the styrene / styrene sulfonic acid copolymer, especially the acrylic resin which has an acidic group are used suitably because it has high heat resistance and transparency.

As active energy ray curable resin which has an ethylenically unsaturated double bond, resin which introduce | transduced ethylenically unsaturated double bond by the method of (i) and (ii) shown below is mentioned, for example.

[Method (i)]

As method (i), the carboxyl group of the unsaturated monobasic acid which has an ethylenically unsaturated double bond is added to the side chain epoxy group of the copolymer obtained by copolymerizing the ethylenically unsaturated monomer which has an epoxy group, and another 1 or more types of monomers, for example. There is a method of reacting the resulting hydroxyl group with a polybasic acid anhydride to introduce an ethylenically unsaturated double bond and a carboxyl group.

As an ethylenically unsaturated monomer which has an epoxy group, glycidyl (meth) acrylate, methylglycidyl (meth) acrylate, 2-glycidoxy ethyl (meth) acrylate, 3,4 epoxy butyl ( Meta) acrylate and 3,4 epoxycyclohexyl (meth) acrylate, and these may be used independently or may use two or more types together. From the viewpoint of reactivity with an unsaturated monobasic acid in the next step, glycidyl (meth) acrylate is preferable.

Examples of unsaturated monobasic acids include monocarboxylic acids such as (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl, alkoxyl, halogen, nitro and cyano substituents of (meth) acrylic acid. These may be used, and these may be used independently or may use two or more types together.

Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride and maleic anhydride, and these may be used alone or in combination of two or more. Hydrolyzing the remaining anhydride groups using tricarboxylic anhydrides, such as trimellitic anhydride, or tetracarboxylic dianhydrides, such as pyromellitic dianhydride, as needed, such as increasing the number of carboxyl groups. Etc. are also possible. Furthermore, when tetrahydrophthalic anhydride or maleic anhydride having an ethylenically unsaturated double bond is used as the polybasic acid anhydride, the ethylenically unsaturated double bond can be further increased.

As a method similar to the method (i), for example, an ethylenically unsaturated monomer having an epoxy group is added to a part of the side chain carboxyl group of the copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group with another one or more types of monomers. The reaction is carried out to introduce an ethylenically unsaturated double bond and a carboxyl group.

[Method (ii)]

As method (ii), the isocyanate of the ethylenically unsaturated monomer which has an isocyanate group in the side chain hydroxyl group of the unsaturated monobasic acid which has another carboxyl group, and the copolymer obtained by copolymerizing another monomer using the ethylenically unsaturated monomer which has a hydroxyl group is used. There is a way to react groups.

As ethylenically unsaturated monomer which has a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, Hydroxyalkyl (meth) acrylates, such as glycerol (meth) acrylate or cyclohexane dimethanol mono (meth) acrylate, are mentioned, These may be used independently or may use two or more types together. Furthermore, polyether mono (meth) acrylate which addition-polymerized ethylene oxide, propylene oxide, and / or butylene oxide, etc. to the said hydroxyalkyl (meth) acrylate, (poly) (gamma) -valerolactone, ( (Poly) ester mono (meth) acrylate which added poly) (epsilon) -caprolactone, and / or (poly) 12-hydroxystearic acid, etc. can also be used. 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferable from the standpoint of suppressing foreign matter on the coating film.

Examples of the ethylenically unsaturated monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis [(meth) acryloyloxy] ethyl isocyanate, and the like, but are not limited to these. You can use together more than a kind.

(Thermosetting resin)

As a thermosetting resin, an epoxy resin, a benzoguanamine resin, a melamine resin, a urea resin, a phenol resin etc. are mentioned, for example.

<Other resin>

In addition to said binder resin (C), the composition for coloring is used, such as rosin ester, for the purpose of the improvement and maintenance of the tolerance of fluorescent dye (A), the improvement of the dispersibility of an organic pigment (D), etc. You may contain resin.

Rosin esters are gum rosin, tol rosin, wood rosin, fire which are mainly composed of rosin derived abies acid, neoabies acid, levopimaric acid, hydroabietic acid, fimaric acid, dextrosemaric acid, etc. Esterified with polyhydric alcohols of equalized rosin, hydrogenated rosin, partially disproportionated rosin, maleized rosin and mixtures thereof (glycerol ester, pentaerythritol ester, diethylene glycol ester, etc., particularly preferably pentaerythritol ester).

Rosin ester is obtained by the following method.

Rosin esters are obtained by esterifying purified rosin, such as purified gum rosin, purified wood rosin, purified polymerized rosin, purified disproportionated rosin, or purified tol rosin, as a starting material. In the said esterification reaction, normal conditions can be employ | adopted as it is, For example, refined rosin and the following alcohols are made to react normally under the heating of 150-300 degreeC under inert gas stream, and the produced | generated water is removed out of the system, Do it.

Although it does not specifically limit as alcohol component used for esterification, For example, Monohydric alcohol, such as n-octyl alcohol, 2-ethylhexyl alcohol, decyl alcohol, or lauryl alcohol; Dihydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, neopentyl glycol or cyclohexanedimethanol; Trihydric alcohols such as glycerin, trimethylol ethane or trimethylolpropane; And tetrahydric alcohols such as pentaerythritol or diglycerin. Especially, it is preferable to use trivalent and tetravalent polyhydric alcohol. These may be used singly or in combination of two or more.

Moreover, you may use an esterification catalyst or antioxidant as needed. Examples of the esterification catalyst include acid catalysts such as acetic acid or paratoluenesulfonic acid, hydroxides of alkali metals such as calcium hydroxide, metal oxides such as calcium oxide or magnesium oxide, and the like.

As rosin ester which can be used as a specific commercial item, the following are mentioned.

As the rosin ester, Acer Wakagaku Kogyo Co., Ltd. Pencel A, AZ, ester gum AAG, AAL, A, AAV, 105, HS, AT, etc., Neotol G2, 101K, NT-15, 125HK, hariester TF, NL, S, P, C, DS-70L, DS-90, DS-130, etc. are mentioned.

Examples of the polymerized rosin esters include Hare Kasei Co., Ltd.'s Haresteri KT-2, such as Pencel D-125, D-135, and D-160.

Moreover, as a disproportionated rosin ester, the superester A-75, A-100, A-115, -125, T-125, etc. by Arakawa Kagaku Kogyo Co., Ltd. are mentioned.

As the rosin-modified maleic resin and the rosin-modified fumaric acid resin, malaki NO., Manufactured by Arakawa Kagaku Kogyo Co., Ltd. 1, 2, 5, 6, 8, 30A, 31, 32, 33, 34, 3002, etc. Harimak T-80, R-100, M-453, M-130A, 135GN, 145P, R- 120AH etc. are mentioned.

Examples of the hydrogenated rosin esters include ester gums H, HP, and HD manufactured by Arakawa Kagaku Kogyo Co., Ltd.

Especially, it is preferable to use a polymeric rosin ester, a disproportionated rosin ester, and rosin-modified maleic acid resin (containing rosin-modified fumaric acid resin).

It is preferable that rosin ester has an acid value of 100 mgKOH / g or less. More preferably, it is 40 mgKOH / g or less. An especially preferable range is the range of 5-40 mgKOH / g, and when it is this range, it acts effectively for the performance maintenance of a xanthene type pigment | dye (A).

In consideration of compatibility with the binder resin (C), storage stability and productivity, the softening point of the rosin ester ring-opening method is preferably in the range of 70 to 150 ° C. When it becomes lower than 70 degreeC, storage stability will fall, a coloring composition will aggregate easily, and when exceeding 150 degreeC, adhesiveness of a filter segment may fall.

It is preferable that the addition amount of rosin ester is 0.3-5 weight part with respect to 100 weight part of binder resins (C). If the addition amount of the rosin ester is less than 0.3 part by weight, the effect is difficult to be obtained. If the amount of the rosin ester is more than 5 parts by weight, the performance of the binder resin (C) may be impaired.

