KR20130137028A - Colored composition for color filters, and color filters - Google Patents

Abstract

(R¹~R¹³은 각각 독립적으로, 수소 원자, 할로겐 원자, 알킬기, 알콕실기, 아릴기, 염기산 및 그 금속염, 알킬암모늄염, 프탈이미도메틸기, 또는 술파모일기이고, R¹~R⁴, R¹⁰~R¹³의 인접한 기는 일체가 되어 치환기를 가져도 좋은 방향환을 형성한다.)The coloring composition for color filters containing the coloring agent, binder resin, and solvent which are represented by General formula (1) is provided:

(R ¹ to R ¹³ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxyl group, an aryl group, a basic acid and a metal salt thereof, an alkylammonium salt, a phthalimidomethyl group, or a sulfamoyl group, and R ¹ to R ⁴ , Adjacent groups of R ¹⁰ to R ¹³ are integrated to form an aromatic ring which may have a substituent.)

Description

Color composition and color filter for color filters {COLORED COMPOSITION FOR COLOR FILTERS, AND COLOR FILTERS}

TECHNICAL FIELD The present invention relates to a color filter, a coloring composition, and a color filter formed by using the color filter used in the production of a color filter for use in a color liquid crystal display device, a color imaging tube element, and the like.

A liquid crystal display is a display device in which a liquid crystal layer sandwiched between two polarizers controls the degree of polarization of light passing through the first polarizer and controls the amount of light passing through the second polarizer. Types using TN) type liquid crystals have become mainstream. The liquid crystal display device is capable of color display by providing a color filter between two polarizing plates, and in recent years, it can be used in televisions and computer monitors, thereby increasing the demand for high contrast, high brightness, and high color reproducibility of the color filter. have.

The color filter is formed by arranging two or more kinds of fine stripe (stripe) shaped filter segments in parallel or alternately on the surface of a transparent substrate such as glass, or by arranging the fine filter segments in a horizontally constant array. have. In general, it is often formed by three color filter segments of red, green, and blue, and each segment is fine from several microns to several hundred microns, and is arranged in a predetermined arrangement for each color.

In general, in a color liquid crystal display, a transparent electrode for driving a liquid crystal is deposited on the color filter or formed by sputtering, and an alignment film for aligning the liquid crystal in a predetermined direction is formed thereon. In order to fully acquire the performance of these transparent electrodes and an oriented film, it is necessary to form in general at 200 degreeC or more, Preferably it is 230 degreeC or more. For this reason, it is required to use the coloring agent excellent in heat resistance and light resistance for manufacture of a color filter.

Yellow pigment is used as a coloring coloring agent for manufacture of a filter segment, and CI pigment yellow 138 is used in many cases, since a high transmittance can be obtained especially. However, although CI Pigment Yellow 138 is relatively excellent in brightness, it is desired to further improve the brightness. In addition, in recent years, high contrast for color filters is strongly required, but CI Pigment Yellow 138 has a problem of low contrast.

A quinophthalone compound is known as a pigment dispersant for stabilizing the dispersion of CI pigment yellow 138. For example, in the patent document 1, the quinophthalone compound which contains the sulfonic acid, and the patent document 2 the quinophthalone compound which added the phthalimidomethyl group are disclosed. By using these pigment dispersants, the dispersibility of CI Pigment Yellow 138 is improved, but it has not reached the extent to which the desired characteristics with respect to contrast ratio are obtained.

In patent document 3, the quinophthalone compound which made following compound (1) the starting material is disclosed as a pigment composition in which dispersion stability improved with time.

[Formula 1]

Patent Literature 4 discloses that a pigment composition having excellent coloring power, sharpness, and the like can be obtained by using a compound obtained by dimerizing a quinophthalone structure.

However, it is a present situation that the coloring agent containing these quinophthalone compounds does not fully improve the problem, such as contrast ratio and lack of coloring power, when used for a color filter use.

In patent document 5, the quinophthalone compound which has a naphthalene ring for coloring of a polymeric material is disclosed. However, all these quinophthalone compounds aim at coloring of plastics, and it is unclear about the suitability for a color filter use.

Moreover, it is known to use an aluminum phthalocyanine pigment as a coloring composition for green color filter segments (patent documents 6-12). When using an aluminum phthalocyanine pigment, it is necessary to use a yellow pigment together. However, since the conventional quinophthalone compound known as a yellow pigment | dye has the problem mentioned above, when using these together, the contrast ratio and coloring power of a color filter were not enough.

In addition, in order to realize high brightness and high contrast of a color filter, the refinement | miniaturization process of the pigment contained in a filter segment is performed. However, even when the pigment is simply miniaturized, the pigments in which the primary particles or the secondary particles have been miniaturized are generally agglomerated, and it is very difficult to obtain a stable coloring composition even when stabilizing. In addition, it is known that pigments subjected to micronization are stable in a pigment carrier, difficult to disperse at high concentrations, and cause various problems with respect to the manufacturing process and the product itself.

There, generally, a pigment dispersant is used in order to maintain a dispersed state favorably. A pigment dispersant has the structure of the site | part which adsorb | sucks to a pigment, the site | part which has a high affinity with the solvent which is a dispersion medium, and performance is determined by the balance of these two sites. Various pigment dispersants are used in accordance with the surface state of the pigment, which is the product to be dispersed, but a pigment having a basic functional group having electrostatic adsorption is generally used for a pigment having an acid-biased surface. In this case, a basic functional group becomes an adsorption site of a pigment. The example which used the basic pigment dispersing agent which has an amino group as a basic functional group for the coloring composition for color filters is described in patent documents 13-17 etc.

However, these have some dispersion ability, but were unable to disperse and stabilize the ultrafine pigments, which are required to be used to cope with high contrast, as the color composition for color filters.

There, the coloring composition for color filters excellent in dispersibility, fluidity | liquidity, and storage stability is proposed by using the pigment dispersant which makes the isocyanate group and the amine compound of the urethane prepolymer which has an isocyanate group at both ends (patent document 18).

However, even if the dispersing agent described in patent document 18 was used, the ability to disperse | distribute to a quinophthalone pigment was inadequate, and high contrast and dispersion stability were not compatible.

Moreover, a voltage retention is mentioned as an index which shows the display performance of a liquid crystal display device. The liquid crystal is a highly insulating material, and when the polar compound remaining in the color composition for color filters melts into the liquid crystal cell, the voltage between the electrodes decreases, causing a drop in voltage retention, display unevenness, and orientation defects. This causes a decrease in performance as a liquid crystal display device. Therefore, the insoluble property to a liquid crystal is calculated | required for the coloring composition for color filters.

In patent documents 19-21, the green coloring composition for color filters containing the phthalocyanine pigment | dye of a various structure and a quinophthalone pigment | dye is proposed. However, these green coloring compositions for color filters have problems of insufficient brightness and poor heat resistance and light resistance.

In patent document 22, the green coloring composition for color filters containing a zinc phthalocyanine type pigment and a quinophthalone type dye is proposed as a means of brightness improvement. However, zinc phthalocyanine-based pigments have high acidity and are easily extracted on the liquid crystal layer laminated on the color filter layer, resulting in a drop in voltage retention, display unevenness, and orientation defects. There was a problem of lowering.

Japanese Patent Application Laid-Open No. 2002-179979 Japanese Patent Laid-Open No. 2008-95007 JP 2008-81566 A Japanese Patent Laid-Open No. 2008-74985 Japanese Patent Application Laid-Open No. 51-147544 Japanese Patent Application Laid-Open No. 2002-131521 Japanese Patent Application Laid-Open No. 2002-250812 JP 2003-4930 A Japanese Patent Application Laid-Open No. 2004-333817 Japanese Patent Application Laid-Open No. 2000-301833 Japanese Patent Laid-Open No. 2010-79247 Japanese Patent Application Laid-Open No. 57-90058 Japanese Patent Application Laid-Open No. 09-176511 Japanese Patent Application Laid-Open No. 10-213898 Japanese Patent Application Laid-Open No. 2001-240780 Japanese Patent Application Laid-Open No. 2002-31713 Japanese Patent Application Laid-Open No. 2004-54213 Japanese Patent Laid-Open No. 2010-39433 Japanese Patent Laid-Open No. 6-220339 Japanese Patent Application Laid-Open No. 8-171201 Japanese Patent Laid-Open No. 2009-51896 Japanese Patent Laid-Open No. 2010-168531

Embodiment of this invention contains a coloring agent, binder resin, and a solvent, The said coloring agent contains the coloring agent represented by General formula (1), It is related with the coloring composition for color filters characterized by the above-mentioned.

(2)

In the above formula, in General Formula (1), R ¹ to R ¹³ each independently represent a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, an aryl group which may have a substituent, -SO ₃ H; -COOH; and the monovalent to trivalent metal salt of these acidic groups; The alkylammonium group, the phthalimidomethyl group which may have a substituent, or the sulfamoyl group which may have a substituent is shown. Adjacent groups of R ¹ to R ⁴ and / or R ¹⁰ to R ¹³ are integrated to form an aromatic ring which may have a substituent. That is, at least one adjacent pair of groups among R ¹ to R ⁴ and / or at least one adjacent pair of groups among R ¹⁰ to R ¹³ may be integrated to form an aromatic ring which may have a substituent.

It is preferable that the coloring agent shown by General formula (1) is a coloring agent chosen from general formula (1A)-(1C).

(3)

In the formulas, in the general formulas (1A) to (1C), each of R ¹⁴ to R ²⁸ , R ²⁹ to R ⁴³ , and R ⁴⁴ to R ⁶⁰ is each independently: a hydrogen atom; A halogen atom; Alkyl group which may have a substituent; An alkoxyl group which may have a substituent; An aryl group which may have a substituent; -SO ₃ H, -COOH, and monovalent to trivalent metal salts of these acid groups; alkylammonium salts; Phthalimidomethyl group which may have a substituent; Or the sulfamoyl group which may have a substituent is shown.

The said coloring agent may further contain the coloring agent chosen from general formula (8A) and (8B).

[Formula 4]

In the above formula, in General Formula (8A), X ₁ to X ₄ are each independently an alkyl group which may have a substituent, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, or a heterocyclic group which may have a substituent , An alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, or the arylthio group which may have a substituent is shown. Y ₁ to Y ₄ each independently represent a halogen atom, a nitro group, a phthalimidomethyl group which may have a substituent, or a sulfamoyl group which may have a substituent. Z represents a hydroxyl group, a chlorine atom, -OP (= O) R ₁ R ₂ , or -O-SiR ₃ R ₄ R ₅ . R ₁ to R ₅ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxyl group which may have a substituent, or an aryloxy group which may have a substituent, and R You may combine with each other and form a ring. m ₁ to m ₄ and n ₁ to n ₄ each independently represent an integer of 0 to 4, and m ₁ + n ₁ , m ₂ + n ₂ , m ₃ + n ₃ , and m ₄ + n ₄ are 0 to 4, respectively, and are the same. You may or may not.

[Chemical Formula 5]

In formula (8B), X ₅ to X ₁₂ are each independently an alkyl group which may have a substituent, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, or a heterocyclic group which may have a substituent. , An alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, or the arylthio group which may have a substituent is shown. Y ₅ to Y ₁₂ each independently represent a halogen atom, a nitro group, a phthalimidomethyl group which may have a substituent, or a sulfamoyl group which may have a substituent. L represents -O-SiR ₆ R ₇ -O-, -O-SiR ₆ R ₇ -O-SiR ₈ R ₉ -O-, or -O-P (= O) R ₁₀ -O-, and R ₆ R <_10> respectively independently represents a hydrogen atom, a hydroxyl group, the alkyl group which may have a substituent, the aryl group which may have a substituent, the alkoxyl group which may have a substituent, or the aryloxy group which may have a substituent. m ₅ to m ₁₂ and n ₅ to n ₁₂ each independently represent an integer of 0 to 4, and m ₅ + n ₅ , m ₆ + n ₆ , m ₇ + n ₇ , m ₈ + n ₈ , m ₉ + n ₉ , and m _{10 + n 10, m 11 + n} 11, m 12 + n 12 may be the same or different may respectively 0-4.

The colorant may further contain a dispersant. The dispersant isocyanate group of the urethane prepolymer (E) having an isocyanate group at both ends formed by reacting the hydroxyl group of the vinyl polymer (A) having two hydroxyl groups in one end region with the isocyanate group of the diisocyanate (B), An ethylenically unsaturated monomer having a pigment dispersant obtained by reacting primary and / or secondary amino groups of an amine compound containing at least a polyamine (C), wherein the vinyl polymer (A) has at least one of an ethylene oxide chain or a propylene oxide chain ( a1) may be included in the copolymerization composition.

The said coloring agent may also contain the coloring agent shown by General formula (6).

[Chemical Formula 6]

In formula (6), R ₁ to R ₆ each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, or- O-R ₇ is shown. R ₇ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group. However, all of R ₁ to R ₆ do not become hydrogen atoms.

Moreover, embodiment of this invention contains a coloring agent, binder resin, and a solvent, The said coloring agent contains the coloring agent shown by General formula (6), It is related with the coloring composition for color filters characterized by the above-mentioned. The said coloring agent may further contain the coloring agent chosen from general formula (8A) and (8B). The said coloring agent may further contain the coloring agent represented by General formula (7).

[Formula 7]

In formula (7), R ₁ to R ₆ each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, or- O-R ₁₁ is shown. R ₁₁ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group. R ₇ to R ₁₀ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a carboxyl group, a substituted or unsubstituted sulfoamide group , A substituted or unsubstituted heterocyclic moiety, -S-R ₁₂ , -O-R ₁₂ , or -COO-R ₁₂ is represented. R ₁₂ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group.

Moreover, embodiment of this invention contains a coloring agent, binder resin, and a solvent, The said coloring agent contains the coloring agent represented by General formula (7A), It is related with the coloring composition for color filters characterized by the above-mentioned.

The colorant represented by General Formula (7A) may be a colorant represented by General Formula (7B).

[Formula 8]

In General Formula (7A), R ₁ to R ₆ each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, or- O-R ₁₁ is shown. R ₁₁ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group. R ₇ to R ₁₀ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a carboxyl group, a substituted or unsubstituted sulfoamide group , A substituted or unsubstituted heterocyclic moiety, -S-R ₁₂ , or -O-R ₁₂ , or -COO-R ₁₂ is represented. R ₁₂ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group. However, at least 1 of R <_7> -R <_10> is -O-R <_12> .

Here, in general formula (7B), R <_13> is a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. R ₁₄ to R ₁₇ each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or -O-R ₁₈ , or -COO-R ₁₂ . R ₁₈ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group. Provided that at least one of R ₁₄ to R ₁₇ is -O-R ₁₈ .