`` Organic solvent ''

In this coloring composition, fluorescent dye (A) which is a coloring agent component, organic pigment (D), etc. are fully disperse | distributed and penetrated in coloring agent carriers, such as binder resin (C), and a dry film thickness on substrates, such as a glass substrate, In order to make it easier to form a filter segment by apply | coating so that it may become 0.2-5 micrometers, it can contain an organic solvent.

As the solvent, for example, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane , 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, 3-ethoxypropionic acid Ethyl, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutylacetate, 3-methoxybutanol, 3-methoxybutylacetate, 4 -Heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol Isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol mono Isopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, Ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol Monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropyl Len glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol Diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl Ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid ester, butyl lactate, etc. Can be.

Among them, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and ethylene glycol monomethyl ether acetate in terms of good dispersibility, solubility and permeability of the fluorescent dye (A) and the organic pigment (D). And aromatic alcohols such as glycol acetates such as ethylene glycol monoethyl ether acetate, benzyl alcohol, and ketones such as cyclohexanone are preferably used. Especially, it is preferable to use propylene glycol monomethyl ether acetate and cyclohexanone which are glycol acetates and ketones.

An organic solvent can be used individually by 1 type or in mixture of 2 or more types. Moreover, since a solvent can adjust the coloring composition to the appropriate viscosity and can form the filter segment of the target uniform film thickness, it is the amount of 800-4000 weight% with respect to 100 weight% of total weight of a coloring agent component. It is preferable to use.

<< photopolymerizable monomer >>

You may add a photopolymerizable monomer further to this coloring composition. As a preferable photopolymerizable monomer, the monomer or oligomer which hardens | cures by an ultraviolet-ray, a heat, etc. and produces a transparent resin is mentioned.

As a monomer and oligomer which harden | cure by an ultraviolet-ray, a heat, etc. and produce a transparent resin, For example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy Propyl (meth) acrylate, cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol Di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6 -Hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipenta Tritolhexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, (meth) acrylic acid ester of methylolated melamine, epoxy (meth) acrylate , Various acrylic acid esters such as urethane acrylate, methacrylic acid ester, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, Although N-hydroxymethyl (meth) acrylamide, N-vinylformamide, an acrylonitrile, etc. are mentioned, It is not necessarily limited to these.

These photopolymerizable compounds can be used individually by 1 type or in mixture of 2 or more types in arbitrary ratio as needed.

It is preferable that it is 5-400 weight part with respect to 100 weight part of coloring agents, and, as for the compounding quantity of a photopolymerizable monomer, it is more preferable that it is 10-300 weight part from a viewpoint of photocurability and developability.

Photopolymerization Initiator

In order to harden this composition by ultraviolet irradiation and to form a filter segment by a port lithography method, this coloring composition can be prepared in the form of a solvent developing type or an alkali developing type photosensitive coloring composition by adding a photoinitiator.

Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxychlorohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl ) Methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one Acetophenone type compounds, such as these; Benzoin type compounds, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; Benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-betayldiphenylsulfide, or 3,3 ', 4,4'-tetra ( benzophenone compounds such as t-butylperoxycarbonyl) benzophenone; Thioxanthones such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropyl thioxanthone, 2,4-diisopropyl thioxanthone, or 2,4-diethyl thioxanthone compound; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis ( Trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho-1-yl) -4,6-bis (trichloromethyl) -s -Triazine, 2- (4-methoxy-naphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl)- Triazine-based compounds such as 6-triazine or 2,4-trichloromethyl- (4'-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], or O- (acetyl) -N- (1-phenyl-2-oxo-2- (4 Oxime ester compounds such as' -methoxy-naphthyl) ethylidene) hydroxyamine; bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine Phosphine compounds such as oxides; Quinone compounds such as 9,10-phenanthrenequinone, camphaquinone, and ethyl anthraquinone; Borate compounds; Carbazole compounds; Imidazole compound; Or a titanocene type compound etc. are used.

These photoinitiators can be used individually by 1 type or in mixture of 2 or more types in arbitrary ratio as needed.

It is preferable that it is 2-200 weight part with respect to 100 weight part of coloring agents, and, as for content of a photoinitiator, it is more preferable that it is 3-150 weight part from a viewpoint of photocurability and developability.

<< sensitizer >>

Moreover, this coloring composition can be made to contain a sensitizer.

Examples of the sensitizer include unsaturated ketones represented by chalcone derivatives, dibenzal acetone and the like, 1,2-diketone derivatives represented by benzyl and camphorquinone, etc., benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, Polymethine pigments such as acidene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, acridine derivatives, azine derivatives, Thiazine derivatives, oxazine derivatives, indolin derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporparagine derivatives, Phthalocyanine derivatives, tetraazaporparagine derivatives, tetraquinoxalinoporpyrazine derivatives, naphthalo Non derivatives, subphthalocyanine derivatives, pyryllium derivatives, thiopyryllium derivatives, tetrapyrine derivatives, anurene derivatives, spiropyrane derivatives, spiroxazine derivatives, thiospyropyran derivatives, metal arene complexes, organic ruthenium complexes, or Michler's ketones Derivatives, α-acyloxyester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4'-diethylisophthalophenone, 3,3 Or 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 4,4'-diethylaminobenzophenone, and the like.

These sensitizers can be used individually by 1 type or in mixture of 2 or more types in arbitrary ratio as needed.

More specifically, Okawara Makoto et al., "The Pigment Handbook" (Kodansha, 1986), Okawara Makoto et al., "Chemicals of Functional Pigments" (CMC, 1981), and Ikemori Churros, et al. Although the sensitizer described in Special Function Materials "(CMC, 1986) is mentioned, it is not limited to these. Moreover, the sensitizer which shows absorption with respect to the light from ultraviolet to a near infrared region can also be contained.

It is preferable that it is 3-60 weight part with respect to 100 weight part of photoinitiators contained in a coloring composition, and, as for content of a sensitizer, it is more preferable that it is 5-50 weight part from a viewpoint of photocurability and developability.

`` Multifunctional thiol ''

This color filter coloring composition can contain the polyfunctional thiol which functions as a chain transfer agent.

The multifunctional thiol may be any compound having two or more thiol groups. Examples of the multifunctional thiol include hexanedithiol, decanedithiol, 1,4-butanediol bisstiouropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bis Trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthioglycolate, Pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethyl mercaptobenzene, 2,4,6-trimercapto-s-triazine , 2- (N, N-dibutylamino) -4,6-dimercapto-s-triazine, and the like.

These polyfunctional thiols can be used individually by 1 type or in mixture of 2 or more types in arbitrary ratio as needed.

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

<< antioxidant >>

This color filter coloring composition may contain antioxidant. Antioxidant can raise the transmittance | permeability of a coating film in order to prevent the photoinitiator and thermosetting compound contained in the coloring composition for color filters oxidizing and yellowing by the thermal process at the time of thermosetting or ITO annealing. Therefore, yellowing by oxidation at the time of a heating process can be prevented by including antioxidant, and the transmittance | permeability of a high coating film can be obtained.

"Antioxidant" should just be a compound which has an ultraviolet absorption function, a radical supplement function, or a peroxide decomposition function, Specifically, as an antioxidant, a hindered phenol type, a hindered amine type, phosphorus type, a sulfur type, a benzotriazole type, Benzophenone type, hydroxylamine type, salicylic acid ester type, and triazine type compound are mentioned, A well-known ultraviolet absorber, antioxidant, etc. can be used.

Among these antioxidants, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, or sulfur-based antioxidants are preferable in view of both the transmittance and sensitivity of the coating film. More preferably, it is a hindered phenolic antioxidant, a hindered amine antioxidant, or a phosphorus antioxidant.

These antioxidant can be used individually by 1 type or in mixture of 2 or more types in arbitrary ratio as needed.

Content of antioxidant is more preferable when it is 0.5-5.0 weight% based on solid content weight of the coloring composition for color filters (100 weight%), since brightness and a sensitivity are favorable.

<< leveling agent >>

In order to improve the leveling property of the composition on a transparent substrate, it is preferable to add a leveling agent to this coloring composition. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. As a specific example of the dimethylsiloxane which has a polyether structure in a principal chain, FZ-2122 by Toray Dow Corning Corporation, BYK-333 by Big Chemical Co., etc. are mentioned. As a specific example of the dimethylsiloxane which has a polyester structure in a principal chain, BYK-310, BYK-370, etc. by Big Chemical Co., Ltd. are mentioned. You may use together the dimethylsiloxane which has a polyether structure in a principal chain, and the dimethylsiloxane which has a polyester structure in a principal chain. It is preferable to use 0.003-0.5 weight% of content of a leveling agent normally based on the total weight of a coloring composition (100 weight%).

Particularly preferred as a leveling agent is a kind of a so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, which has a feature of having low hydrophobicity and low surface tension when added to a coloring composition while having a hydrophilic group. In addition, it is useful to have good hygroscopicity to the glass plate even though the surface tension lowering ability is low, and one capable of sufficiently inhibiting chargeability in an amount of addition in which defects in the coating film due to foaming do not appear can be preferably used. As the leveling agent having such desirable properties, dimethylpolysiloxanes having polyalkylene oxide units can be preferably used. As a polyalkylene oxide unit, there exist a polyethylene oxide unit and a polypropylene oxide unit, and dimethyl polysiloxane may have a polyethylene oxide unit and a polypropylene oxide unit together.

In addition, the bond form of the polyalkylene oxide unit with the dimethylpolysiloxane is a pendant block in which the polyalkylene oxide unit is bound in the repeating unit of dimethylpolysiloxane, a terminal modified form bonded to the terminal of the dimethylpolysiloxane, and a linear block alternately repeating the dimethylpolysiloxane. Any of copolymer type may be sufficient. Dimethyl polysiloxanes having polyalkylene oxide units are commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, Although FZ-2207 is mentioned, it is not limited to these.

It is also possible to add anionic, cationic, nonionic or amphoteric surfactants to the leveling agent in an auxiliary manner. You may use surfactant in mixture of 2 or more types.

Examples of the anionic surfactant added to the leveling agent include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salts of styrene-acrylic acid copolymer, sodium alkylnaphthalin sulfonate, sodium alkyldiphenyl ether disulfonate, and lauryl sulfate Monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate ester, etc. are mentioned. have.

Examples of the cationic surfactant added to the leveling agent auxiliary include alkyl quaternary ammonium salts and ethylene oxide adducts thereof. As nonionic surfactant added to a leveling agent auxiliary, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate, polyethylene Glycol monolaurate and the like; Amphoteric surfactants, such as alkylbetaines, such as alkyldimethylamino acetate betaine, and alkyl imidazoline, and fluorine type and silicone type surfactant are mentioned.

<< hardening agent, hardening accelerator >>

Moreover, in order to assist hardening of a thermosetting resin, this coloring composition may contain a hardening | curing agent, a hardening accelerator, etc. as needed. As the curing agent, a phenolic resin, an amine curing agent, an acid anhydride, an active ester, a carboxylic acid compound, a sulfonic acid compound or the like is effective, but it is not particularly limited to these, and any curing agent can be used as long as it can react with the thermosetting resin. You may also These may be used alone, or two or more of them may be used in combination. As content of the said hardening accelerator, 0.01-15 weight% is preferable with respect to the thermosetting resin whole quantity.

(Other additive components)

This coloring composition can contain a storage stabilizer in order to stabilize the time-lapse viscosity of a composition. Moreover, in order to improve adhesiveness with a transparent substrate, you may contain adhesive improvers, such as a silane coupling agent.

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

As an adhesion improving agent, (meth) acrylsilanes, such as vinylsilanes, such as a vinyl tris ((beta) -methoxyethoxy) silane, vinylethoxysilane, and a vinyl trimethoxysilane, (gamma) -methacryloxypropyl trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane , epoxy silanes such as β- (3,4-epoxycyclohexyl) methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane and γ-glycidoxypropyltriethoxysilane, and N-β (amino Ethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysisilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltrie Oxyoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxyoxy Silane coupling agents such as aminosilanes such as silane, thiosilanes such as γ-mercaptopropyltrimethoxysilane, and γ-mercaptopropyltriethoxysilane. The adhesion promoter can be used in an amount of 0.01 to 10% by weight, preferably 0.05 to 5% by weight, based on the total amount of the colorant components in the coloring composition (100% by weight).

<< the manufacturing method of a coloring composition >>

This color filter coloring composition comprises a dye, a two-roll mill, a three-roll mill, a ball mill, a fluorescent dye (A) in a colorant carrier comprising a binder resin (C) and / or an organic solvent. It can manufacture by disperse | distributing finely using various dispersion means, such as a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor. Moreover, when the solubility of a coloring agent is high, it is not necessary to disperse | distribute finely as mentioned above, and to manufacture, if the solubility to the solvent to be used is high, and a melt | dissolution and a foreign material are not confirmed by stirring.

In addition, when it contains an organic pigment (D) as a coloring agent, you may mix and disperse | distribute all the fluorescent dye (A), organic pigment (D), and other coloring agents, etc., or melt | dissolved or disperse | distributed in the coloring agent carrier, respectively. You may mix and manufacture it.

When using as a photosensitive coloring composition (resist material) for color filters, it can be prepared as a solvent developing type or an alkali developing type coloring composition. Solvent development type or alkali development type coloring composition mixes the resin solution containing the said fluorescent dye (A), a photopolymerizable monomer and / or a photoinitiator, and a solvent, a dispersion adjuvant, an additive, etc. as needed. Can be adjusted. An organic compound (B) may be added at the stage of preparing a coloring composition, and the same effect can be obtained even if it adds later to the prepared coloring composition.

(Dispersion auxiliary)

When disperse | distributing a coloring agent in a coloring agent support | carrier, dispersion adjuvant, such as a resin type dispersing agent and surfactant, can be used suitably. The dispersion aid is excellent in dispersion of the colorant and has a great effect of preventing re-agglomeration of the colorant after dispersion. Therefore, when using a coloring composition obtained by dispersing the colorant in the colorant carrier using the dispersion aid, a color filter having a high spectral transmittance Is obtained.

[Resin Dispersant]

The resinous dispersant has a pigment affinity site having a property of being adsorbed to the colorant and a site compatible with the colorant carrier, and is adsorbed by the colorant to stabilize the dispersion to the colorant carrier. Specific examples of the resinous dispersant include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) amine salt, polycarboxylic acid ammonium salt and polycarboxylic acid. Alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, amides formed by reaction of these modified substances, poly (lower alkylene imines) and polyesters having free carboxyl groups, and the like Water-soluble resins, such as oil-based dispersing agents, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, Polymer compound, polyester type, modified polyacrylate type, ethylene oxide / propylene oxide addition compound, phosphate ester type They are used, and these can be used alone or by mixing two or more of, but are not necessarily limited to these.

As a commercially available resin type dispersant, Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167, 168, manufactured by BIC Chemi Japan Co., Ltd. 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164 or Anti-Terra- U, 203, 204 or BYK-P104, P104S, 220S, 6919, 21116, 21324 or Lactimon, Lactimon-WS or Bykumen et al., SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, manufactured by Nippon Lubrizol, Inc. 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 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, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc. Another Fine Techno Company Ath wave PA111, PB711, PB821, PB822, PB824, etc. can be mentioned.

[Surfactants]

As surfactant, sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, the alkali salt of a styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalin sulfonate, sodium alkyl diphenyl ether disulfonate, lauryl sulfate Anionic surfactants such as monoethanolamine, lauryl triethanolamine, lauryl ammonium sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, and polyoxyethylene alkyl ether phosphate ester; Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate; Cationic surfactants such as alkyl quaternary ammonium salts and ethylene oxide adducts thereof; Amphoteric surfactants, such as alkyl betaine, such as alkyldimethylamino acetate betaine, and alkyl imidazoline, are mentioned, These can be used individually or in mixture of 2 or more types, It is not necessarily limited to these.

When adding a resin type dispersing agent and surfactant, it is 0.1-55 weight part with respect to 100 weight part of coloring agents, More preferably, it is 0.1-45 weight part. When the compounding quantity of a resin type dispersing agent and surfactant is less than 0.1 weight part, the added effect is hard to be acquired, and when a compounding quantity is more than 55 weight part, an excessive dispersing agent may affect dispersion.