In addition, the colorant may contain a yellow colorant. The yellow colorant is preferably selected from the group consisting of CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, and CI Pigment Yellow 185. Furthermore, the said coloring agent may contain the coloring agent chosen from the group which consists of a green coloring agent, a blue coloring agent, and a red coloring agent. Moreover, the coloring composition for color filters may contain a photopolymerizable monomer and / or a photoinitiator.

Furthermore, embodiment of this invention relates to the color filter provided with the filter segment formed using the said coloring composition for color filters.

Moreover, this invention relates to the following Embodiments I-VIII.

<Embodiment I>

The subject of this embodiment is providing the coloring agent for coloring filters, coloring composition, and the color filter using the same which have the outstanding coloring power and can obtain high brightness and a high contrast ratio when used for a color filter.

The present inventors found that when used as a color filter coloring agent containing a quinophthalone compound having a certain structure, it is possible to produce a color filter having excellent dispersibility and coloring power and providing high brightness and contrast ratio. The present embodiment has been reached.

That is, this embodiment is related with the coloring agent for color filters containing the quinophthalone compound represented by General formula (1). It is preferable that the quinophthalone compound represented by General formula (1) is one of General formula (1A)-(1C). In General Formulas (1A) to (1C), R ¹⁴ to R ²⁸ , R ²⁹ to R ⁴³ , and R ⁴⁴ to R ⁶⁰ may each independently be a hydrogen atom or a halogen atom. In addition, the colorant preferably contains a yellow colorant. Furthermore, it is preferable that the yellow colorant is at least one kind selected from at least CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, and CI Pigment Yellow 185. Moreover, it is good also as a coloring composition for color filters which consists of at least the said coloring agent, binder resin, and the organic solvent. In addition, the coloring composition for color filters may contain the green coloring agent and / or the blue coloring agent. In addition, the coloring composition for color filters may contain the photopolymerizable monomer and / or the photoinitiator. Furthermore, in the color filter provided with at least 1 red filter segment, at least 1 green filter segment, and at least 1 blue filter segment, at least 1 green filter segment is a color filter formed with the said coloring composition for color filters. good.

According to this embodiment, by using the quinophthalone compound represented by the said General formula (1) as a color filter colorant, it is high brightness, high contrast ratio, the coloring agent for color filters, coloring composition excellent in coloring power, and using the same Color filters can be provided.

<Embodiment II>

The subject of this embodiment is providing the coloring composition for color filters which can obtain high brightness and a high contrast ratio, and when using for a color filter, while having outstanding coloring power and dispersibility, and the color filter using the same.

MEANS TO SOLVE THE PROBLEM The present inventors can produce the color filter which is excellent in dispersibility and coloring power, and provides high brightness and contrast ratio, when the pigment containing the quinophthalone compound which has a specific structure, and an aluminum phthalocyanine pigment are used as a color filter colorant. It was found that the present invention and the present embodiment.

That is, this embodiment is a coloring composition for color filters containing a coloring agent, binder resin, and the organic solvent, The quinophthalone compound which the said coloring agent shows in General formula (1A), General formula (1B), and General formula (1C). It is related with the coloring composition for color filters containing at least 1 sort (s) of pigment chosen from and aluminum phthalocyanine pigment. Moreover, it is preferable that aluminum phthalocyanine pigment is either General formula (8A) or General formula (8B). Moreover, it is preferable that the coloring composition for color filters contains a photopolymerizable monomer and / or a photoinitiator. Moreover, the color filter provided with the filter segment formed from the said coloring composition for color filters on a board | substrate may be sufficient.

According to this embodiment, when using together at least 1 sort (s) of pigment chosen from the quinophthalone compound represented by General formula (1A), General formula (1B), and General formula (1C), and an aluminum phthalocyanine pigment, At the same time, it is possible to provide a color filter coloring composition having a high contrast ratio, excellent coloring power and low viscosity, and a color filter using the same.

<Embodiment III>

An object of this embodiment is to provide the coloring composition for color filters excellent in dispersibility, fluidity | liquidity, and storage stability, and the color filter using the same.

In this embodiment, the pigment dispersant which consists of a vinyl polymer containing the ethylenically unsaturated monomer (a1) which has at least one of an ethylene oxide chain or a propylene oxide chain with respect to a quinophthalone pigment is used.

That is, this embodiment is a coloring composition for color filters containing a coloring agent, a pigment dispersing agent, and an organic solvent, The said coloring agent is a quinophthalone pigment, The said pigment dispersing agent has a vinyl which has two hydroxyl groups in one terminal area | region. Primary and the isocyanate groups of the urethane prepolymer (E) having an isocyanate group at both ends, which are reacted with the hydroxyl group of the polymer (A) and the isocyanate group of the diisocyanate (B), and at least the primary amine compound containing a polyamine (C) and And / or a pigment dispersant formed by reacting a secondary amino group, wherein the vinyl polymer (A) comprises an ethylenically unsaturated monomer (a1) having at least one of an ethylene oxide chain or a propylene oxide chain in the copolymerization composition. It relates to the coloring composition for.

It is preferable that the sum total of the repeating unit number of the ethylene oxide chain | strand and the propylene oxide chain | strand of an ethylenically unsaturated monomer (a1) is 1-50. Moreover, it is preferable that content of an ethylenically unsaturated monomer (a1) exists in the range of 10 to 90 weight% in 100 weight% of a total of the copolymerization composition of a vinyl polymer (A). Moreover, it is preferable that the weight average molecular weights of the vinyl polymer (A) which has two hydroxyl groups in one end area | region are 500-20,000. It is preferable that a quinophthalone pigment contains the quinophthalone compound represented by CI pigment yellow 138 and / or General formula (1). Moreover, it is preferable that a quinophthalone compound is represented by either of General formula (1A)-(1C). Moreover, you may contain the photopolymerizable monomer and a photoinitiator. Moreover, the color filter provided with the filter segment formed from the said coloring composition for color filters on a board | substrate may be sufficient.

According to this embodiment, a high contrast contrast and dispersion stability are used by using together the pigment dispersing agent which consists of a quinophthalone pigment and the vinyl polymer which contains the ethylenically unsaturated monomer which has at least one of an ethylene oxide chain or a propylene oxide chain in a copolymerization composition. It can provide the coloring composition for color filters which made this compatible, and the color filter with high contrast ratio using the same.

<Embodiment IV>

The problem which this embodiment tries to solve is providing the coloring composition for color filters which is excellent in brightness, contrast ratio, and coloring power, and has other characteristics (heat resistance, light resistance, and sensitivity) when used for a color filter, and the color filter using the same. It is in doing it.

MEANS TO SOLVE THE PROBLEM The present inventors discovered that the coloring composition for color filters can solve the said subject because a coloring agent contains the quinophthalone pigment [A] of a specific structure and the quinophthalone dye [B] of a specific structure, and this embodiment. Reached.

That is, this embodiment is a coloring composition for color filters containing a coloring agent, binder resin, and an organic solvent, The said coloring agent is 1 or more types chosen from general formula (1A), general formula (1B), and general formula (1C). It relates to the coloring composition for color filters containing a quinophthalone pigment [A] and the quinophthalone dye [B] shown by General formula (6). It is preferable that R <^14> -R <^28> , R <^29> -R <^43> and R <^44> -R <^{60> in} General formula (1A)-(1C) are respectively independently a hydrogen atom or a halogen atom. Moreover, it is preferable that at least 1 of R <^1> -R <^6> in General formula (6) is -OR <^7> . Moreover, you may contain the photopolymerizable monomer and / or the photoinitiator. Furthermore, the color filter provided with the filter segment formed from the coloring composition for color filters on a board | substrate may be sufficient.

By using the coloring composition for color filters of this embodiment, the color filter which is excellent in brightness, contrast ratio, and coloring power, and which is excellent in heat resistance and light resistance can be provided.

<Embodiment V>

The objective of this embodiment is the color filter which was excellent in the color characteristic (brightness), satisfy | filled other physical properties (heat resistance, light resistance, solvent resistance), the coloring composition which mix | blended it, and the color filter excellent in the color characteristic (brightness) using the same. To provide.

MEANS TO SOLVE THE PROBLEM This inventor discovers the quinophthalone pigment | dye excellent in the color characteristic (brightness), and forms this embodiment based on this knowledge.

That is, this embodiment relates to the quinophthalone pigment | dye characterized by being represented by General formula (6). Moreover, in the coloring composition for color filters which consists of a coloring agent and binder resin at least, the coloring agent may be the coloring composition for color filters containing the said quinophthalone pigment | dye. Moreover, the coloring agent may contain the pigment. Moreover, in the color filter which has at least a red filter segment, a green filter segment, and a blue filter segment, the color filter in which at least 1 filter segment is formed of the said coloring composition for color filters may be sufficient.

In this embodiment, the quinophthalone pigment | dye which was excellent in the color characteristic (brightness) and also satisfied other physical properties (heat resistance, light resistance, solvent resistance) can be obtained. Moreover, it becomes possible to form a color filter excellent in color characteristics (brightness) by creating a color filter with the coloring composition for color filters which mix | blended this quinophthalone pigment | dye. Moreover, other physical properties (heat resistance, light resistance, solvent resistance) of the formed color filter are also favorable.

<Embodiment VI>

An object of the present embodiment is to provide a green coloring composition for color filters that is excellent in brightness and excellent in heat resistance, light resistance and voltage retention, and a color filter using the same.

MEANS TO SOLVE THE PROBLEM The present inventors discovered that the green coloring composition for color filters containing the phthalocyanine pigment | dye of a specific structure and the quinophthalone pigment | dye of a specific structure can solve the said subject, and came to this embodiment.

That is, this embodiment is a green coloring composition for color filters containing a coloring agent, binder resin, and an organic solvent, The coloring agent shows the phthalocyanine pigment | dye represented by following General formula (8C), and the quinophthalone pigment | dye represented by General formula (6). It is related with the green coloring composition for color filters containing it.

[Chemical Formula 9]

[In General Formula (8C), A <^1> -A <^16> respectively independently represents a hydrogen atom, a halogen atom, a nitro group, the alkyl group which may have a substituent, or the aryl group which may have a substituent. R ¹ and R ² each independently represent a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, or —OR ³ , and R ¹ and R ² may be bonded to each other to form a ring; good. R ³ is an alkyl group which may have a substituent or an aryl group which may have a substituent.]

Moreover, it is preferable that at least 1 of R <^1> and R <^2> in General formula (8C) is an aryl group which may have a substituent, or -OR <^3> . In addition, the green coloring composition for color filters may contain the photopolymerizable monomer and / or the photoinitiator. Moreover, the color filter provided with the filter segment formed from the said green coloring composition for color filters on a board | substrate may be sufficient. In addition, although the expression method of general formula (8A) and a substituent differs in general formula (8C), it is the same structure.

By using the green coloring composition for color filters of this embodiment, the color filter which is excellent in brightness and excellent in heat resistance, light resistance, and voltage retention can be provided.

<Embodiment VII>

The problem which this embodiment is going to solve is to provide the coloring composition for color filters excellent in contrast ratio and coloring power, and the color filter using the same.

MEANS TO SOLVE THE PROBLEM The present inventors discovered that the coloring composition for color filters can solve the said subject by containing the quinophthalone pigment | dye [A1] of a specific structure and the quinophthalone pigment | dye [A2] of a specific structure, and this embodiment Reached.

That is, in this embodiment, in the coloring composition for color filters containing a coloring agent, binder resin, and the organic solvent, a coloring agent is represented by the quinophthalone pigment | dye [A1] which is represented by General formula (6), and following General formula (7). It relates to the coloring composition for color filters containing a quinophthalone pigment | dye [A2].

[Formula 10]

In formula (7), R ₁ to R ₆ each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, or It represents an -O-R _11. R ₁₁ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group. R ₇ to R ₁₀ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a carboxyl group, a substituted or unsubstituted sulfoamide Group, a substituted or unsubstituted heterocyclic moiety, -S-R ₁₂ , -O-R ₁₂ , or -COO-R ₁₂ are represented. R ₁₂ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group.

By using the coloring composition for color filters of this embodiment, the color filter excellent in contrast ratio and coloring power can be provided.

<Embodiment VIII>

The objective of this embodiment is to provide the pigment | dye which is excellent in color characteristic (brightness), the coloring composition formed by mix | blending it, and the color filter which is excellent in color characteristic (brightness) using it.

MEANS TO SOLVE THE PROBLEM This inventor discovers the quinophthalone pigment | dye excellent in the color characteristic (brightness), and forms this embodiment based on this knowledge.

That is, this embodiment is represented by the following general formula (7A), and relates to the quinophthalone pigment | dye for color filters.

[Formula 11]

In formula (7A), R ₁ to R ₆ each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, or- O-R ₁₁ is shown. R ₁₁ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group. R ₇ to R ₁₀ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a carboxyl group, a substituted or unsubstituted sulfoamide Group, a substituted or unsubstituted heterocyclic moiety, -S-R ₁₂ , -O-R ₁₂ , or -COO-R ₁₂ are represented. R ₁₂ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group. However, at least 1 of R <_7> -R <_10> is -O-R <_12> .

In addition, it is preferable that a quinophthalone pigment | dye is represented by following General formula (7B).

[Chemical Formula 12]

Here, in general formula (7B), R <_13> is a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. R ₁₄ to R ₁₇ each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or —O-R ₁₈ . R ₁₈ is a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Provided that at least one of R ₁₄ to R ₁₇ is -O-R ₁₈ .

Moreover, in the coloring composition for color filters which consists of a coloring agent and binder resin, it is preferable that the said coloring agent contains the said quinophthalone pigment | dye. Moreover, the coloring agent may contain the pigment. Furthermore, in the color filter which has at least a red filter segment, a green filter segment, and a blue filter segment, the color filter in which at least 1 filter segment is formed by the said coloring composition for color filters may be sufficient.

In this embodiment, the quinophthalone pigment | dye for color filters which is excellent in color characteristic (brightness) can be obtained. Moreover, it becomes possible to form the color filter excellent in color characteristics (brightness) by creating a color filter with the coloring composition for color filters which mix | blended this quinophthalone pigment | dye. Moreover, other physical properties (heat resistance, light resistance, solvent resistance) of the formed color filter are also favorable.

The subject of this invention is 2011-60734 for which it applied on March 18, 2011, Special application 2011-093515 for which it applied for April 19, 2011, Special application 2011-93705 for which it applied for April 20, 2011, May 27, 2011. Filed Application 2011-118726, filed June 29, 2011 Filed Application 2011-143658, filed July 7, 2011 Filed Application 2011-150514, filed July 15, 20112011-156970, August 2011 It is based on description of Japanese Patent Application No. 2011-174656 for which it applied on August 10, 2011-181111 for which it applied for August 23, 2011, and Japanese Patent Application No. 2011-286172 for which it applied for December 27, 2011. It shall be included in.