《Removal of Coarse Particles》

This color filter coloring composition is a means of centrifugation, a sintering filter, a membrane filter, etc., and removes coarse particles of 5 μm or more, preferably 1 μm or more of coarse particles, more preferably 0.5 μm or more of coarse particles, and mixed dust. It is preferable to carry out. Thus, it is preferable that the coloring composition for color filters does not contain particle | grains 0.5 micrometer or more substantially. More preferably, all the particles are substantially 0.3 µm or less. In addition, it measured here using the particle size distribution measuring apparatus "Nano-S" (sysmex Co., Ltd.) using the dynamic light scattering method.

<< color filter >>

A color filter according to the present aspect comprises at least one red filter segment, at least one green filter segment, and at least one blue filter segment, wherein the at least one filter segment is formed using the coloring composition for the color filter. do. Especially, it is preferable to form in a red filter segment and a blue filter segment using said coloring composition.

<< manufacturing method of color filter >>

This color filter can be manufactured by the printing method or the photolithography method.

Since formation of the filter segment by the printing method can be patterned only by repeating printing and drying of the blue coloring composition prepared as a printing ink, it is low cost and excellent in mass productivity as a manufacturing method of a color filter. Further, with the development of printing technology, it is possible to print fine patterns having high dimensional accuracy and smoothness. In order to perform printing, it is preferable to set it as the composition which ink does not dry and solidify on a printing plate or a blanket. Moreover, control of the fluidity | liquidity of the ink on a printing press is also important, and ink viscosity can be adjusted with a dispersing agent and a extender pigment.

In the case of forming the filter segment by the photolithography method, the photosensitive coloring composition containing the blue coloring composition prepared as the solvent developing type or the alkali developing type coloring resist is spray coated, spin coated, slit coated, rolled on a transparent substrate. By coating methods, such as coating, it apply | coats so that dry film thickness may be 0.2-5 micrometers. An ultraviolet-ray exposure is performed to the film dried as needed through the mask which has a predetermined | prescribed pattern provided in the contact or non-contact state with this film. Thereafter, the developer can be immersed in a solvent or an alkaline developer or sprayed with a spray or the like to remove the uncured portion to form a desired pattern, and then the same operation can be repeated for another color to produce a color filter. Moreover, in order to accelerate superposition | polymerization of a coloring resist material, you may heat as needed. According to the photolithography method, a color filter having higher precision than the printing method described above can be manufactured.

At the time of image development, aqueous solution, such as sodium carbonate and sodium hydroxide, is used as alkaline developing solution, Organic alkali, such as dimethylbenzylamine and triethanolamine, can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.

Further, in order to increase the ultraviolet exposure sensitivity, after coating and drying the colored resist material, a water-soluble or alkali water-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film to prevent polymerization inhibition by oxygen. After that, ultraviolet light exposure may be performed.

This color filter can be manufactured by an electrodeposition method, a transfer method, etc. other than the said method, but this coloring filter coloring composition can be used also in any method. In addition, the electrodeposition method is a method of manufacturing a color filter by electrodepositing each color filter segment on a transparent conductive film by the electrophoresis of colloidal particle using the transparent conductive film formed on the board | substrate. The transfer method is a method in which filter segments are formed in advance on the surface of the peelable transfer base sheet, and the filter segments are transferred to a desired substrate.

Before forming each color filter segment on the transparent substrate or the reflective substrate, a black matrix may be formed in advance. As a black matrix, inorganic films, such as a chromium, a chromium / chromium oxide multilayer film, and titanium nitride, and the resin film which disperse | distributed the light-shielding agent are used, It is not limited to these. In addition, a thin film transistor (TFT) may be formed on the transparent substrate or the reflective substrate in advance, and thereafter, each color filter segment may be formed. Furthermore, an overcoat film, a transparent conductive film, etc. are formed on this color filter as needed.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In addition, in an Example, "part" and "%" represent a "weight part" and "weight%", respectively.

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

(Weight average molecular weight (Mw) of the resin)

The weight average molecular weight (Mw) of the resin was measured by using HLC-8220GPC (manufactured by Tosoh Corp.) as a device, connecting TSK-GEL SUPER HZM-N in double columns as a column, and using THF as a solvent. It is one polystyrene conversion molecular weight.

(Measurement of contrast ratio)

Light originating from the backlight unit for liquid crystal displays passes through a polarizing plate, and is polarized, passes through the dry coating film of the coloring composition apply | coated on a glass substrate, and reaches a polarizing plate. When the polarizing planes of the polarizing plate and the polarizing plate are parallel, light passes through the polarizing plate, but when the polarizing planes are orthogonal, the light is blocked by the polarizing plate. However, when the light polarized by the polarizing plate passes through the dry coating film of the coloring composition, scattering by the pigment particles occurs, and when a deviation occurs in a part of the polarizing plane, when the polarizing plates are parallel, the amount of light passing through the polarizing plate decreases, When the polarizing plate is orthogonal, some light passes through the polarizing plate. This transmitted light was measured as the luminance on a polarizing plate, and the ratio (contrast ratio) of the luminance when a polarizing plate is parallel and the luminance when it is orthogonal was computed.

(Contrast ratio) = (luminance when parallel) / (luminance when orthogonal)

Therefore, when scattering is caused by the pigment in the coating film, the brightness in parallel decreases and the brightness in orthogonality increases, so the contrast ratio is lowered.

As the luminance meter, a color luminance meter ("BM-5A" manufactured by Topcon Corporation) and a polarizing plate ("NPF-G1220DUN" manufactured by Nitto Denko Corporation) were used as the polarizing plate. At the time of measurement, in order to block unnecessary light, a black mask having a hole of 1 cm in width and width was placed on the measurement portion.

First, the manufacturing method of the binder resin (C) solution used by the Example and the comparative example, the preparation method of the resin type dispersant solution, the fluorescent pigment | dye (A), its manufacturing method, the organic compound represented by General formula (B) The manufacturing method of a pigment dispersion, and the manufacturing method of the photosensitive coloring composition are demonstrated.

<Method for producing binder resin (C) solution>

(Preparation of acrylic resin solution)

800 parts of cyclohexanone were put into a reaction container, and it heated at 100 degreeC, injecting nitrogen gas into a container, At the same temperature, 80.0 parts of styrene, 40.0 parts of methacrylic acid, 85.0 parts of methyl methacrylate, n-butyl methacrylate A mixture of 95.0 parts and 10.0 parts of azobisisobutyronitrile was added dropwise over 1 hour to conduct a polymerization reaction.

After dripping, it was made to react further at 100 degreeC for 3 hours, Then, the thing which melt | dissolved 2.0 parts of azobisisobutyronitrile in 50 parts of cyclohexanone was added, The reaction was further continued at 100 degreeC, and a weight average molecular weight is about 30,000 The cyclohexanone solution of acrylic resin of the acid value of 87 mgKOH / g was obtained.

After cooling to room temperature, approximately 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and ethylene glycol monomethyl ether acetate was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. To prepare an acrylic resin solution.

<Method of Preparing Resin Dispersant Solution>

Using a BASF company EFKA4300, a commercially available resin type dispersant, and ethylene glycol monomethyl ether acetate, a non-volatile content of 40% by weight solution was used, and was used as a resin type dispersant solution.

<Method for producing fluorescent dye (A)>

(Xanthene dye (A-1); Rhodamine salt forming compound)

Xanthene dye (A-1) which consists of CI acid red 52 and dialkyl (alkyl is C14-C18) dimethylammonium chloride (arquad 2HT-75) (molecular weight of the cation part is 438-550) by the following procedure Made.

In 7-15 mol% sodium hydroxide solution, C. I. acid red is melt | dissolved, it fully mixes and stirs, after heating to 70-90 degreeC, the arcade 2HT-75 is dripped gradually. Arquad 2HT-75 may be dissolved in water and used as an aqueous solution. After dropping the Arquad 2HT-75, the mixture is stirred at 70 to 90 ° C. for 60 minutes to sufficiently react. As confirmation of the end point of reaction, a reaction liquid is dripped at the filter paper, and it can be judged that the salt forming compound was obtained by making into the end point the time when the bleeding disappeared. After cooling to room temperature with stirring, suction filtration was carried out, and after washing with water, the salt-containing compound remaining on the filter paper was dried by removing water from a drier, followed by CI acid red 52 and dialkyl (alkyl C14-C18) dimethylammonium chloride. Xanthene type dye (A-1) which is a salt-forming compound of was obtained.

(Xanthene dye (A-2); Rhodamine salt forming compound)

In the following procedure, xanthene dye (A-2) consisting of C. I. acid red 52 and distearyldimethylammonium chloride (cotamine D86P) (molecular weight of cation moiety is 550) was produced.

In 7-15 mol% sodium hydroxide solution, C. I. acid red 52 is dissolved, thoroughly mixed and stirred, and heated to 70-90 ° C., followed by dropwise addition of cotamine D86P. Cotamine D86P may be dissolved in water and used as an aqueous solution. After dropping the cotamine D86P, the mixture is stirred at 70 to 90 ° C. for 60 minutes to sufficiently react. As confirmation of the end point of reaction, a reaction liquid is dripped at the filter paper, and it can be judged that the salt forming compound was obtained by making into the end point the time when the bleeding disappeared. After cooling to room temperature with stirring, suction filtration was carried out, and after washing with water, the salt-containing compound remaining on the filter paper was dried by removing water from a dryer and dried, and a xanthene-based compound which is a salt compound of CI acid red 52 and distearyldimethylammonium chloride. Dye (A-2) was obtained.

(Xanthene dye (A-3); Rhodamine sulfonic acid amide compound)

Based on the description of Japanese Patent Application Laid-Open No. 6-194828, after CI acid red 52 is sulfonyl chloride by a conventional method, the reaction is carried out with a theoretical equivalent of 2-ethylhexylamine in dioxane to give CI acid red 52. Xanthene type dye (A-3) which is a sulfonic acid amide compound was obtained.

(Xanthene dye (A-4); Rhodamine salt forming compound)

In the following procedure, xanthene dye (A-4) consisting of C. I. basic red 1 and 2-amino-1-naphthalenesulfonic acid (tobias acid) (molecular weight 223) was produced.

2-amino-1-naphthalenesulfonic acid (tobias acid) (molecular weight 223) is dissolved in 9 mol% of sodium hydroxide solution, sufficiently mixed and stirred to obtain the sodium salt. After heating this aqueous 2-amino-1-naphthalene sulfonic acid (tobias) sodium salt solution at 85 degreeC, rhodamine 6GCP dye (C.I. basic red 1) is dripped gradually. Rhodamine 6GCP dye may be dissolved in water and used as an aqueous solution. After adding rhodamine 6GCP dye, it stirred at 85 degreeC for 55 minutes, and fully reacts. As confirmation of the end point of reaction, a reaction liquid is dripped at the filter paper, and it can be judged that the salt forming compound was obtained by making into the end point the time when the bleeding disappeared. After cooling to room temperature with stirring, suction filtration is performed and washed with water. After washing with water, the salt-containing compound remaining on the filter paper was dried by removing moisture from the dryer, and the salt-forming compound of rhodamine 6GCP dye and 2-amino-1-naphthalenesulfonic acid (tobias acid) and the rhodamine salt-forming compound (A-4) were dried. Got it.

(Triphenylmethane dye (A-5); Triphenylmethane salt forming compound)

In the following procedure, triphenylmethane dye (A-5) consisting of C. I. basic blue 7 and 2-amino-1-naphthalenesulfonic acid (tobias acid) (molecular weight 223) was produced.

2-amino-1-naphthalenesulfonic acid (Tobias acid) (molecular weight: 223) is dissolved in 9 mol% sodium hydroxide solution and sufficiently mixed and stirred to obtain the sodium salt. After heating this aqueous 2-amino-1-naphthalenesulfonic acid (tobias acid) (molecular weight 223) sodium salt solution to 85 degreeC, Victoria pure blue dye (C.I. basic blue 7) is dripped gradually. In addition, the Victorian pure blue dye may be dissolved in water and used as an aqueous solution. After dropping the Victorian pure blue dye, the mixture is stirred at 85 ° C for 55 minutes to sufficiently react. As confirmation of the end point of reaction, a reaction liquid is dripped at the filter paper, and it can be judged that the salt forming compound was obtained by making into the end point the time when the bleeding disappeared. After cooling to room temperature with stirring, suction filtration is performed and washed with water. After washing with water, the salt-containing compound remaining on the filter paper was dried by removing moisture from the dryer, and the salt-containing compound and triarylmethane salt-containing compound (A-) of Victoria pure blue dye and 2-amino-1-naphthalenesulfonic acid (tobias acid) 5) was obtained.

(Triphenylmethane dye (A-6); Triphenylmethane salt forming compound)

In the following procedure, triphenylmethane dye (A-6) consisting of C. I. basic blue 7 and perchloric acid (molecular weight 100.5) was produced.

Perchloric acid (molecular weight: 100.5) is dissolved in a sodium hydroxide solution of 9 mol% and sufficiently mixed and stirred to obtain a sodium salt thereof. After heating this aqueous sodium perchlorate salt at 85 degreeC, Victorian pure blue dye (C.I. basic blue 7) is dripped gradually. In addition, the Victorian pure blue dye may be dissolved in water and used as an aqueous solution. After dropping the Victoria pure blue dye, the mixture is stirred at 85 ° C. for 55 minutes to sufficiently react. As confirmation of the end point of reaction, a reaction liquid is dripped at the filter paper, and it can be judged that a salt forming compound was obtained by making into the end point the time when the bleeding disappeared. After cooling to room temperature with stirring, suction filtration is performed and washed with water. After washing with water, the salt-containing compound remaining on the filter paper was removed by drying in a drier to obtain a salt-containing compound and a triarylmethane salt-forming compound (A-6) of Victoria pure blue dye and perchloric acid.

(Quinoline dyes (A-7))

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 naphthalenedicarboxylic acid anhydrides, and 30 parts of benzoic acid were mixed, and it stirred at 200 degreeC for 7 hours. 100 parts of methanol was added after cooling, and it stirred for 1 hour. The precipitated solid was collected by suction filtration. Further, the solid was put into 200 parts of methanol, and after stirring for 1 hour, the solid was collected by suction filtration. It dried with the vacuum dryer (40 degreeC) overnight, and obtained the product of 3.1 parts. Yield 67%. The product identified the compound by the mass spectrometer (TOF-MS: Bruker Daltonics make autoflexII). m / z = 366 (molecular weight: 365.4).

(Quinoline Pigment (A-8))

As a quinoline pigment, C. I. Pigment Yellow 138 (paliotol yellow K0961-HD manufactured by BASF) was used.

(Phenylmethane Dye (A-9); Triphenylmethane Dye Salting Compound)

The triphenylmethane salt salt compound obtained by the following method was used as (A-9). By the method disclosed in document BIOS 1157,53, 106 g (1 mol) of benzaldehyde is condensed with 508 g (2 mol) of N-benzyl-N-butyl-m-toluidine, sulfonated, a trisulfonic acid group is introduced, and this is manganese dioxide (MnO). After oxidizing with ₂ ), it was reacted with 137 g (1 mol) of p-phenetidine to obtain 500 g of anion component.

This 91 g (0.1 mol) was melt | dissolved in the water of 60 degreeC of water temperature, and the aqueous solution of 3% was obtained. This was prepared to pH7 and filtered. While stirring the filtrate, an acetic acid aqueous solution of 22.5 g (0.12 mol) of 3- (2-ethylhexyloxy) propylamine as a cation component was added dropwise over 40 minutes. After the reaction at room temperature for 2 hours, the mixture was prepared at pH = 5 to 6, and then heated to 40 ° C to form coarse particles. Then, it filtered and washed with water and dried, and obtained 97 g of blue salt dyes.