1 is a spectrum of a coating film in Example 5 of Embodiment V. FIG.
2 is a spectrum of the coating film in Reference Example 1 of Embodiment V. FIG.
3 is a spectrum of the coating film of Reference Example 3 of Embodiment V. FIG.
4 is a spectrum of the coating film in Example 1 of Embodiment VIII.
5 is a spectrum of the coating film in Reference Example 1 of Embodiment VIII.
6 is a spectrum of the coating film of Reference Example 4 of Embodiment VIII.

<Colorant>

In embodiment of this invention, the coloring composition for color filters is the quinophthalone compound represented by General formula (1), the quinophthalone pigment | dye represented by General formula (6), and the quinophthalone represented by General formula (7). It contains a coloring agent chosen from a pigment individually or in combination. In addition, the coloring composition for color filters may contain the phthalocyanine pigment represented by General formula (8A) or (8B), and may contain the other coloring agent. Each coloring agent is demonstrated below.

(Kinophthalone Compound Represented by General Formula (1))

Hereinafter, it is also called the quinophthalone pigment represented by General formula (1).

R ¹ to R ¹³ , R ¹⁴ to R ²⁸ , R ²⁹ to R ⁴³ , and R ⁴⁴ to R ⁶⁰ of General Formulas (1) and (1A) to (1C) are fluorine, chlorine, bromine, and iodine as halogen atoms. Can be mentioned.

Moreover, as an alkyl group which may have a substituent, a methyl group, an ethyl group, a propyl group, isopropyl group, a butyl group, isobutyl group, tert- butyl group, neopentyl group, n-hexyl group, n-octyl group, stearyl group Trichloromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, 2,2-dibromoethyl group, in addition to linear or branched alkyl groups such as 2-ethylhexyl group, 2,2,3,3-tetrafluoropropyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2-nitropropyl group, benzyl group, 4-methylbenzyl group, 4-tert- butylbenzyl group, 4 And alkyl groups having substituents such as -methoxybenzyl group, 4-nitrobenzyl group and 2,4-dichlorobenzyl group.

Moreover, as an alkoxyl group which may have a substituent, a methoxy group, an ethoxy group, a propoxy group, isopropoxy group, n-butoxy group, isobutyloxy group, tert- butyloxy group, neopentyl oxy group, 2,3 In addition to the linear or branched alkoxyl groups, such as a -dimethyl- 3-pentoxy, n-hexyloxy group, n-octyloxy group, a stearyloxy group, and 2-ethylhexyloxy group, a trichloromethoxy group and a trifluoromethoxy group , 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropyloxy group, 2,2-ditrifluoromethylpropoxy group, 2-ethoxyethoxy group, The alkoxyl group which has substituents, such as a 2-butoxyethoxy group, 2-nitropropoxy group, a benzyloxy group, is mentioned.

Moreover, as an aryl group which may have a substituent, in addition to aryl groups, such as a phenyl group, a naphthyl group, and anthranyl group, p-methylphenyl group, p-bromophenyl group, p-nitrophenyl group, p-methoxyphenyl group, 2,4- Dichlorophenyl group, pentafluorophenyl group, 2-aminophenyl group, 2-methyl-4-chlorophenyl group, 4-hydroxy-1-naphthyl group, 6-methyl-2-naphthyl group, 4,5,8-trichloro- The aryl group which has substituents, such as a 2-naphthyl group, an anthraquinonyl group, and a 2-amino anthraquinonyl group, is mentioned.

Examples of the acidic group include -SO ₃ H and -COOH, and examples of the monovalent to trivalent metal salts of these acidic groups include sodium salts, potassium salts, magnesium salts, calcium salts, iron salts and aluminum salts. have. As the alkylammonium salt of the acidic group, quaternary alkylammonium salts such as ammonium salts of long-chain monoalkylamines such as octylamine, laurylamine and stearylamine, palmityl trimethylammonium, dilauryldimethylammonium and distearyldimethylammonium salts Can be mentioned.

Import good phthalimide yimido group a substituent _{(C 6 H 4 (CO)} 2 N-CH 2 -) , and a substituent is also good sulfamoyl (H ₂ NSO ₂ -) as the "substituents" in the halogen atom And an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, an aryl group which may have a substituent, etc. are mentioned.

At least one adjacent pair of groups of R ¹ to R ⁴ of General Formula (1), and / or at least one adjacent pair of groups of R ¹⁰ to R ¹³ may be integrated to form an aromatic ring which may have a substituent. Form. Examples of the aromatic ring include a hydrocarbon aromatic ring and a heteroaromatic ring, and examples of the hydrocarbon aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and the like. Ring, pyrrole ring, quinoline ring, quinoxaline ring, furan ring, benzofuran ring, thiophene ring, benzothiophene ring, oxazole ring, thiazole ring, imidazole ring, pyrazole ring, indole ring, carbazole ring and the like Can be.

It is preferable that the quinophthalone compound used for the coloring agent for color filters is either of General formula (1A)-(1C). Here, in R ¹⁴ to R ²⁸ , R ²⁹ to R ⁴³ , and R ⁴⁴ to R ⁶⁰ , a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, or a substituent may be used. Aryl group, -SO ₃ H; -COOH; And monovalent to trivalent metal salts of these acid groups; alkylammonium salts, phthalimidomethyl groups which may have a substituent, or sulfamoyl groups which may have a substituent are the same as those described in the general formula (1).

Moreover, as for the quinophthalone compound used for the coloring agent for color filters, R <^14> -R <^28> , R <^29> -R <^43> , R <^44> -R <^60> of general formula (1A)-(1C) is a hydrogen atom or a halogen atom It is more preferable from the viewpoint of the low viscosity of a dispersion.

Although the quinophthalone compound (a)-(r) etc. which are shown below as a specific example of the quinophthalone compound used for the coloring agent for color filters are mentioned, It is not limited to these.

[Chemical Formula 13]

(Manufacturing method of a quinophthalone compound represented by General formula (1))

A quinophthalone compound can be manufactured, for example by the method of patent publication 2930774. Hereinafter, the general manufacturing method of the quinophthalone compound represented by General formula (1) is said. To 1 equivalent of 8-aminoquinaldine represented by the following General Formula (2), 2-3 equivalents of phthalic anhydride represented by the following General Formula (3) are heated to 160 to 200 ° C in a benzoic acid under a nitrogen atmosphere for condensation reaction. . When reacting, condensation of phthalic anhydride can be advanced in a two-step process by maintaining it at 140-160 degreeC for 1 to 3 hours before reaching 160-200 degreeC.

[Formula 14]

[In formula, R <^61> -R <^65> is the same as R <^5> -R <^9> in General formula (1).]

[Formula 15]

Wherein in, the same as R ⁶⁶ ~ R ^{69 is, R 1 ~ R 4, R} 10 ~ R 13 in the formula (1).]

When reacting, 1-2 equivalents of phthalic anhydride represented by General formula (3) is added with respect to 1 equivalent of 8-amino quinaldine represented by General formula (2), and it heat-stirred at 140-160 degreeC for 1-3 hours, 1 to 2 equivalents of phthalic anhydride represented by the general formula (3) having a different structure, heated at 160 to 200 ° C, and condensation reaction to form phthalic anhydride having a different structure from the amino group side and the methyl group side of 8-aminoquinaldine. Can be condensed.

Moreover, two or more types of structurally different quinophthalone compounds can be synthesize | combined simultaneously by making two or more types of structurally different phthalic anhydrides react simultaneously with 8-aminoquinaldine (henceforth a "combination method"). . For example, CI pigment yellow 138 and a specific quinophthalone compound can be produced simultaneously by condensing 1.8 equivalents of tetrachlorophthalic anhydride and 1.2 equivalents of other phthalic anhydride with respect to 1 equivalent of 8-aminoquinaldine. have.

Moreover, according to the synthesis method of patent document 3, the compound of General formula (5) can be synthesize | combined from the quinophthalone compound represented by compound (1). Moreover, it is also possible to synthesize | combine the quinophthalone compound represented by General formula (1) by condensing the phthalic anhydride represented by General formula (5) and General formula (3) at 160-200 degreeC in benzoic acid. The manufacturing method of a quinophthalone compound is not limited to these methods.

[Chemical Formula 16]

[In formula, R <^70> -R <^78> is the same as R <^5> -R <^13> in General formula (1).

The coloring agent of this embodiment may contain two or more types of quinophthalone compounds. At this time, the separately prepared quinophthalone compounds may be mixed, and at the same time, two or more types of quinophthalone compounds may be manufactured according to a synthesizing method, and may be used for a coloring agent.

In the case of using these separately prepared quinophthalone compounds, two types of pigments may be simply mixed before dispersing, or may be pulverized and mixed by the salt milling treatment described later.

When CI pigment yellow 138 is contained especially as a coloring agent, it is preferable to use it, grind | mixing and mixing by a synthesizing method or a salt milling process. By pulverizing and mixing CI Pigment Yellow 138 having a quinophthalone skeleton and the quinophthalone compound represented by the general formula (1) together, fine particles can be obtained compared to when the salt milling process is performed alone, resulting in a high contrast ratio. .

The coloring composition containing the quinophthalone compound represented by General formula (1) shows the color itself yellow, and uses the other color agent in combination, and uses the yellow filter segment of the same color, and also the green filter segment and the red filter. It can be set as the coloring composition for forming a segment. Especially, the coloring composition of this embodiment can obtain the coloring composition used for the green filter segment which has high brightness and high contrast contrast by using together a green coloring agent and / or a blue coloring agent.

(Kinophthalone pigment | dye represented by General formula (6))

The quinophthalone dye represented by General formula (6) is also called "kinophthalone dye" represented by General formula (6) in this specification.

As a substituted or unsubstituted alkyl group in R <_1> -R <_7> in general formula (6), a C1-C30 linear, branched, monocyclic or condensed polycyclic alkyl group, Or a linear, branched, monocyclic or condensed polycyclic alkyl group having 2 to 30 carbon atoms and containing one or more ester bonds (-COO-) and / or ether bonds (-O-). Specific examples of the linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 30 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, Dodecyl group, octadecyl group, trifluoromethyl group, isopropyl group, isobutyl group, isopentyl group, 2-ethylhexyl group, sec-butyl group, tert-butyl group, sec-pentyl group, tert-pentyl group, tert-octyl group, neopentyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, 4-decylcyclohexyl group, etc. are mentioned, It is not limited to.

As a specific example of a linear, branched alkyl group having 2 to 30 carbon atoms and containing one or more ester bonds, -CH ₂ -CH ₂ -CH ₂ -COO-CH ₂ -CH ₃ , -CH ₂ -CH (-CH ₃ ) -CH ₂ -COO-CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OCO-CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -CH ₂ -COO-CH _2- CH (CH ₂ -CH ₃ ) -CH ₂ -CH ₂ -CH ₂ -CH ₃ ,-(CH ₂ ) ₅ -COO- (CH ₂ ) ₁₁ -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -CH _{- (COO-CH 2 -CH 3} ) there can be _2, and so on, but is not limited to these.

In addition, the carbon number of from 2 30, and specific examples of straight-chain, branched-chain alkyl group containing at least one ether _{bond, -CH 2 -O-CH 3,} -CH 2 -CH 2 -O-CH 2 -CH 3, - CH ₂ -CH ₂ -CH ₂ -O-CH ₂ -CH ₃ ,-(CH ₂ -CH ₂ -O) _n -CH ₃ (where n is 1 to 8),-(CH ₂ -CH _2- CH ₂ -O) _m -CH ₃ (where m is from 1 to 5), -CH ₂ -CH (CH ₃ ) -O-CH ₂ -CH _3- , -CH ₂ -CH- (OCH ₃ ) ₂ Although these etc. are mentioned, it is not limited to these.

Specific examples of the monocyclic or condensed polycyclic alkyl group having 2 to 30 carbon atoms and optionally containing one or more ether bonds include, but are not limited thereto.

[Chemical Formula 17]

In addition, as a specific example of a linear, branched, alkyl group having 3 to 30 carbon atoms and containing at least one ester bond (-COO-) and an ether bond (-O-), -CH ₂ -CH ₂ -COO-CH ₂ -CH ₂ -O-CH ₂ -CH (CH ₂ -CH ₃ ) -CH ₂ -CH ₂ -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -COO-CH ₂ -CH ₂ -O-CH _{2 -CH 2 -O-CH 2 -CH (} CH 2 -CH 3) -CH there can be a ₂ -CH ₂ -CH ₂ -CH _3, not limited to these.

As a substituted or unsubstituted alkenyl group in R <_1> -R <_7> , a C1-C18 linear, branched, monocyclic or condensed polycyclic alkenyl group is mentioned. They may have a plurality of carbon-carbon double bonds in the structure. As a specific example, a vinyl group, 1-propenyl group, an allyl group, 2-butenyl group, 3-butenyl group, isopropenyl group, isobutenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, and 4-pentene Neyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, cyclopentenyl group, cyclohexenyl group, 1, 3- butadienyl group, cyclo Although a hexadienyl group, a cyclopentadienyl group, etc. are mentioned, It is not limited to these.

The substituted or unsubstituted aryl group in R ₁ to R ₇ is a substituted or unsubstituted monocyclic or condensed polycyclic aromatic group having 6 to 18 carbon atoms, for example, a phenyl group or a 1-naphthyl group , 2-naphthyl group, p-biphenyl group, m-biphenyl group, 2-anthryl group, 9-anthryl group, 2-phenanthryl group, 3-phenanthryl group, 9-phenanthryl group, 2-fluore Neyl group, 3-fluorenyl group, 9-fluorenyl group, 1-pyrenyl group, 2-pyrenyl group, 3-perylenyl group, o-tril group, m-tril group, p-tril group, 4-methyl ratio Phenyl group, taphenyl group, 4-methyl-1- naphthyl group, 4-tert- butyl- naphthyl group, 4-naphthyl-1- naphthyl group, 6-phenyl-2- naphthyl group, 10-phenyl-9- Anthryl group, a spirofluorenyl group, 4-maleimyl phenyl group, 2-benzocyclo butenyl group, etc. are mentioned.

It is preferable from the viewpoint of lightness, heat resistance, and light resistance that at least one of R ₁ to R ₆ in General Formula (6) is —OR ₇ .

The quinophthalone pigment | dye represented by General formula (6) can be obtained by making corresponding 2-methylquinoline and naphthalenedicarboxylic anhydride react at high temperature in benzoic acid like the following reaction formula.

[Chemical Formula 18]

In addition, the quinophthalone pigment | dye of General formula (6) exists tautomers of structures, such as the following general formula (6a) and (6b), However, such a tautomer is also within the scope of the present invention.