(Thiazine dye (A-10); thiazine salt forming compound)

A thiazine dye (A-8) consisting of C. I. basic blue 9 and 2,8-diamino-1-naphthol-5,7-disulfonic acid (molecular weight 334) was produced in the following procedure. In a 7-15 mol% sodium hydroxide solution, 2,8-diamino-1-naphthol-5,7-disulfonic acid (molecular weight 334) is dissolved, thoroughly mixed and stirred to obtain the sodium salt. After heating this 2,8- diamino-1- naphthol-5, 7- disulfonate sodium salt aqueous solution to 70-90 degreeC, the methylene blue FZ dye (C.I. basic blue 9) is dripped gradually. The methylene blue FZ dye may be dissolved in water and used as an aqueous solution. After dropping methylene blue FZ dye, the mixture is stirred at 70 to 90 ° C. for 40 to 60 minutes to sufficiently react. As confirmation of the end point of reaction, a reaction liquid is dripped at the filter paper, and it can be judged that the salt forming compound was obtained by making into the end point the time when the bleeding disappeared. After cooling to room temperature with stirring, suction filtration is performed and washed with water. After washing with water, the salt-containing compound remaining on the filter paper was dried by removing moisture from the dryer, and the salt-containing compound and thiazine-based salt compound of methylene blue FZ dye and 2,8-diamino-1-naphthol-5,7-disulfonic acid ( A-10) was obtained.

(Thiazole dye (A-11); thiazole salt forming compound)

The thiazole dye (A-9) which consists of C. I. direct yellow 8 and distearyl dimethylammonium chloride (cotamine D86P) (molecular weight of cationic part is 550) was produced with the following procedure.

After dissolving C. I. direct yellow 8 in 7-15 mol% sodium hydroxide solution, fully mixing and stirring, heating to 70-90 degreeC, the kotamine D86P is dripped gradually. Cotamine D86P may be dissolved in water and used as an aqueous solution. After dropping the cotamine D86P, the mixture is stirred at 70 to 90 ° C. for 60 minutes to sufficiently react. As confirmation of the end point of reaction, it can be judged that a salt-forming compound was obtained by making a reaction liquid dropwise into a filter paper, and making the end point into the end point where bleeding disappeared. After cooling to room temperature while stirring, suction filtration was carried out, and after washing with water, the salt-containing compound remaining on the filter paper was removed by drying with moisture in a drier, and a thiazole dye as a salt-forming compound of CI direct yellow 8 and distearyldimethylammonium chloride. (A-11) was obtained.

(Diketopyrrolopyrrole Pigment (A-12))

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

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

Table 1 shows the details of the organic compound (Bb) used in the examples.

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

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

<Organic compound (Bp) having a functional group having an organic pigment skeleton or an aminobenzene skeleton and a phthalimide skeleton>

Table 3 shows the details of the organic compound (Bp) used in the examples.

&Lt; Production method of pigment dispersion >

(Blue Pigment Dispersion (P-1))

CI pigment blue 15: 6 (PB 15: 6) (11.0 parts for "LIONOL BLUE ES" made by Toyo Inky Sejo Co., Ltd., 35.0 parts for acrylic resin solution, 5 parts for resin type dispersant solution, ethylene glycol monomethyl ether After uniformly mixing 49 parts of acetate, the mixture was dispersed in an Eiger mill (`` Mini Model M-250 MKII '' manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm, and then filtered through a 5 μm filter. The blue pigment dispersion (P-1) of PB 15: 6 was produced.

(Purple Pigment Dispersion (P-2))

Except for changing CI Pigment Blue 15: 6 to CI Pigment Violet 23 (PV23) (`` LIONOGEN VIOLET RL '' manufactured by Toyo Inky Seiko Co., Ltd.). The purple pigment dispersion (P-2) was produced.

(Red Pigment Dispersion (P-3))

Except for changing CI Pigment Blue 15: 6 to CI Pigment Red 254 (PR254) (`` IRGAPHOR RED B-CF '' manufactured by Chiba Specialty Chemicals), in the same production method as the blue pigment dispersion (P-1). , Red pigment dispersion (P-3) of PR254 was produced.

(Red Pigment Dispersion (P-4))

The red pigment dispersion of PR177 by the same manufacturing method as the blue pigment dispersion (P-1) except having changed CI pigment blue 15: 6 into CI pigment red 177 (PR177) ("A2B" made by BASF Corporation). (P-4) was produced.

(Green Pigment Dispersion (P-5))

Except for changing CI Pigment Blue 15: 6 to CI Pigment Green 58 (PG58) (&quot; A110 &quot; manufactured by Dainippon Ink and Chemical Industries, Ltd.), PG58 was produced in the same manner as in the blue pigment dispersion (P-1). The green pigment dispersion (P-4) was produced.

(Yellow Pigment Dispersion (P-6))

Yellow pigment dispersion of PY150 by the same manufacturing method as Blue pigment dispersion (P-1) except having changed CI Pigment Blue 15: 6 to CI Pigment Yellow 150 (PY150) ("E4GN" by LANXESS company). (P-5) was produced.

(Orange Pigment Dispersion (P-7))

Except for changing CI Pigment Blue 15: 6 to CI Pigment Red 242 (PY242) (`` SandorinScarlet4RF '' manufactured by Clariant), the orange pigment dispersion of PY242 by the same production method as the blue pigment dispersion (P-1). (P-7) was produced.

(Blue Pigment Dispersion (P-8))

By the same production method as blue pigment dispersion (P-1) except having changed CI Pigment Blue 15: 6 to CI Pigment Blue 15: 1 ("LIONOL BLUE 7120-V" made by Toyo Ink Corporation) , PB15: 1, a blue pigment dispersion (P-8) was produced.

(Green Pigment Dispersion (P-9))

Except for changing CI Pigment Blue 15: 6 to CI Pigment Green 36 (PG36) (`` LIONOL BGREEN 2YS '' manufactured by Toyo Inkes Co., Ltd.). The green pigment dispersion (P-9) of PG36 was produced.

Example 1

(Dye Containing Resin Solution (DA-1))

After stirring and mixing each mixture so that it may become uniform with the following composition, it disperse | distributes for 2 hours with the Eiger mill ("mini-model M-250 MKII" by Eiger Japan company) using the zirconia bead of diameter 0.5mm, and also it is 5.0 micrometers It filtered with the filter of and produced the dye containing resin solution (DA-1).

Xanthene dye (A-1): 3.0 parts

Acrylic resin solution: 57.5 parts

Organic compound (Ba-19): 0.5 part

Cyclohexanone: 39.0 parts

Examples 2 to 36 and Comparative Examples 1 to 12

(Dye-containing resin solution (DA-2 to 48))

Hereinafter, as shown in Table 2, the dye-containing resin solutions (DA-2 to 48) were obtained in the same manner as the dye-containing resin solution (DA-1) except that the composition and the compounding amount were changed. When using (A-8) and (A-12) as a pigment | dye (A), 0.8 part of EFKA4300 by BASF Corporation which is a commercially available resin type dispersing agent was added.

[Evaluation of Coloring Composition]

About the obtained dye containing resin solution (DA-1-48), evaluation about contrast ratio was performed by the following method. The results are shown in Table 5.

(Contrast ratio)

The dye-containing resin solution (DA-1 to 48) was applied onto a glass substrate 100 mm × 100 mm, 1.1 mm thick, using a spin coater, so that the film thickness of the dry coating film was 1.2 μm, and the temperature was increased to 230 ° C. in an oven at 20 ° C. The powder was fired to prepare a coated substrate. The contrast ratio (CR) was measured using the obtained coating substrate.

The criteria are as follows. In the evaluation results, ○ indicates a good result, and △ has a problem slightly, but the level where there is no problem in use, and × corresponds to the use failure.

○: 10000 or more

(Triangle | delta): 7000 or more and less than 10000

×: less than 7000

The coloring compositions including the fluorescent dye (A), and the organic pigment skeleton or the aminobenzene skeleton and the organic compound (B) having an acidic functional group, a basic functional group or a phthalimide skeleton, all had excellent contrast ratios. It is thought that the fluorescence of the fluorescent dye (A) is suppressed by the organic compound (B).