[Chemical Formula 19]

Although the following pigment | dyes are mentioned as a specific example of the quinophthalone pigment | dye represented by General formula (6), The pigment | dye of this invention is not limited to these.

[Chemical Formula 20]

The quinophthalone pigment | dye represented by General formula (6) can be used for coloring of printing ink, IJ ink, plastics, paint, fiber, stationery, writing implements, cosmetics, etc. as a coloring material.

(Kinophthalone pigment | dye represented by General formula (7))

Although the halogen atom in R <_1> -R <_10> in general formula (7) and general formula (7A), a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, It is not limited to these.

As a substituted or unsubstituted alkyl group in R <_1> -R <_12> , it is a C1-C30 linear, branched, monocyclic or condensed polycyclic alkyl group, or C2-C30, Ester bond (-COO-), Linear, branched, monocyclic or condensed polycyclic alkyl groups containing at least one bond selected from ether bonds (-O-) and sulfide bonds (-S-). Specific examples of the linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 30 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, Dodecyl group, octadecyl group, trifluoromethyl group, isopropyl group, isobutyl group, isopentyl group, 2-ethylhexyl group, 2-hexyl dodecyl group, sec-butyl group, tert-butyl group, sec-pentyl group , tert-pentyl group, tert-octyl group, neopentyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, 4-decylcyclohexyl group, etc. Although it is mentioned, it is not limited to these.

Specific examples of the linear and branched chain having 2 to 30 carbon atoms include -CH ₂ -CH ₂ -CH ₂ -COO-CH ₂ -CH ₃ , -CH ₂ -CH (-CH ₃ ) -CH ₂ -COO- CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OCO-CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -CH ₂ -COO-CH ₂ -CH (CH ₂ -CH ₃ ) -CH ₂ -CH ₂ -CH ₂ -CH ₃ ,-(CH ₂ ) ₅ -COO-(CH ₂ ) ₁₁ -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -CH- (COO-CH ₂ -CH ₃ ) ₂

-CH ₂ -O-CH ₃ , -CH ₂ -CH ₂ -O-CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -O-CH ₂ -CH ₃ ,-(CH ₂ -CH _2- O) _n- CH ₃ (where n is from 1 to 8),-(CH ₂ -CH ₂ -CH ₂ -O) _m -CH ₃ (where m is 1 to 5), -CH ₂ -CH (CH ₃ ) -O-CH ₂ -CH _3- , -CH ₂ -CH- (OCH ₃ ) ₂

-CH ₂ -S-CH ₃ , -CH ₂ -CH ₂ -S-CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -S-CH ₂ -CH ₃ ,-(CH ₂ -CH _2- S) _n- CH ₃ (where n is 1 to 8),-(CH ₂ -CH ₂ -CH ₂ -S) _m -CH ₃ (where m is 1 to 5), -CH ₂ -CH (CH ₃ ) -S-CH ₂ -CH _3- , -CH ₂ -CH- (SCH ₃ ) ₂

-CH ₂ -CH ₃ , -CH ₂ -CH ₂ -COO-CH ₂ -CH ₂ -O-CH ₂ -CH (CH ₂ -CH ₃ ) -CH ₂ -CH ₂ -CH ₂ -CH ₃ , -CH _2- CH ₃ , -CH ₂ -CH ₂ -COO-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -O-CH ₂ -CH (CH ₂ -CH ₃ ) -CH ₂ -CH ₂ -CH ₂ there can be -CH _3, but is not limited to these.

Monocyclic or condensed containing at least one bond selected from an ester bond (-COO-), an ether bond (-O-) and a sulfide bond (-S-), optionally having 2 to 30 carbon atoms Although the following are mentioned as a specific example of a polycyclic alkyl group, It is not limited to these.

[Chemical Formula 21]

As a substituted or unsubstituted alkenyl group in R <_1> -R <_12> , a C1-C18 linear, branched, monocyclic or condensed polycyclic alkenyl group is mentioned. They may have a plurality of carbon-carbon double bonds in the structure. As a specific example, a vinyl group, 1-propenyl group, an allyl group, 2-butenyl group, 3-butenyl group, isopropenyl group, isobutenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, and 4-pentene Neyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, cyclopentenyl group, cyclohexenyl group, 1, 3- butadienyl group, cyclo Although a hexadienyl group, a cyclopentadienyl group, etc. are mentioned, It is not limited to these.

The substituted or unsubstituted aryl group in R ₁ to R ₁₂ is a monocyclic or condensed polycyclic aromatic group which may include a substituted or unsubstituted hetero atom having 6 to 30 carbon atoms, for example, a phenyl group, 1- Naphthyl group, 2-naphthyl group, p-biphenyl group, m-biphenyl group, 2-anthryl group, 9-anthryl group, 2-phenanthryl group, 3-phenanthryl group, 9-phenanthryl group, 2- Fluorenyl group, 3-fluorenyl group, 9-fluorenyl group, 1-pyrenyl group, 2-pyrenyl group, 3-perylenyl group, taphenyl group, thienyl group, benzothienyl group, naphthyl enyl group, prill group, A pyranyl group, a pyridyl group, an imidazole group, a pyridyl group, an indole group, a thiazole group, etc. are mentioned.

In addition, the hydrogen atom of the substituted or unsubstituted alkyl group and the substituted or unsubstituted aryl group in R ₁ to R ₁₂ may be further substituted with another substituent.

As such a substituent, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a nitro group, a hydroxyl group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted aryloxy group is mentioned.

Here, is the same halogen atom, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted aryl group R ₁ ~ R ₁₂ halogen atom, an alkyl group substituted or unsubstituted in the, and a substituted or unsubstituted aryl group .

In addition, as a substituted or unsubstituted alkoxyl group, it is group which the oxygen atom couple | bonded with the substituted or unsubstituted alkyl group in R <_1> -R <_12> .

Moreover, as a substituted or unsubstituted aryloxy group, it is group which the oxygen atom couple | bonded with the substituted or unsubstituted aryl group in R <_1> -R <_12> .

Especially among the quinophthalone pigment | dye for color filters shown by General formula (7A), It is the quinophthalone pigment | dye for color filters shown by General formula (7B).

In the general formula (7B), the halogen atom in R ₁₃ to R ₁₈ , the substituted or unsubstituted alkyl group, the substituted or unsubstituted alkyl group, and the substituted or unsubstituted aryl group are the halogen atoms in R ₁ to R ₁₂ . , A substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted aryl group.

The quinophthalone pigment | dye for color filters shown by General formula (7) can be obtained by making a corresponding 2-methylquinoline and a corresponding phthalic anhydride react at high temperature in benzoic acid like the following reaction formula.

[Chemical Formula 22]

In addition, the quinophthalone pigment | dye of General formula (7) exists although tautomers of structures, such as the following general formula (7a) and (7b), are also within the scope of the present invention with respect to such tautomer.

(23)

Although the following pigment | dyes are mentioned as a specific example of the quinophthalone pigment | dye represented by General formula (7A), The pigment | dye of this invention is not limited to these.

&Lt; EMI ID =

(Pthalocyanine Pigment Appearing in General Formulas (8A) and (8B))

There is no restriction | limiting in particular as an aluminum phthalocyanine pigment used for this embodiment as long as it has a structure which trivalent aluminum arrange | positions to the center of a phthalocyanine ring. In the aluminum phthalocyanine pigment, aluminum is known to have a bond in addition to the phthalocyanine in the trivalent point, and have a structure such as dimer and trimer in addition to the monomer. Moreover, it is also possible to chemically modify a phthalocyanine ring and to take various structures is known. The aluminum phthalocyanine pigment in this embodiment may take any form, such as not only a monomer but a structure of a dimer, a trimer, or a chemical modification of the phthalocyanine ring.

Among these, as an aluminum phthalocyanine pigment, what is represented by the structure of General formula (8A) or General formula (8B) is preferable at the point of a color characteristic and dispersibility.

In General Formula (8A), X <_1> -X <_4> may be same or different, As a specific example, it has an alkyl group which may have a substituent, the aryl group which may have a substituent, the cycloalkyl group which may have a substituent, and a substituent The heterocyclic group which may have a substituent, the alkoxyl group which may have a substituent, the aryloxy group which may have a substituent, the alkylthio group which may have a substituent, and the arylthio group which may have a substituent are mentioned. When said X <_1> -X <_4> has a substituent, a substituent may be same or different, As a specific example, In addition to the characteristic groups, such as halogen groups, such as fluorine, chlorine, and bromine, an amino group, a hydroxyl group, a nitro group, an alkyl group and an aryl group , Cycloalkyl group, alkoxyl group, aryloxy group, alkylthio group, arylthio group and the like. In addition, a plurality of such substituents may be present.

Examples of the "alkyl group" of the alkyl group which may have a substituent include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, neopentyl group, n-hexyl group, n-octyl group and ste Linear or branched alkyl groups such as an aryl group and a 2-ethylhexyl group, and examples of the "alkyl group having a substituent" include trichloromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, and 2,2. -Dibromoethyl group, 2,2,3,3-tetrafluoropropyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2-nitropropyl group, benzyl group, 4-methylbenzyl group, 4-tert -Butyl benzyl group, 4-methoxybenzyl group, 4-nitrobenzyl group, 2, 4- dichlorobenzyl group, etc. are mentioned.

As an "aryl group" of the aryl group which may have a substituent, a phenyl group, a naphthyl group, an anthryl group, etc. are mentioned, As a "aryl group which has a substituent", p-methylphenyl group, p-bromophenyl group, p- Nitrophenyl group, p-methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, 2-aminophenyl group, 2-methyl-4-chlorophenyl group, 4-hydroxy-1-naphthyl group, 6-methyl-2 -Naphthyl group, 4,5,8- trichloro-2- naphthyl group, anthraquinonyl group, 2-aminoanthraquinonyl group, etc. are mentioned.

As a "cycloalkyl group" of the cycloalkyl group which may have a substituent, a cyclopentyl group, a cyclohexyl group, an adamantyl group, etc. are mentioned, As a "cycloalkyl group which has a substituent", a 2, 5- dimethyl cyclopentyl group, 4 -Tert- butylcyclohexyl group, etc. are mentioned.

As a "heterocyclic group" of the heterocyclic group which may have a substituent, a pyridyl group, a pyrazyl group, a piperidino group, a pyranyl group, a morpholine group, an acridinyl group, etc. are mentioned, As a "heterocyclic group which has a substituent," 3 -Methylpyridyl group, N-methylpiperidyl group, N-methylpyrrolyl group, etc. are mentioned.

Examples of the "alkoxyl group" of the alkoxyl group which may have a substituent include methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group, neopentyloxy group, 2, Straight-chain or branched alkoxyl groups such as 3-dimethyl-3-pentyloxy, n-hexyloxy group, n-octyloxy group, stearyloxy group, and 2-ethylhexyloxy group can be given. ", Trichloromethoxy group, trifluoromethoxy group, 2,2,2-trifluoroethoxy group, 2,2,3,3- tetrafluoropropoxy group, 2,2-ditrifluoro" Methyl propoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2-nitropropoxy group, benzyloxy group, etc. are mentioned.

As an "aryloxy group" of the aryloxy group which may have a substituent, a phenoxy group, a naphthoxy group, an anthryloxy group, etc. are mentioned, As a "aryloxy group which has a substituent", p-methylphenoxy group, p -Nitrophenoxy group, p-methoxyphenoxy group, 2,4-dichlorophenoxy group, pentafluorophenoxy group, 2-methyl-4- chlorophenoxy group, etc. are mentioned.

Examples of the "alkylthio group" of the alkylthio group which may have a substituent include methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, octylthio group, decylthio group, and dodecylti. A group, an octadecylthio group, etc. are mentioned, As a "alkylthio group which has a substituent", a methoxyethylthio group, an aminoethylthio group, a benzylaminoethylthio group, methylcarbonylaminoethylthio group, phenylcarbonyl Amino ethylthio group etc. are mentioned.

Examples of the "arylthio group" of the arylthio group which may have a substituent include a phenylthio group, 1-naphthylthio group, 2-naphthylthio group, 9-anthrylthio group, and the like. Chlorophenylthio group, trifluoromethylphenylthio group, cyanophenylthio group, nitrophenylthio group, 2-aminophenylthio group, 2-hydroxyphenylthio group and the like.

Next, specific examples of Y ₁ to Y ₄ include a phthalimidomethyl group (C ₆ H ₄ (CO) ₂ N—CH ₂ —) and a sulfamoyl group (H ₂ NSO) which may have a halogen atom, a nitro group, and a substituent. _2- ) can be mentioned. In addition, the phthalimidomethyl group which has a substituent shows the structure where the hydrogen atom in the phthalimidomethyl group was substituted by the substituent, and the sulfamoyl group which has a substituent shows the structure where the hydrogen atom in the sulfamoyl group was substituted by the substituent. Preferable Y is a halogen atom and sulfamoyl group. Phthalocyanine compounds in which m _l to m ₄ are zero (ie, there is no Y _l to Y ₄ ) can also be suitably used. Examples of the halogen atom include fluorine, chlorine, bromine and iodine. The "substituent" of the phthalimidomethyl group which may have a substituent and the sulfamoyl group which may have a substituent is the same as the substituent of X <_1> -X <_4> .

Z is represented by a hydroxyl group, a chlorine atom, -OP (= O) R ₁ R ₂ , or -O-SiR ₃ R ₄ R ₅ , wherein R ₁ and R ₂ each have a hydrogen atom, a hydroxyl group and a substituent A good alkyl group, an aryl group which may have a substituent, the alkoxyl group which may have a substituent, and the aryloxy group which may have a substituent are shown, and R <_1> , R <_2> may combine with each other and may form the ring.

Here, as an alkyl group in R <_1> and R <_2> , a methyl group, an ethyl group, a propyl group, isopropyl group, a butyl group, isobutyl group, tert- butyl group, neopentyl group, n-hexyl group, n-octyl group And linear or branched alkyl groups such as stearyl group and 2-ethylhexyl group. Examples of the substituent in the case where the alkyl group is an alkyl group having a substituent include halogen atoms such as chlorine, fluorine and bromine, alkoxyl groups such as methoxy group, Aromatic groups such as a phenyl group and a tril group, and a nitro group. In addition, a plurality of substituents may be present. Examples of the alkyl group having a substituent include trichloromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, 2,2-dibromoethyl group, 2-ethoxyethyl group and 2-butoxyethyl group. And 2-nitropropyl group, benzyl group, 4-methylbenzyl group, 4-tert-butylbenzyl group, 4-methoxybenzyl group, 4-nitrobenzyl group, and 2,4-dichlorobenzyl group.