Example 37

(Blue Photosensitive Coloring Composition (RB-1))

After stirring and mixing the following mixture to make it uniform, it filtered by 1.0 micrometer filter and produced the blue photosensitive coloring composition (RB-1).

Pigment Dispersion (P-1): 40.0 parts

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

Acrylic resin solution: 7.5 parts

Photopolymerizable monomer: 2.0 parts

(Dipentaerythritol hexaacrylate)

Photopolymerization initiator: 1.5 parts

(2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one ("irgacure 907" made by Chiba Japan Corporation))

Organic solvents: 39.0 parts

(Ethylene Glycol Monomethyl Ether Acetate)

[Examples 38-46 and Comparative Examples 13-19]

(Blue Photosensitive Coloring Composition (RB-2 to 17))

Except having changed the kind of dye containing resin solution as shown in Table 6, it carried out similarly to blue photosensitive coloring composition (RB-1), and produced blue photosensitive coloring composition (RB-2-17). Here, the compounding amount (weight part) of a pigment dispersion and a dye containing resin solution is made so that it may match x = 0.150 and y chromaticity of y = 0.060 by C light source after baking at 230 degreeC, when all the coating substrates were produced, Selected ratio. In addition, the sum total content of a pigment dispersion and dye containing resin solution is 50.0 parts.

[Example 47]

(Green Photosensitive Coloring Composition (RG-1))

After stirring and mixing the following mixture to make it uniform, it filtered by 1.0 micrometer filter and produced the red 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 parts

Photopolymerizable monomer: 2.0 parts

(Dipentaerythritol hexaacrylate)

Photopolymerization initiator: 1.5 parts

(2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one ("irgacure 907" made by Chiba Japan Corporation))

Organic solvents: 39.0 parts

(Ethylene Glycol Monomethyl Ether Acetate)

[Examples 47-52 and Comparative Examples 20-22]

(Green Photosensitive Coloring Composition (RG-2-9))

Except having changed the kind of pigment dispersion and dye containing resin solution as shown in Table 7, it carried out similarly to green photosensitive coloring composition (RG-1), and produced green photosensitive coloring composition (RG-2-9). . Here, the compounding quantity (weight part) of a pigment dispersion and a dye containing resin solution is made so that it may match x = 0.290 and y = 0.600 chromaticity with C light source after baking at 230 degreeC, when all the coating substrates were produced, Selected ratio. In addition, the sum total content of a pigment dispersion and dye containing resin solution is 50.0 parts.

[Example 53]

(Red Photosensitive Coloring Composition (RR-1))

After stirring and mixing the following mixture to make it uniform, it filtered by 1.0 micrometer filter and produced the 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 parts

Photopolymerizable monomer: 2.0 parts

(Dipentaerythritol hexaacrylate)

Photopolymerization initiator: 1.5 parts

(2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one ("irgacure 907" made by Chiba Japan Corporation))

Organic solvents: 39.0 parts

(Ethylene Glycol Monomethyl Ether Acetate)

[Examples 54-59 and Comparative Examples 22-27]

(Red Photosensitive Coloring Composition (RR-2 to 13))

Except having changed the kind of pigment dispersion and dye containing resin solution as shown in Table 8, it carried out similarly to red photosensitive coloring composition (RR-1), and produced red photosensitive coloring composition (RB-2-13). . Here, the compounding quantity (weight part) of a pigment dispersion and a dye containing resin solution is matched with chromaticity of x = 0.645 and y = 0.323 by C light source after baking at 230 degreeC, even when any coating substrate is produced, Selected ratio. In addition, the sum total content of a pigment dispersion and dye containing resin solution is 50.0 parts.

[Evaluation of the photosensitive coloring composition]

The obtained photosensitive coloring compositions (RB-1 to 17, RG-1 to 9, and RR-1 to 13) were evaluated for lightness (spectral transmittance) and contrast ratio (CR) by the following method. The results are shown in Tables 6-8.

(Brightness (spectral transmittance))

Each photosensitive coloring composition was applied onto a glass substrate 100 mm × 100 mm, 1.1 mm thick with a spin coater, exposed to UV light at an exposure dose of 50 mJ / cm ² , and then sprayed for 30 seconds with an aqueous solution of 0.2 wt% sodium carbonate at 23 ° C. It baked at 230 degreeC in the oven for 30 minutes, and obtained the coating substrate of the obtained photosensitive coloring composition. Brightness (spectral transmittance) was measured using the obtained coating substrate.

In addition, the blue coating film by the blue photosensitive coloring composition was apply | coated so that it might match x chromaticity of x = 0.150 and y = 0.060 with C light source during baking at 230 degreeC. In addition, the green coating film by a green photosensitive coloring composition by the same method is 230 degreeC, and the red coating film by a red photosensitive coloring composition is 230 so that it may match chromaticity of x = 0.290 and y = 0.600 in C light source. During firing at ° C., coating was performed to match chromaticity of x = 0.645 and y = 0.323 in the C light source.

In addition, the measurement of the lightness (spectral transmittance) in an XYZ colorimeter chromaticity diagram was performed using the spectrophotometer (OTSUKA LCF-1100M).

Judgment criteria are as follows. In an evaluation result, (circle) shows a favorable result and (triangle | delta) is corresponded to the level which has a problem although there is a little problem.

Blue photosensitive coloring composition

○; 11.8 or more

?; 11.5 or more but less than 11.8

×; Less than 11.5

Green photosensitive coloring composition

○: 61 or more

△: 60 or more and less than 61

×: less than 60

Red photosensitive coloring composition

○: 20.4 or more

△: 20.0 or more but less than 20.4

×: less than 20.0

(Contrast ratio)

Contrast ratio (CR) was measured using the same board | substrate as the coating substrate used for brightness measurement.

The criteria are as follows. In an evaluation result, (circle) shows a favorable result and (triangle | delta) is corresponded to the level which has a problem although there is a little problem.

Blue photosensitive coloring composition

○: 11000 or more

△: more than 8000 less than 11000

×: less than 8000

Green photosensitive coloring composition

○: 11000 or more

△: more than 9000 less than 11000

×: less than 9000

Red photosensitive coloring composition

○: 22000 or more

△: 20000 or more but less than 22000

×: less than 20000

The coloring composition containing the fluorescent dye (A) and the organic pigment skeleton or the organic compound (B) which has an aminobenzene skeleton and a basic functional group are all very excellent in contrast ratio, This is an organic compound (B), It is considered that the fluorescence of the fluorescent dye (A) is suppressed.

[Example 60]

(Color filter (CF-1))

The black matrix was pattern-processed on the glass substrate, and the red photosensitive coloring composition (RR-13) was apply | coated with the spin coater on this board | substrate, and the coloring film was formed. The film was irradiated with ultraviolet light of 150 mJ / cm ² using an ultrahigh pressure mercury lamp through a photomask. Subsequently, spray development was carried out with an alkali developer composed of 0.2% by weight aqueous sodium carbonate solution to remove the unexposed portions, and then washed with ion-exchanged water, and the substrate was heated at 220 ° C. for 20 minutes to form a red filter segment. Here, after the heat processing at 220 degreeC, the red filter segment was made to match chromaticity of x = 0.645 and y = 0.323 in C light source (it also uses green and blue hereafter). Also by the same method, the green filter segment is matched to the chromaticity of x = 0.290, y = 0.600 using the green photosensitive coloring composition (RG-9), and the blue filter segment is used for the blue photosensitive coloring composition (RB-1). Each filter segment was formed so that it might match chromaticity of x = 0.150 and y = 0.060, and obtained color filter (CF-1).

Examples 61-74 and Comparative Examples 28-34

(Color filter (CF-2 to 22))

Hereinafter, except for changing to the combination of the red photosensitive coloring composition, green photosensitive coloring composition, and blue photosensitive coloring composition shown in Table 9, it carried out similarly to color filter (CF-1), and obtained color filters (CF-2-22).

[Evaluation of Color Filters]

About the obtained color filter, the evaluation about the brightness (spectrum transmittance) and contrast ratio was performed by the following method. The results are shown in Table 9.