Examples of the aryl group in R ₁ and R ₂ include a phenyl group, a naphthyl group, an anthryl group and the like, and examples of the substituent when the aryl group has a substituent include halogen atoms such as chlorine, fluorine and bromine, alkyl groups, alkoxyl groups and amino groups. And nitro groups. In addition, a plurality of substituents may be present. Examples of the aryl group having a substituent include p-tril group, p-bromophenyl group, p-nitrophenyl group, p-methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, and 2-dimethylaminophenyl group. , 2-methyl-4-chlorophenyl group, 4-methoxy-1-naphthyl group, 6-methyl-2-naphthyl group, 4,5,8-trichloro-2-naphthyl group, anthraquinonyl group, and the like.

As an alkoxyl group in R <_1> and R <_2> , a methoxy group, an ethoxy group, a propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert- butoxy group, neopentyloxy group, 2,3- Linear or branched alkoxyl groups such as dimethyl-3-pentyloxy group, n-hexyloxy group, n-octyloxy group, stearyloxy group, and 2-ethylhexyloxy group, and the substituent of an alkoxyl group having a substituent Examples thereof include halogen atoms such as chlorine, fluorine and bromine, aryl groups such as alkoxyl groups, phenyl groups and tril groups, and nitro groups. In addition, a plurality of substituents may be present. As an alkoxyl group which has a substituent, For example, a trichloromethoxy group, a trifluoro methoxy group, a 2, 2, 2- trifluoro ethoxy group, a 2, 2, 3, 3- tetrafluoro propoxy group, 2,2-ditrifluoromethyl propoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2-nitropropoxy group, benzyloxy group, etc. are mentioned.

Examples of the aryloxy group in R ₁ and R ₂ include a phenoxy group, a naphthaloxy group, an anthryloxy group and the like, and examples of the substituent in the case where the aryloxy group has a substituent include halogen atoms such as chlorine, fluorine and bromine and an alkyl group. , Alkoxyl groups, amino groups, nitro groups and the like. In addition, a plurality of substituents may be present. Examples of the aryloxy group having a substituent include p-methylphenoxy group, p-nitrophenoxy group, p-methoxyphenoxy group, 2,4-dichlorophenoxy group, pentafluorophenoxy group, and 2-methyl-4. Chlorophenoxy group and the like.

As an aluminum phthalocyanine pigment represented by General formula (8A), it is preferable that at least 1 of R <_1> , R <_{2> may} be an aryl group which may have a substituent, or an aryloxy group which may have a substituent from a viewpoint of dispersibility and a color characteristic. More preferably, both R ₁ and R ₂ are aryl groups or aryloxy groups. More preferably, both R ₁ and R ₂ are phenyl groups or phenoxy groups.

In general formula (8A), R <_3> , R <_4> and R <_5> are respectively independently C1-C18 alkyl groups or aromatic groups whose number of rings is four or less. If it is in the said range, the extinction coefficient about unit weight is enough, and the pigment concentration in a coloring composition can be made into a suitable range.

As an alkyl group in R <_3> , R <_4> and R <_5> , it may be branched or cyclic besides linear, and may have a functional group in the range of 3 or less heteroatoms in total. For example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, octadecyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 1-ethyl Pentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1-naphthoylmethyl group, 2-naphthoylmethyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanyl Phenacyl, 4-dimethylaminophenacyl, 4-cyanophenacyl, 4-methylphenacyl, 2-methylphenacyl, 3-fluorophenacyl, 3-trifluoromethylphenacyl, and 3-nitropena Practical skills etc. are mentioned.

As an aromatic group in R <_3> , R <_4> and R <_5> , a hetero atom may be included in an aromatic ring, and each aromatic ring may have a functional group in the range of 2 or less heteroatoms. For example, a phenyl group, a biphenyl group, 1-naphthyl group, 2-naphthyl group, 9- anthryl group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, and 2-azre Nyl group, 9-fluorenyl group, taphenyl group, quarterphenyl group, o-, m- and p-trilyl group, xylyl group, o-, m- and p-cumenyl group, mesityl group, pentarenyl group, vinaphthale Neyl group, tanaphthalenyl group, quarternaphthalenyl group, heptarenyl group, biphenylenyl group, indasenyl group, fluoranthhenyl group, acenaphthylenyl group, aceanthrylenyl group, phenenalenyl group, fluorenyl group, anthryl Group, bianthracenyl group, taanthracenyl group, quarter anthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, Perylene group, tetraphenylenyl group, coronyl group, etc. are mentioned.

Among the phthalocyanine compounds represented by General Formula (8A), Z is more preferably -OP (= 0) R ₁ R ₂ from the viewpoint of heat resistance and light resistance.

In Formula (8B), X ₅ to X ₁₂ may be the same as or different from each other, and specific examples thereof include an alkyl group which may have a substituent, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, and a substituent. The heterocyclic group which may have a substituent, the alkoxyl group which may have a substituent, the aryloxy group which may have a substituent, the alkylthio group which may have a substituent, and the arylthio group which may have a substituent are mentioned. When said X <_5> -X <_12> has a substituent, a substituent may be same or different, As a specific example, In addition to the characteristic groups, such as halogen groups, such as fluorine, chlorine, and bromine, an amino group, a hydroxyl group, a nitro group, an alkyl group and an aryl group , Cycloalkyl group, alkoxyl group, aryloxy group, alkylthio group, arylthio group and the like. In addition, a plurality of these substituents may be present.

Examples of the "alkyl group" of the alkyl group which may have a substituent include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, neopentyl group, n-hexyl group, n-octyl group and ste Linear or branched alkyl groups such as an aryl group and a 2-ethylhexyl group, and examples of the "alkyl group having a substituent" include trichloromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, and 2,2. -Dibromoethyl group, 2,2,3,3-tetrafluoropropyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2-nitropropyl group, benzyl group, 4-methylbenzyl group, 4-tert -Butyl benzyl group, 4-methoxybenzyl group, 4-nitrobenzyl group, 2, 4- dichlorobenzyl group, etc. are mentioned.

As an "aryl group" of the aryl group which may have a substituent, a phenyl group, a naphthyl group, an anthryl group, etc. are mentioned, As a "aryl group which has a substituent", p-methylphenyl group, p-bromophenyl group, p- Nitrophenyl group, p-methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, 2-aminophenyl group, 2-methyl-4-chlorophenyl group, 4-hydroxy-1-naphthyl group, 6-methyl-2 -Naphthyl group, 4,5,8- trichloro-2- naphthyl group, anthraquinonyl group, 2-aminoanthraquinonyl group, etc. are mentioned.

As a "cycloalkyl group" of the cycloalkyl group which may have a substituent, a cyclopentyl group, a cyclohexyl group, an adamantyl group, etc. are mentioned, As a "cycloalkyl group which has a substituent", a 2, 5- dimethyl cyclopentyl group, 4 -Tert- butylcyclohexyl group, etc. are mentioned.

As a "heterocyclic group" of the heterocyclic group which may have a substituent, a pyridyl group, a pyrazyl group, a piperidino group, a pyranyl group, a morpholine group, an acridinyl group, etc. are mentioned, As a "heterocyclic group which has a substituent," 3 -Methylpyridyl group, N-methylpiperidyl group, N-methylpyrrolyl group, etc. are mentioned.

Examples of the "alkoxyl group" of the alkoxyl group which may have a substituent include methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group, neopentyloxy group, 2, Straight-chain or branched alkoxyl groups such as 3-dimethyl-3-pentyloxy, n-hexyloxy group, n-octyloxy group, stearyloxy group, and 2-ethylhexyloxy group can be given. ", Trichloromethoxy group, trifluoromethoxy group, 2,2,2-trifluoroethoxy group, 2,2,3,3- tetrafluoropropoxy group, 2,2-ditrifluoro" Methyl propoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2-nitropropoxy group, benzyloxy group, etc. are mentioned.

As an "aryloxy group" of the aryloxy group which may have a substituent, a phenoxy group, a naphthoxy group, an anthryloxy group, etc. are mentioned, As a "aryloxy group which has a substituent", p-methylphenoxy group, p -Nitrophenoxy group, p-methoxyphenoxy group, 2,4-dichlorophenoxy group, pentafluorophenoxy group, 2-methyl-4- chlorophenoxy group, etc. are mentioned.

Examples of the "alkylthio group" of the alkylthio group which may have a substituent include methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, octylthio group, decylthio group, and dodecylti. A group, an octadecylthio group, etc. are mentioned, As a "alkylthio group which has a substituent", a methoxyethylthio group, an aminoethylthio group, a benzylaminoethylthio group, methylcarbonylaminoethylthio group, phenylcarbonyl Amino ethylthio group etc. are mentioned.

Examples of the "arylthio group" of the arylthio group which may have a substituent include a phenylthio group, 1-naphthylthio group, 2-naphthylthio group, 9-anthrylthio group, and the like. Chlorophenylthio group, trifluoromethylphenylthio group, cyanophenylthio group, nitrophenylthio group, 2-aminophenylthio group, 2-hydroxyphenylthio group and the like.

Next, specific examples of Y ₅ to Y ₁₂ include a phthalimidomethyl group (C ₆ H ₄ (CO) ₂ N—CH ₂ —) and sulfamoyl group (H ₂ NSO) which may have a halogen atom, a nitro group, or a substituent. _2- ) can be mentioned. In addition, the phthalimidomethyl group which has a substituent shows the structure where the hydrogen atom in the phthalimidomethyl group was substituted by the substituent, and the sulfamoyl group which has a substituent shows the structure where the hydrogen atom in the sulfamoyl group was substituted by the substituent. Preferable Y is a halogen atom and sulfamoyl group. Phthalocyanine compounds in which m ₁ to m ₄ are 0 (ie, there are no Y ₅ to Y ₁₂ ) can also be suitably used. Examples of the halogen atom include fluorine, chlorine, bromine and iodine. The "substituent" of the phthalimidomethyl group which may have a substituent and the sulfamoyl group which may have a substituent is the same as the substituent of X <_5> -X <_12> .

General formula (8B) of the, L is _{-O-SiR 6 R 7 -O-,} -O-SiR 6 R 7 -O-SiR 8 R 9 -O-, or -O-P (= O) R 10 - O-, and R ₆ to R ₁₀ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxyl group which may have a substituent, or an aryloxy which may have a substituent Group.

Here, as an alkyl group in R <_6> -R <_10> , a methyl group, an ethyl group, a propyl group, isopropyl group, a butyl group, isobutyl group, tert- butyl group, neopentyl group, n-hexyl group, n-octyl group And linear or branched alkyl groups such as stearyl group and 2-ethylhexyl group. Examples of the substituent in the case where the alkyl group is an alkyl group having a substituent include halogen atoms such as chlorine, fluorine and bromine, alkoxyl groups such as methoxy group, Aromatic groups such as a phenyl group and a tril group, and a nitro group. In addition, a plurality of substituents may be present. Examples of the alkyl group having a substituent include trichloromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, 2,2-dibromoethyl group, 2-ethoxyethyl group and 2-butoxyethyl group. And 2-nitropropyl group, benzyl group, 4-methylbenzyl group, 4-tert-butylbenzyl group, 4-methoxybenzyl group, 4-nitrobenzyl group, and 2,4-dichlorobenzyl group.

As an aryl group in R <_6> -R <_10> , there exist a phenyl group, a naphthyl group, an anthryl group, etc. As a substituent in the case where an aryl group has a substituent, halogen atoms, such as chlorine, fluorine, and bromine, an alkyl group, an alkoxyl group, an amino group And nitro groups. In addition, a plurality of substituents may be present. Examples of the aryl group having a substituent include p-tril group, p-bromophenyl group, p-nitrophenyl group, p-methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, and 2-dimethylaminophenyl group. , 2-methyl-4-chlorophenyl group, 4-methoxy-1-naphthyl group, 6-methyl-2-naphthyl group, 4,5,8-trichloro-2-naphthyl group, anthraquinonyl group, and the like.

As an alkoxyl group in R <_6> -R <_10> , a methoxy group, an ethoxy group, a propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert- butoxy group, neopentyloxy group, 2,3- Linear or branched alkoxyl groups such as dimethyl-3-pentyloxy group, n-hexyloxy group, n-octyloxy group, stearyloxy group, and 2-ethylhexyloxy group, and the substituent of an alkoxyl group having a substituent Examples thereof include halogen atoms such as chlorine, fluorine and bromine, aryl groups such as alkoxyl groups, phenyl groups and tril groups, and nitro groups. In addition, a plurality of substituents may be present. As an alkoxyl group which has a substituent, For example, a trichloromethoxy group, a trifluoro methoxy group, a 2, 2, 2- trifluoro ethoxy group, a 2, 2, 3, 3- tetrafluoro propoxy group, 2,2-ditrifluoromethyl propoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2-nitropropoxy group, benzyloxy group, etc. are mentioned.

Examples of the aryloxy group in R ₆ to R ₁₀ include a phenoxy group, a naphthaloxy group, an anthryloxy group and the like, and examples of the substituent when the aryloxy group has a substituent include halogen atoms such as chlorine, fluorine and bromine and an alkyl group. , Alkoxyl groups, amino groups, nitro groups and the like. In addition, a plurality of substituents may be present. Examples of the aryloxy group having a substituent include p-methylphenoxy group, p-nitrophenoxy group, p-methoxyphenoxy group, 2,4-dichlorophenoxy group, pentafluorophenoxy group, and 2-methyl-4. Chlorophenoxy group and the like.

As the phthalocyanine compound represented by General Formula (8B), at least one of R ₆ to R ₇ , R ₆ to R ₉ , and R ₁₀ may have a substituent from the viewpoint of the viscosity and color characteristics of the dispersion. Or it is preferable that it is an aryloxy group which may have a substituent. More preferably, R ₆ to R ₇ , R ₆ to R ₉ , and R ₁₀ are all aryl groups or aryloxy groups. More preferably, R ₆ to R ₇ , R ₆ to R ₉ , and R ₁₀ are all phenyl groups or phenoxy groups.

(Other colorant)

The coloring composition containing the coloring agent represented by General formula (1), (6) or (7) shows the color itself yellow, and if necessary, uses yellow, further green, red by using together with another pigment. It can be set as the coloring composition shown, and it is excellent in tolerance, and the coloring agent excellent in color development and color reproducibility can be obtained. By using together with a green pigment and / or a blue pigment, the green colorant which is high brightness and is used for a green filter segment can be obtained. Moreover, by using together with a red pigment (using an orange pigment as needed), the red coloring agent used for the red filter segment of high brightness can be obtained. Moreover, by using together with a yellow pigment, the yellow coloring agent used for the yellow filter segment which is excellent in tolerance and has coloring power, maintaining high brightness can be obtained. Moreover, dye can be used together for said filter segment. Hereinafter, a pigment and dye are illustrated.

As a green pigment, it is preferable to use a polyhalogenated phthalocyanine pigment. The polyhalogenated phthalocyanine pigment refers to a phthalocyanine pigment having at least two halogen atoms. Specifically, CI pigment green 7, 10, 36, 37, 58, etc. are mentioned. Especially, CI pigment green 36 and 58 are preferable.

As a blue pigment, it is preferable to use an aluminum phthalocyanine pigment. An aluminum phthalocyanine pigment is a preferable pigment from a point with high coloring power compared with a halogenated phthalocyanine pigment. Thereby, the addition amount of a pigment can be reduced or the thickness of the film | membrane of a color filter can be made thin. In addition, the viscosity which does not contain a halogen atom is preferable when environmental safety is considered.

As a 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, And yellow pigments such as 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, or 221. Especially, CI pigment yellow 138, 139, 150, and 185 are preferable from a viewpoint of heat resistance, light resistance, and lightness.

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 or 287 and the like are used. Especially, it is preferable to use CI pigment red 177, 179, 254. Moreover, red dyes, such as xanthene type, azo type, disazo type, anthraquinone type, can also be used. Specifically, salt-forming compounds of xanthene-based acid dyes such as CI acid red 52, 87, 92, 289, 338, etc. may be mentioned. Particularly preferred pigments here are CI Pigment Red 177 and 254.

CI pigment orange 38, 43, 71, 73, etc. are mentioned as an orange pigment.

As a yellow dye, azo dye, azo metal complex dye, anthraquinone dye, indigo dye, thioindigo dye, phthalocyanine dye, diphenylmethane dye, triphenylmethane dye, xanthene dye, thiazine dye, cationic dye, cyanine dye, Nitro dyes, quinoline dyes, naphthoquinone dyes, and oxazine dyes.

Specific examples of the yellow dye include CI acid yellow 2, 3, 4, 5, 6, 7, 8, 9, 9: 1, 10, 11, 11: 1, 12, 13, 14, 15, 16, 17, 17: 1, 18, 20, 21, 22, 23, 25, 26, 27, 29, 30, 31, 33, 34, 36, 38, 39, 40, 40: 1, 41, 42, 42: 1 43, 44, 46, 48, 51, 53, 55, 56, 60, 63, 65, 66, 67, 68, 69, 72, 76, 82, 83, 84, 86, 87, 90, 94, 105, 115, 117, 122, 127, 131, 132, 136, 141, 142, 143, 144, 145, 146, 149, 153, 159, 166, 168, 169, 172, 174, 175, 178, 180, 183, 187, 188, 189, 190, 191, 192, 199, etc. are mentioned.

In addition, CI direct yellow 1, 2, 4, 5, 12, 13, 15, 20, 24, 25, 26, 32, 33, 34, 35, 41, 42, 44, 44: 1, 45, 46, 48 , 49, 50, 51, 61, 66, 67, 69, 70, 71, 72, 73, 74, 81, 84, 86, 90, 91, 92, 95, 107, 110, 117, 118, 119, 120 , 121, 126, 127, 129, 132, 133, 134 and the like.

In addition, CI basic yellow 1, 2, 5, 11, 13, 14, 15, 19, 21, 24, 25, 28, 29, 37, 40, 45, 49, 51, 57, 79, 87, 90, 96 , 103, 105, 106 and the like.

In addition, CI solvent yellow 2, 3, 4, 7, 8, 10, 11, 12, 13, 14, 15, 16, 18, 19, 21, 22, 25, 27, 28, 29, 30, 32, 33 , 34, 40, 42, 43, 44, 45, 47, 48, 56, 62, 64, 68, 69, 71, 72, 73, 77, 79, 81, 82, 83, 85, 88, 89, 90 , 93, 94, 98, 104, 107, 114, 116, 117, 124, 130, 131, 133, 135, 138, 141, 143, 145, 146, 147, 157, 160, 162, 163, 167, 172 , 174, 175, 176, 177, 179, 181, 182, 183, 184, 185, 186, 187, 188, 190, 191, 192, 194, 195, and the like.

In addition, CI Disperse Yellow 1, 2, 3, 5, 7, 8, 10, 11, 13, 13, 23, 27, 33, 34, 42, 45, 48, 51, 54, 56, 59, 60, 63, 64, 67, 70, 77, 79, 82, 85, 88, 93, 99, 114, 118, 119, 122, 123, 124, 126, 163, 184, 184: 1, 202, 211, 229, 231, 232, 233, 241, 245, 246, 247, 248, 249, 250, 251, etc. are mentioned.

As content of the preferable coloring agent in all the non volatile components of the coloring composition which concerns on this embodiment, it is 10-90 weight% from a viewpoint of sufficient color reproducibility and stability, More preferably, it is 15-85 weight%, Most preferably 20 to 80% by weight.

When using a yellow pigment | dye, the weight ratio of the aluminum phthalocyanine pigment represented by a yellow pigment | dye / general formula (8A) and / or (8B) has preferable 80/20-10/90. By satisfying this range, it is possible to form green filter segments having excellent brightness and a wide chromaticity range.

When using together the quinophthalone compound represented by General formula (1), and the quinophthalone pigment | dye represented by General formula (6), it is a general formula (6) with respect to 100 weight part of the quinophthalone compounds represented by General formula (1). The range of 10-1500 weight part of quinophthalone pigment | dyes shown by () is preferable, More preferably, it is the range of 100-1200 weight part. When the quinophthalone pigment | dye represented by General formula (6) is more than 10 weight part, the effect of brightness improvement can be exhibited. Moreover, when it is less than 1500 weight part, since the sensitivity at the time of using with contrast ratio and the photosensitive coloring composition becomes favorable, it is preferable.

In the case of the coloring agent (or coloring composition) which forms a green filter segment, the use ratio of a green pigment and / or a blue pigment and the quinophthalone pigment represented by General formula (6) is a general formula (6) with respect to 100 weight part of pigments. 1-1200 weight part is preferable, and, as for the quinophthalone pigment | dye shown by (), More preferably, it is 5-600 weight part. If the addition amount of the quinophthalone pigment | dye represented by General formula (6) is 1 weight part or more, a reproducible chromaticity area | region is large, and when it is 1200 weight part or less, a hue does not change.

Moreover, when using together a yellow pigment and the quinophthalone pigment | dye represented by General formula (6) as a coloring agent (or coloring composition) which forms a green filter segment, a green pigment and / or a blue pigment and a yellow coloring agent (yellow pigment) And the use ratio with the quinophthalone pigment | dye mixture represented by General formula (6), 1-1200 weight part of yellow colorants is preferable with respect to 100 weight part of pigments, More preferably, it is 5-600 weight part. If the addition amount of the yellow colorant is 1 part by weight or more, the reproducible chromaticity region is wide, and if it is 1200 parts by weight or less, the color does not change.

When using together a yellow pigment and the quinophthalone pigment | dye represented by General formula (6) as a coloring agent (or coloring composition) which forms a green filter segment, when it considers a color structure, it appears in a yellow pigment and General formula (6). It is preferable that the mixture ratio of content of a quinophthalone pigment | dye is 1-400 weight part with respect to the quinophthalone pigment | dye represented by General formula (6) with respect to 100 weight part of yellow pigments, More preferably, it is 5-300 weight part.

In the case of the coloring agent (or coloring composition) which forms a red filter segment, the usage ratio of a red pigment and the quinophthalone pigment | dye represented by General formula (6) is a kinoph represented by General formula (6) with respect to 100 weight part of red pigments. 1-800 weight part of talon dyes is preferable, More preferably, it is 5-400 weight part. If the addition amount of the quinophthalone pigment | dye represented by General formula (6) is 1 weight part or more, a reproducible chromaticity area | region is large and if it is 800 weight part or less, a hue does not change. Moreover, when the color structure is considered, the mixing ratio of the red pigment and the quinophthalone pigment | dye represented by General formula (6) is 1-400 to the quinophthalone pigment | dye represented by General formula (6) with respect to 100 weight part of red pigments. It is preferable that it is a weight part, More preferably, it is the range of 5-300 weight part.

When using together the phthalocyanine pigment | dye represented by General formula (8A) or (8B) and the quinophthalone pigment | dye represented by General formula (6), it is general formula (6) with respect to 100 weight part of phthalocyanine pigment | dye represented by General formula (6). The range of 3-1200 weight part of quinophthalone pigment | dye shown by this is preferable, More preferably, it is the range of 5-800 weight part. When the quinophthalone pigment | dye represented by General formula (8A) or (8B) is more than 3 weight part, the effect of brightness improvement can fully be exhibited. Moreover, when it is less than 1200 weight part, since heat resistance and light resistance become favorable, it is preferable.

When using together the quinophthalone pigment | dye represented by General formula (6) and the quinophthalone pigment | dye represented by General formula (7), it is general formula (7) with respect to 100 weight part of quinophthalone pigment | dyes represented by General formula (6). The range of 11-900 weight part of the quinophthalone pigment | dye shown by is preferable. More preferably, it is the range of 27-650 weight part, More preferably, it is the range of 43-400 weight part. When the quinophthalone pigment | dye represented by General formula (7) is 11 weight part or more, the fluorescence of the quinophthalone pigment | dye represented by General formula (6) is fully extinguished, contrast ratio will become high, and when 900 weight part or less, since the coloring power is a practical use level, , desirable.

As for the usage ratio of a green pigment and / or a blue pigment and the quinophthalone pigment | dye represented by General formula (6) and (7), 5-1000 weight part of quinophthalone pigment | dyes is preferable with respect to 100 weight part of pigments, More preferably, Is 17 to 600 parts by weight. If the addition amount of the quinophthalone pigment | dye represented by General formula (6) and (7) is 5 weight part or more, the reproducible chromaticity area | region becomes narrow, and when it is 1000 weight part or less, a hue does not change.

In addition, when using together a yellow pigment and the quinophthalone pigment | dye represented by General formula (6) and (7), a green pigment and / or a blue pigment and a yellow coloring agent (yellow pigment and General formula (6) and (7) As for the usage ratio of the mixture of the quinophthalone pigment | dye shown by (), 5-1000 weight part of yellow colorants is preferable with respect to 100 weight part of green pigments and / or blue pigment, More preferably, it is 17-600 weight part. If the addition amount of the yellow colorant is 5 parts by weight or more, the reproducible chromaticity region is wide, and if it is 600 parts by weight or less, the color does not change.

When using in combination with a yellow pigment and the quinophthalone pigment | dye represented by General formula (6) and (7), when a color structure is considered, the yellow pigment and the quinophthalone pigment | dye represented by General formula (6) and (7) It is preferable that the quinophthalone pigment | dye represented by General formula (6) and (7) is 1-400 weight part with respect to the compounding ratio of content, and 100 weight part of yellow pigments, More preferably, it is the range of 5-300 weight part.

When using as a coloring agent (or coloring composition) which forms a red filter segment, the usage ratio of a red pigment and the quinophthalone pigment | dye represented by General formula (6) and (7) is a general formula (6) with respect to 100 weight part of red pigments. 1-100 weight part is preferable, and, as for the quinophthalone pigment | dye shown to (7), More preferably, it is 5-50 weight part. If the addition amount of the quinophthalone pigment | dye represented by General formula (6) and (7) is 1 weight part or more, a reproducible chromaticity area | region is large and if it is 100 weight part or less, a hue does not change.

As for the usage ratio of the green pigment and / or blue pigment and the quinophthalone pigment | dye represented by General formula (7A), 1-1200 weight part of the quinophthalone pigment | dye represented by General formula (7A) with respect to 100 weight part of pigments is preferable, More preferably, it is 5-600 weight part. If the addition amount is 1 part by weight or more, the reproducible chromaticity region is wide, and if it is 1200 parts by weight or less, the color does not change.

In addition, when using together a yellow pigment and the quinophthalone pigment | dye represented by General formula (7A), a green pigment and / or a blue pigment and a yellow coloring agent (a yellow pigment and the quinophthalone pigment mixture represented by General formula (7A)) As for the use ratio of, 1-1200 weight part of yellow colorants is preferable with respect to 100 weight part of pigments, More preferably, it is 5-600 weight part. If the addition amount is 1 part by weight, the reproducible chromaticity region is wide, and if it is 1200 parts by weight or less, the color does not change.

When using together a yellow pigment and the quinophthalone pigment | dye represented by General formula (7A), and using it as a pigment for green filter segments, when a color structure is considered, the combination of a yellow pigment and the quinophthalone pigment content represented by General formula (7A) It is preferable that the ratio is 1-400 weight part of the quinophthalone pigment | dye represented by General formula (7A) with respect to 100 weight part of yellow pigments, More preferably, the key represented by general formula (7A) with respect to 100 weight part of yellow pigments Nophthalone pigment | dye is the range of 5-300 weight part.

The use ratio of the yellow pigment and the quinophthalone pigment | dye represented by General formula (7A) in the case of using as the coloring agent (or coloring composition) which forms for a yellow filter segment is based on General formula (7A) with respect to 100 weight part of yellow pigments. 1-1200 weight part is preferable, and, as for the quinophthalone pigment | dye shown, More preferably, it is 5-600 weight part. Moreover, when the color structure is considered, the mixing ratio of the yellow pigment and the quinophthalone pigment | dye represented by General formula (7A) is 1-400 of the quinophthalone pigment | dye represented by General formula (7A) with respect to 100 weight part of yellow pigments. It is preferable that it is a weight part, More preferably, it is the range of 5-300 weight part.

When it is set as the coloring agent (or coloring composition) which forms for a red filter segment, the use ratio of the red pigment and the quinophthalone pigment | dye represented by General formula (7A) is represented by General formula (7A) with respect to 100 weight part of red pigments. 1-800 weight part of a quinophthalone pigment | dye is preferable, More preferably, it is 5-400 weight part. If the addition amount of the quinophthalone pigment | dye represented by General formula (7A) is 1 weight part or more, a reproducible chromaticity area | region is wide and if it is 800 weight part or less, a hue does not change. Moreover, when the color structure is considered, the mixing ratio of the red pigment and the quinophthalone pigment | dye represented by General formula (7A) is 1-400 weight of the quinophthalone pigment | dye represented by General formula (7A) with respect to 100 weight part of red pigments. The denier is preferable, More preferably, it is the range of 5-300 weight part.

All of the said combinations can be adjusted and used suitably, considering the heat resistance, light resistance, and lightness of a coloring agent.