(Brightness (spectral transmittance))

The measurement of the lightness (spectral transmittance) in an XYZ colorimeter chromaticity diagram was performed using the spectrophotometer (OTSUKA LCF-1100M).

Judgment criteria are as follows. In an evaluation result, (circle) shows a favorable result and (triangle | delta) is corresponded to the level which has a problem although there is a little problem.

○; 28.80 or more

?; 28.60 or more but less than 28.80

×; Less than 28.60

(Contrast ratio)

Judgment criteria are as follows. In an evaluation result, (circle) shows a favorable result and (triangle | delta) is corresponded to the level which has a problem although there is a little problem.

○; 18000 or more

?; 16500 or more but less than 18000

×; Less than 16500

Example 75 and Comparative Example 35

In order to confirm the fluorescence quenching effect with respect to the pigment | dye A of the organic compound B, the fluorescence emission intensity of the application | coating board | substrate created in Example 20 was compared with the thing of the comparative example 7 on condition of the following.

Measuring apparatus: Nippon Bunko Fluorometer FP-750

Measuring conditions:

Excitation wavelength 420 nm (selected as wavelength with dye absorption in visible region)

570 nm measurement wavelength (on the longer wavelength than the excitation wavelength, selected in the maximum region of the fluorescence intensity distribution)

Receive Sensitivity Condition High

Measurement result: Coating substrate of Example 20 (Example 75) --- fluorescence intensity 10

Coating Substrate of Comparative Example 7 (Comparative Example 35) --- Fluorescence Intensity 28

The above-mentioned "fluorescence intensity" is the intensity of the light of fluorescent light emission from the film surface confirmed when the excitation light is irradiated to the film, and the larger the number, the stronger the light emission intensity. The stronger the fluorescence emission intensity is, the more the ratio of unpolarized light increases when the polarized light is transmitted, and it is considered that the CR value is lowered.

It is thought that the fluorescent quenching effect to the pigment | dye (A) exists by addition of an organic compound (B), and the effect of CR value improvement with respect to the comparative example 7 confirmed in Example 20 was obtained.

Therefore, it is confirmed that the fluorescence quenching effect to the pigment | dye (A) of an organic compound (B) exists and contributes to the improvement of CR value.

By using this coloring composition for color filters, it was possible to suppress the fluorescence emission by the fluorescent dye, and to produce the color filter of high brightness and high contrast ratio.

While certain embodiments have been described, these embodiments have been presented by way of example only, and are not intended to limit the scope of the inventions. These novel embodiments can be implemented in other various forms, and various omissions, substitutions, and changes can be made without departing from the gist of the invention. These embodiments and modifications thereof are included in the scope and spirit of the invention, and are included in the invention and equivalent scope of the claims.

Claims (9)

A coloring composition for color filters, comprising a fluorescent dye (A), an organic compound represented by the formula (B), and a binder resin (C).
(Formula 1)
P-Lm
[Formula 1,
P is an organic pigment skeleton or an aminobenzene skeleton,
L is a basic functional group Lb, an acidic functional group La or a functional group Lp having a phthalimide backbone,
m is an integer of 1-4 and shows the number of functional groups.] The fluorescent dye (A) is a triphenylmethane dye, a diphenylmethane dye, a quinoline dye, a thiazine dye, a thiazole dye, a xanthene dye, and a diketopyrrolopyrrole dye. It is any one selected from the group which consists of a coloring composition for color filters. The organic pigment skeleton is a phthalocyanine pigment, a benzimidazolone pigment, a dioxazine pigment, an azo pigment, an anthraquinone pigment, a dianthraquinone pigment, or a diketopyrrolopyrrole pigment. , Thiazine indigo pigment, and a quinophthalone pigment, any one selected from the group consisting of color composition for color filters. The basic functional group Lb has a basic functional group represented by the formula (2) or (5), and the acidic functional group La has an acidic functional group represented by the formula (3) or (5), and a phthalimide skeleton. The functional group Lp which has a has a functional group shown by General formula (4) or (5), The coloring composition for color filters characterized by the above-mentioned.
(2)

(Formula 3)

(Formula 4)

(Formula 5)

[Formula 2-4,
X ¹ is -SO _2- , -CO-, -CH _2- , -NH-, -O-, an alkenyl group having 2 to 36 carbon atoms, an alkylene group having 1 to 20 carbon atoms, an arylene group 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 a direct bond,
In Formulas 2 and 4,
Y ¹ is -NH-, -O-, or a direct bond, n is an integer from 0 to 10,
In Formula 2,
R ¹ and R ² are, each independently, a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, having a carbon number of 2 to 30 alkenyl group, or hydrogen atom, -NR ₄ R ₅ or -NR at the terminal of the ⁴ R ⁵ H ⁺ U ^- An alkanediyl group having 1 to 30 carbon atoms or a heterocycle which may further include a nitrogen, oxygen, or sulfur atom formed by uniting R ¹ and R ² ,
Art alkanediyl group is -CH ₂ included - may be replaced by a -O-, U ^- denotes an anion, a halogen _{^{ion, BF 4 -, PF 6 -}} , ClO 4 -, R 6 -CO 2 -, R ⁷ -SO ₃ ^- represents [R ⁶ , R ⁷ is a monovalent organic group containing an aromatic],
R ³ is a ring substituent when R ¹ and R ² are united, o is the number thereof, and when o is 2 or more, R ³ may have a different structure, and each independently a hydrogen atom or C 1-20 It is an alkyl group, a C2-C20 alkenyl group, or a C6-C20 arylene group,
In Formula 3,
G is -COO-, -SO _3- , -PO ₃ ^2- , -OPO ₃ ^2- , benzoic acid terminal (-Ph-COO-), salicylic acid terminal (-Ph (OH) -COO-), benzenesulfonic acid terminal ( -Ph-SO _3- ), and benzenephosphonic acid terminal (-Ph-PO ₃ ^2- ), M is a cation containing a hydrogen cation equivalent to G (Ph is a phenylene group),
In Formula 4,
R ⁸ is a hydrogen atom, a halogen atom, -NO ₂ , -NH ₂ or -SO ₃ H, P is an integer from 1 to 4,
In Formula 5,
R ⁹ is a functional group represented by Chemical Formulas 2 to 4,
Q ¹ is a hydrogen atom, a hydroxyl group, an alkoxyl group having 1 to 20 carbon atoms, or a functional group represented by Formulas 2 to 4,
X ² is -SO _2- , -CO-, -CH _2- , -NH-, -O-, an alkenyl group having 2 to 36 carbon atoms, an alkylene group having 1 to 20 carbon atoms, an arylene group 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 a direct bond,
Y ² is —NH—, —NR ¹¹ —Z—NR ¹² —, —SO ₂ —Z—NR ¹³ —, —N = N— or a direct bond, and R ¹¹ to R ¹³ are each independently a hydrogen atom; , An alkyl group having 1 to 36 carbon atoms, an alkenyl group having 2 to 36 carbon atoms, or a phenyl group,
Z is an alkylene group having 1 to 20 carbon atoms or an arylene group having 1 to 20 carbon atoms,
T are each independently a nitrogen atom or a carbon atom which may have a substituent.] The color filter according to claim 4, wherein the cation M of the formula (3) is any one of a hydrogen ion, an alkali metal ion, an alkaline earth metal ion, a rare earth metal ion, a transition metal ion, and a cation represented by the formula (8). Coloring composition.
(Formula 6)

[Formula 6,
R ¹⁴ to R ¹⁷ represent a hydrogen atom or an alkyl group having 1 to 30 carbon atoms (but not all of them become hydrogen atoms).] The fluorescent dye (A) is a salt salt compound of a fluorescent acid dye and / or a sulfonic acid amide compound of a fluorescent acid dye. Coloring composition for color filters. The weight ratio (B / A) of the organic compound (B) with respect to the fluorescent dye (A) is 0.05-2.0, The coloring composition for color filters in any one of Claims 1-6 characterized by the above-mentioned. . The coloring composition for color filters in any one of Claims 1-7 which further contains an organic pigment (D). On the board | substrate, the filter segment formed from the coloring composition for color filters in any one of Claims 1-8 was provided. The color filter characterized by the above-mentioned.