<Miniaturization of pigment>

When a coloring agent is a pigment, it is preferable to refine | miniaturize and to use. The miniaturization method is not particularly limited, and for example, wet grinding, dry grinding, and dissolution precipitation can be used, and salt milling, etc., by a kneader method, which is a kind of wet grinding, is performed. Can be refined. It is preferable that the primary particle diameter of a pigment is 5 nm or more from the point which the dispersion | distribution to a coloring agent support is favorable. Moreover, it is preferable that it is 100 nm or less from the point which can form the filter segment with high contrast ratio. Especially preferable range is the range of 10-80 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 diameter of the pigment particle.

Salt milling treatment is a batch or continuous kneader, such as a kneader, a two-stage roll mill, a three-stage roll mill, a ball mill, an atrito, a sand mill, a planetary mixer, and a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent. After kneading while heating mechanically, it is a process of removing water-soluble inorganic salt and water-soluble organic solvent by washing with water. A water-soluble inorganic salt functions as a crushing adjuvant, and grind | pulverizes a pigment using the high hardness of an inorganic salt at the time of 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 diameter of the primary particles, a narrow distribution, and a sharp particle size distribution.

As a water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate, etc. can be used, but it is preferable to use sodium chloride (salt) from a cost viewpoint. It is preferable to use 50-2000 weight part with respect to 100 weight part of total weight of a pigment, and, as for a water-soluble inorganic salt, it is most preferable to use 300-1000 weight part from both processing efficiency and production efficiency.

The water-soluble organic solvent is not particularly limited as long as it functions to wet the pigment and the water-soluble inorganic salt, and dissolves (mixes) in water and does not substantially dissolve the inorganic salt to be used. However, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety, because the temperature rises during salt milling and the solvent is easily evaporated. For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl Ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, Dipropylene glycol monoethyl ether, liquid polypropylene glycol, etc. are used. 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 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. It is preferable that resin used is solid at room temperature, and is water-insoluble, and it is still more preferable to melt | dissolve in part in the said 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.

<Binder Resin>

As binder resin disperse | distributing, dyeing, or infiltrating, a conventionally well-known thermoplastic resin, thermosetting resin, etc. are mentioned. The binder resin is preferably a resin having a spectral transmittance of 80% or more, more preferably 95% or more in the full-wavelength region of 400 to 700 nm which is the visible light region. Moreover, binder resin is preferable because it has the effect of improving the contrast ratio by quenching fluorescence by chemically interacting with the quinophthalone type pigment | dye represented by General formula (6).

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, polyester Resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins.

In addition, when using in the form of an alkali developing type coloring resist material, it is preferable to use alkali-soluble resin which copolymerized the acidic group containing ethylenically unsaturated monomer. Moreover, in order to improve light sensitivity further, active energy ray curable resin which has an ethylenically unsaturated double bond can also be used.

In particular, the use of an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain in an alkali developing resist for color filters prevents coating film foreign matters after applying the colorant and improves the stability of the colorant in the resist material. . In the case of using a linear resin having no ethylenically unsaturated double bond in the side chain, the colorant component does not adhere to the resin and has a degree of freedom in the mixed solution of the resin and the colorant. By using an active energy ray-curable resin having a unsaturated unsaturated double bond, the colorant tends to adhere to the resin in a mixture of the resin and the colorant, so that the pigment is difficult to dissolve in the solvent resistance test, and the colorant component is difficult to aggregate and precipitate. In addition, when light is exposed to active energy rays to form a film, the resin is three-dimensionally crosslinked to fix the colorant molecule, and it is estimated that the colorant component is unlikely to aggregate and precipitate even if the solvent is removed in a subsequent development step.

As 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 / (anhydride) maleic acid copolymer, styrene / styrene sulfonic acid copolymer, ethylene / (meth) acrylic acid copolymer, or isobutylene / (anhydride) Maleic acid copolymer etc. are mentioned. Among these, acrylic resins having acidic groups and at least one resin selected from styrene / styrene sulfonic acid copolymers, particularly acrylic resins having acidic groups, are suitably used because of their high heat resistance and transparency.

Moreover, it is preferable that alkali-soluble resin has a hydrophilic functional group separately from acidic groups, such as acrylic acid, from a viewpoint of quinophthalone pigment dispersibility. In introducing a hydrophilic functional group, the ethylenically unsaturated monomer which has a hydroxyl group and / or a (poly) alkylene oxide structure, and does not have an aromatic ring is used suitably. Specific examples of such ethylenically unsaturated monomers include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and glycerol mono (meth) acrylate. Hydroxyl group-containing (meth) acrylates such as 4-hydroxyvinylbenzene and 2-hydroxy-3-phenoxypropyl acrylate; 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, diethylene glycol monomethyl ether (Meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol mono-2-ethylhexyl ether (meth) acrylate, dipropylene glycol monomethyl ether (meth) acrylate, triethylene glycol mono Methyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, tripropylene glycol monomethyl ether (meth) acrylate, tetraethylene glycol monomethyl ether (meth) acrylate, polyethylene glycol monomethyl ether ( Meta) acrylate, polypropylene glycol monomethyl ether (meth) acrylate, polyethylene glycol monolauryl ether (meth) acrylic (Poly) alkylene glycol monoalkyl ether (meth) acrylates, such as a nitrate, polyethyleneglycol monostearyl ether (meth) acrylate, and an octoxy polyethyleneglycol polypropylene glycol (meth) acrylate; These are mentioned, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, polyethylene glycol monomethyl ether (Meth) acrylate and polypropylene glycol monomethyl ether (meth) acrylate are used preferably.

Although the content of the ethylenically unsaturated monomer which has the said hydroxyl group and / or (poly) alkylene oxide structure and does not have an aromatic ring can be suitably selected in the range which does not impair the solubility in a synthetic solvent, propylene glycol monomethyl When ether acetate is used as a synthetic solvent, Preferably it can be used suitably in the range of 5-50 weight%, More preferably, it is 10-35 weight%.

The weight average molecular weight (Mw) of the alkali-soluble resin is preferably in the range of 5,000 to 100,000, more preferably in the range of 5,000 to 40,000. Moreover, the range of 2,500-50,000 is preferable, and, as for number average molecular weight (Mn), it is preferable that the value of Mw / Mn is 10 or less.

Moreover, as for the glass transition temperature (henceforth, it may be described as Tg) of alkali-soluble resin, -40-70 degreeC is preferable from a viewpoint of dispersion stability, -30-30 degreeC is more preferable, -20 ~ 10 degreeC is more preferable.

Tg of alkali-soluble resin used the value computed by the following Fox formula. In 1 / Tg = W1 / Tg1 + W2 / Tg2 + ... + Wn / TgnW1, Wn represents the weight fraction of each monomer used, and Tg1 to Tgn represent the glass transition temperature of each homopolymer obtained from each monomer. Represents absolute temperature "K").

Tg of the main homopolymer used for calculation is illustrated below. Methacrylic acid: 130 degrees Celsius (403K) butyl acrylate: -54 degrees Celsius (219K) benzyl methacrylate: 55 degrees Celsius (328K) paracumyl phenol ethylene oxide modified acrylate (Toagosei Co., Ltd. product, M-110): 35 degrees Celsius (308K) 4-hydroxybutyl acrylate: -80 degrees Celsius (193K) 2-hydroxyethyl methacrylate: 55 degrees Celsius (328K) methoxy polyethylene glycol methacrylate (made by Nihon Oil Holding Co., Ltd., PME- 400): -60 degrees Celsius (213K) butyl methacrylate: 20 degrees Celsius (293K)

As a method for producing an active energy ray-curable resin having an ethylenically unsaturated active double bond, a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group or an amino group is prepared as a precursor of the resin, for example, an isocyanate group, an aldehyde group, an epoxy group, or the like. A method of obtaining a resin in which photo-crosslinkable groups such as a (meth) acryloyl group and a styryl group are introduced into the linear polymer by reacting a (meth) acrylic compound having a reactive substituent of styrene and a styryl group, or styrene-maleic anhydride copolymerization Method of semi-esterifying the linear polymer containing acid anhydrides, such as water and an alpha-olefin- maleic anhydride copolymer, with the (meth) acryl compound which has hydroxyl groups, such as hydroxyalkyl (meth) acrylate, and hydroxy Copolymerize (meth) acryl compounds which have hydroxyl groups, such as alkyl (meth) acrylate Method for adding a (meth) acryl compound having an isocyanate group such as (meth) acryloyloxyethyl isocyanate to the linear polymer, and glycidyl (meth) to the linear polymer containing carboxyl groups such as (meth) acrylic acid The method of adding the (meth) acryl compound which has epoxy groups, such as an acrylate, etc. are mentioned.

It is also preferable as a coloring composition for color filters to have alkali-soluble ability and energy-beam hardening performance as a thermoplastic resin.

The following are mentioned as a monomer which comprises the said thermoplastic resin. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acryl Rate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl ( Meth) acrylate, isobonyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, methoxy polypropylene (Meth) acrylates, such as glycol (meth) acrylate or ethoxy polyethylene glycol (meth) acrylate, or (meth) acrylamide, N, N- dimethyl (meth) acrylamide, N, N-diethyl (Meth) acrylic army (Meth) acrylamides, such as N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, or acryloyl morpholine, styrene, such as styrene, or (alpha) -methylstyrene, ethyl vinyl ether, and vinyl ethers such as n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether or isobutyl vinyl ether, and fatty acid vinyls such as vinyl acetate or vinyl propionate.

Alternatively, cyclohexyl maleimide, phenyl maleimide, methyl maleimide, ethyl maleimide, 1,2-bismaleimide ethane 1,6-bismaleimide hexane, 3-maleimide propionic acid, 6,7-methylenedioxy- 4-methyl-3-maleimide coumarin, 4,4'- bismaleimide diphenylmethane, bis (3-ethyl-5-methyl- 4-maleimide phenyl) methane, N, N'-1, 3-phenyl Rendymaleimide, N, N'-1,4-phenylenedimaleimide, N- (1-pyrenyl) maleimide, N- (2,4,6-trichlorophenyl) maleimide, N- (4- Aminophenyl) maleimide, N- (4-nitrophenyl) maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-3-maleimide propionic acid, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide hexanoate, N- [4- (2-benzoy N-substituted maleimide, such as midazolyl) phenyl] maleimide and 9-maleimide acridine, is mentioned.

As a thermosetting resin, an epoxy resin, benzoguanamine resin, rosin modified maleic acid resin, rosin modified fumaric acid resin, melamine resin, urea resin, a phenol resin etc. are mentioned, for example. Especially, from a viewpoint of heat resistance improvement, an epoxy resin and a melamine resin are used more suitably.

In order for the weight average molecular weight (Mw) of binder resin to disperse | distribute a coloring agent preferably, the range of 5,000-100,000 is preferable, As a more preferable range, the range of 5,000-80,000, 10,000-80,000, 7,000-50,000, 8,000-50,000 is preferable. Can be taken. The number average molecular weight (Mn) is preferably in the range of 2,500 to 50,000, and more preferably in the range of 5,000 to 50,000 and 2,500 to 40,000. It is preferable that the value of Mw / Mn is 10 or less. Here, a weight average molecular weight (Mw) and a number average molecular weight (Mn) connect four separation columns in series in gel osmosis chromatography "HLC-8120GPC" by Tosoh Corporation, and tosoh is added to a filler in order. It is a polystyrene conversion molecular weight measured using tetrahydrofuran using "TSK-GEL SUPER H5000", "H4000", "H3000", and "H2000" by the company.

In addition, when using HLC-8220GPC (made by Tosoh Corporation) as an apparatus, connecting TSK-GEL SUPER HZM-N as two columns continuously, and setting it as the polystyrene conversion molecular weight measured using THF as a solvent, In order for the weight average molecular weight (Mw) of binder resin to disperse | distribute a coloring agent preferably, the range of 5,000-80,000 is preferable, 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.

When the binder resin is used as the color composition for color filters, the balance between the carboxyl group functioning as the colorant adsorber and the alkali soluble group at the time of development, the aliphatic group and the aromatic group functioning as the affinity group for the colorant, It is important also in dispersibility, permeability, developability, and also durability, and it is preferable to use resin of 20-300 mgKOH / g of acid value. If the acid value is less than 20 mgKOH / g, the solubility in the developer is poor, and it is difficult to form a fine pattern. If it exceeds 300 mgKOH / g, there will be no fine pattern left in the development.

It is preferable to use binder resin in the quantity of 20-500 weight part with respect to 100 weight part of coloring agents, More preferably, it is 30-500 weight part. When it is 20 weight part or more, film-forming property and agent resistance are favorable, and when it is 500 weight part or less, the expression of a color characteristic is favorable. Moreover, it is preferable to use in the quantity of 20 weight part-400 weight part from a viewpoint of fluorescent quenching. If it is 20 weight part or more, fluorescence will be fully extinguished. Moreover, if it is 400 weight part or less, the self-quenching by the quinophthalone pigment | dye represented by General formula (6) will not be inhibited. Moreover, it is preferable from a viewpoint of fluorescent quenching to contain an aromatic ring in the structure of binder resin. In particular, it is more preferable to include more aromatic rings.

<Organic solvent>

The coloring composition of this embodiment contains an organic solvent in order to fully disperse | disperse and penetrate a coloring agent in a coloring agent support | carrier, and to apply the thickness of a dry film to 0.2-5 micrometers on board | substrates, such as a glass substrate, and to facilitate formation of a filter segment. Let's do it. The organic solvent is selected in consideration of the solubility of each component of the coloring composition, and also the safety, in addition to having good applicability of the coloring composition.

As the organic solvent, for example, ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1, 4-dioxane, 2-heptanone, 2-methyl- 1, 3- propanediol, 3, 5, 5- trimethyl- 2-cyclohexene 1-one, 3, 3, 5- trimethyl cyclohexanone, 3 Ethyl ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxy Butyl acetate, 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 and γ-butyrolactone Isobutyl alcohol Isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol mono tertiary butyl ether, ethylene glycol monobutyl ether, Ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, Diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone , Dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tri Propylene 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 propionic acid, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, acetic acid Isobutyl, propyl acetate, dibasic acid ester, etc. are mentioned.

Especially, since the dispersibility of a coloring agent, the permeability, and the applicability | paintability of a coloring composition are favorable, alkyl heritages, such as ethyl lactate, a propylene glycol monomethyl ether acetate, a propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene It is preferable to use glycol acetates, such as glycol monoethyl ether acetate, alcohols, such as benzyl alcohol and diacetone alcohol, and ketones, such as cyclohexanone.

An organic solvent can be used individually by 1 type or in mixture of 2 or more types in arbitrary ratio as needed. Further, the organic solvent is preferably used in an amount of 500 to 4000 parts by weight based on 100 parts by weight of the coloring agent, since the coloring composition can be adjusted to an appropriate viscosity and a filter segment having a desired uniform film thickness can be formed. More preferably, it is 800-4000 weight part.

<Dispersion aid>

One embodiment of the coloring composition may contain a dispersing aid. When disperse | distributing a coloring agent in a coloring agent support | carrier, dispersion adjuvant, such as a dye derivative, resin type dispersing agent, and surfactant, can be used suitably. Since the dispersion aid has a great effect of preventing re-agglomeration of the colorant after dispersion, the coloring composition obtained by dispersing the colorant in the colorant carrier using the dispersion aid has good brightness and viscosity stability.

In addition, when the quinophthalone-based dye emits fluorescence, as the quinophthalone-based dye and the dye derivative or resinous dispersant chemically interact, the fluorescence of the quinophthalone-based dye is quenched, resulting in a good contrast ratio.

(Color derivative)

As a dye derivative, the compound which introduce | transduced the phthalimidomethyl group which may have a basic substituent, an acidic substituent, or a substituent to an organic pigment, anthraquinone, an acridon, or a triazine is mentioned, for example. 305173, JP-A 57-15620, JP-A 59-40172, JP-A 63-17102, JP-A-5-9469, JP 2001-335717, JP 2003-128669, Japanese Patent Application Laid-Open No. 2004-900997, 2007-156395, 2008-094873, 2008-094986, 2008-095007, 2008-1995916, and 4585781. What exists can be used and these can be used individually or in mixture of 2 or more types. When using a dye derivative, it is preferable to have a quinophthalone skeleton and an azo skeleton from a viewpoint of lightness.

Moreover, when a quinophthalone type pigment | dye emits fluorescence, it is preferable to have an anthraquinone skeleton, an acridon skeleton, and a phthalocyanine skeleton from a viewpoint of fluorescence quenching. Moreover, it is preferable to have sulfonamide as a substituent.

The content of the dye derivative is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, and most preferably 3 parts by weight or more based on 100 parts by weight of the colorant from the viewpoint of dispersibility improvement. Moreover, it is 40 weight part or less from a viewpoint of heat resistance and light resistance, More preferably, it is 35 weight part or less.

(Resin Dispersant)

The resinous dispersant has a colorant affinity site having a property of adsorbing to a colorant and a site compatible with the colorant carrier, and serves to stabilize the dispersion of the colorant into the colorant carrier by adsorbing the colorant. 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 salt, Oily acidic acids such as polyamides, long-chain polyaminoamide phosphoric acid, hydroxyl-containing polycarboxylic acid esters, amides formed by the reaction of modified substances thereof, poly (lower alkyleneimines) and polyesters having free carboxyl groups, and salts thereof; Water-soluble resin, water-soluble high molecular compound, polyester type, such as (meth) acrylic-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, Modified polyacrylates, ethylene oxide / propylene oxide addition compounds, phosphate esters, and the like, They can be used singly or in combination of two or more thereof, but are not necessarily limited to these.

In addition, when using the quinophthalone compound represented by General formula (1), the dispersing agent which contains the ethylenically unsaturated monomer (a1) which has at least one of an ethylene oxide chain | strand or a propylene oxide chain | strand as a resin type dispersing agent in a copolymerization composition is used. It is preferable from the viewpoint of dispersibility, flowability and storage stability. This resin type dispersing agent is demonstrated in the item of the following pigment dispersing agents.

Among the resinous dispersants, a polymer dispersant having a basic functional group is preferable because of the low viscosity of the coloring composition and a high contrast ratio, and a graft copolymer containing a nitrogen atom or a tertiary chain in the side chain is preferable. Preferred are nitrogen atom-containing acrylic block copolymers and urethane polymer dispersants having a functional group including an amino group, a quaternary ammonium base, a nitrogen-containing heterocycle, and the like.

As a commercially available resin type dispersing agent, Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167, made by Bigg Chemi Japan Co., Ltd. 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164 or Anti Terra-U, 203, 204 or BYK-P104, P104S, 220S, 6919, 21116, 21324, 21407, 21715 or SOLSPERSE-3000, 9000, 13000, manufactured by Nihon Lubrijorus, such as Lactimon, Lactimon-WS or Bykumen 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, etc. made in 55000, 56000, 76500, etc. 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. Ajispa-PA111, PB711, PB821, PB822, PB824 by Ajinomoto Fine Techno Co., etc. are mentioned.

The content of the resinous dispersant is preferably 0.1 to 55 parts by weight, more preferably 0.1 to 45 parts by weight with respect to 100 parts by weight of the colorant. If content of a resinous dispersing agent is 0.1 weight part or more, the added effect can fully be acquired, and if content is 55 weight part or less, dispersion will be very favorable.

Or it is preferable to use about 5-200 weight% with respect to pigment whole quantity, and, as for a resin type dispersing agent, it is more preferable to use about 10-100 weight% from a film formability viewpoint.

<Pigment dispersant>

The pigment dispersing agent is the hydroxyl group of the vinyl polymer (A) which has two hydroxyl groups in one end area | region which contains in an copolymerization composition the ethylenically unsaturated monomer (a1) which has at least one of an ethylene oxide chain or a propylene oxide chain. By reacting an isocyanate group of a urethane prepolymer (E) having an isocyanate group at both ends with an isocyanate group of diisocyanate (B) and a primary and / or secondary amino group of an amine compound containing at least polyamine (C) Are synthesized.

The vinyl polymer moiety derived from the vinyl polymer (A) having two hydroxyl groups in one end region has excellent affinity with a wide range of pigment carriers and dispersion mediums by selecting an ethylenically unsaturated monomer constituting it, and a solvent. It functions as an affinity site. On the other hand, the amino group introduced by unwinding the hydroxyl group present in one end region of the vinyl polymer moiety and the urea binding moiety function as adsorption sites on the pigment surface oriented in acid.

Hereinafter, each component of a pigment dispersant is demonstrated.

(Vinyl polymer (A) having two hydroxyl groups in one end region)

The vinyl polymer (A) (hereinafter sometimes referred to as vinyl polymer (A)) having two hydroxyl groups in one end region constituting the pigment dispersant may have at least one of an ethylene oxide chain or a propylene oxide chain. The branch is obtained by radical polymerization of an ethylenically unsaturated monomer (a1) and an ethylenically unsaturated monomer (a2) copolymerizable with (a1) in the presence of a compound (a3) having two hydroxyl groups and one thiol group in a molecule thereof. It is preferable. The radical polymerization is preferably used in the presence of a polymerization initiator and a polymerization solvent.

(Ethylenic unsaturated monomer (a1) having at least one of an ethylene oxide chain or a propylene oxide chain))

The ethylenically unsaturated monomer (a1) is not particularly limited as long as it has at least one of an ethylene oxide chain or a propylene oxide chain, and conventionally known monomers can be used. As a specific example, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene Glycol monoethyl ether (meth) acrylate, diethylene glycol mono-2-ethylhexyl ether (meth) acrylate, dipropylene glycol monomethyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, Triethylene glycol monoethyl ether (meth) acrylate, tripropylene glycol monomethyl ether (meth) acrylate, tetraethylene glycol monomethyl ether (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate, polypropylene glycol Monomethyl ether (meth) acrylate, polyethylene glycol monolauryl ether (meth) acrylate, polyester Glycol monostearyl ether (meth) acrylate and octoxy polyethylene glycol polypropylene glycol (meth) acrylate of (poly) alkylene glycol monoalkyl ether (meth) acrylates; Phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxy tetraethylene glycol (meth) acrylate, phenoxy hexaethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate , Paracumylphenoxyethyl (meth) acrylate, paracumylphenoxyethylene glycol (meth) acrylate, paracumylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxy (Poly) alkylene glycol (meth) acrylates which have aromatic rings, such as polypropylene glycol (meth) acrylate and nonyl phenoxy poly (ethylene glycol propylene glycol) (meth) acrylate, etc. are mentioned. These ethylenically unsaturated monomers (a1) can be used individually or in combination of 2 or more types. The ethylene oxide chain and / or the propylene oxide chain of the ethylenically unsaturated monomer (a1) are used for the purpose of improving the dispersibility to the quinophthalone pigment. The ethylenically unsaturated monomer (a1) may have at least one of an ethylene oxide chain or a propylene oxide chain, and preferably has at least an ethylene oxide chain. The dispersibility with respect to a quinophthalone pigment is the number of moles of addition of ethylene oxide and / or propylene oxide in the ethylenically unsaturated monomer (a1) which forms a vinyl polymer (A), and the ethylenically unsaturated monomer which occupies in a vinyl polymer (A) It is influenced by the blending ratio of a1). As a preferable range, although it changes also with a quinophthalone pigment and a pigment dispersing agent, in the case of addition mole number of ethylene oxide and / or propylene oxide in an ethylenically unsaturated monomer (a1), 1-50 are preferable and 1-20 are More preferably, 4-13 are especially preferable. When the added mole number is 50 or less, compatibility with the solvent and dispersibility are good, and the viscosity hardly rises at the time of dispersion. Moreover, as for the compounding ratio of an ethylenically unsaturated monomer (a1), 10-90 weight% is preferable with respect to a total of 100 weight% with the ethylenically unsaturated monomer (a2) mentioned later, 20-80 weight% is more preferable, 30 ˜70 parts by weight is particularly preferred. Dispersibility is good when it is 10 weight% or more, and when it is 90 weight% or less, it is excellent in compatibility with a solvent, dispersibility is favorable, and the viscosity at the time of dispersion is favorable.

(Ethylenically unsaturated monomer (a2))

It will not specifically limit, if it is a monomer other than an ethylenically unsaturated monomer (a1), and is a monomer copolymerizable with an ethylenically unsaturated monomer (a1) as ethylenically unsaturated monomer (a2), According to a use, it can select suitably. For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth), tertiary butyl ( Meta) acrylate, isoamyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cetyl (meth) acrylate, decyl (meth) acrylic Latex, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, isomyristyl (meth) acrylate, stearyl (meth) acrylate, and isostearyl (meth) Linear or branched alkyl (meth) acrylates such as acrylate;

Cyclic alkyl, such as cyclohexyl (meth) acrylate, tertiary butyl cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and isobornyl (meth) acrylate (Meth) acrylates;

(Meth) acrylates having heterocycles such as tetrahydrofurfuryl (meth) acrylate and 3-methyl-3-oxetanyl (meth) acrylate;

(Meth) acrylates having an aromatic ring of benzyl (meth) acrylate and phenoxyethyl (meth) acrylate;

Fluoroalkyl (meth) acrylates such as trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, pafluorooctylethyl (meth) acrylate and tetrafluoropropyl (meth) acrylate (Meth) acryloxy modified polydimethylsiloxane (silicone large size); N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethyl (Meth) acrylates having tertiary amino groups such as aminopropyl (meth) acrylate and N, N-diethylaminopropyl (meth) acrylate; (meth) acrylamide, dimethyl (meth) acrylamide, N, N-substituted (meth) acrylamides such as N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, and acryloyl morpholine; and (meth) Nitriles such as acrylonitrile There. Furthermore, styrene, such as styrene and (alpha) -methylstyrene;

Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether and isobutyl vinyl ether; and fatty acid vinyls such as vinyl acetate and vinyl propionate.

Moreover, a carboxyl group-containing ethylenically unsaturated monomer can also be used together. Examples of the carboxyl group-containing ethylenically unsaturated monomer include (meth) acrylic acid, (meth) acrylic acid dimer, itaconic acid, maleic acid, fumaric acid, crotonic acid, 2- (meth) acryloyloxyethyl phthalate, and 2- (meth) acrylo Hydroxypropyl phthalate, 2- (meth) acryloyloxyethylhexahydrophthalate, 2- (meth) acryloyloxypropylhexahydrophthalate, β-carboxyethyl (meth) acrylate and ω-carboxypolycaprolactone ( Meth) acrylate, etc. are mentioned.

From the ethylenically unsaturated monomer mentioned above, 1 type, or 2 or more types can be selected and it is a methyl (meth) acrylate, ethyl (meth) acrylate, n- at least from a viewpoint of the solubility to solvent and tolerance. Some ethylenically unsaturated monomers are selected from propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and t-butyl (meth) acrylate. It is preferred to be used.

(Compound (a3) having two hydroxyl groups and one thiol group in a molecule)

As compound (a3) (hereinafter sometimes referred to as compound (a3)) having two hydroxyl groups and one thiol group in a molecule, a compound having two hydroxyl groups and one thiol group in a molecule is particularly It is not limited, For example, 1-mercapto- 1,1-methanediol, 1-mercapto- 1,1- ethanediol, 3-mercapto- 1, 2- propanediol (thioglycerine), 2- Mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,2 -Propanediol, 2-mercaptoethyl- 2-methyl- 1, 3- propanediol, 2-mercaptoethyl- 2-ethyl- 1, 3- propanediol, etc. are mentioned. Among these, 3-mercapto- 1,2-propanediol is preferable.

A compound (a3), an ethylenically unsaturated monomer (a1), an ethylenically unsaturated monomer (a2), and a polymerization initiator are optionally mixed in accordance with the molecular weight of the vinyl polymer (A) having two hydroxyl groups in one end region of interest. And heating to obtain a vinyl polymer (A). It is preferable to obtain compound (a3) by lump-shaped polymerization or solution polymerization using 0.5-30 weight part with respect to a total of 100 weight part of ethylenically unsaturated monomers (a1) and (a2), More preferably, 1- 20 weight part, More preferably, it is 2-15 weight part, Especially preferably, it is 2-10 weight part.

By using a compound (a3) in the said preferable range, the molecular weight of a vinyl polymer (A) can be adjusted to an appropriate range. 500-20,000 are preferable, as for the weight average molecular weight (Mw) of polystyrene conversion in the gel osmosis chromatography (GPC) of a vinyl polymer (A), 1,000-10,000 are more preferable, 2,000-7,500 are especially preferable. If it is 20,000 or less, the molecular weight of a vinyl polymer site | part becomes a suitable range, and a dispersibility effect is favorable, and if it is 500 or more, the molecular weight of a vinyl polymer site | part becomes a suitable range, and the effect of the steric repulsion as an affinity site | part to a pigment carrier and a solvent is It is enough, and aggregation of a pigment is fully suppressed.

(Polymerization initiator)

When superposing | polymerizing, 0.001-5 weight part of polymerization initiators can be used arbitrarily with respect to a total of 100 weight part of ethylenically unsaturated monomers (a1) and (a2). As the polymerization initiator, an azo compound and an organic peroxide can be used. Examples of the azo compound include 2,2'-azobisisobutylonitrile, 2,2'-azobis (2-methylbutylonitrile), 1,1'-azobis (cyclohexane1-carbonitrile), 2,2'- azobis (2, 4- dimethylvaleronitrile), 2, 2 -'- azobis (2, 4- dimethyl- 4-methoxyvaleronitrile), dimethyl 2, 2 -'- azobis ( 2-methylpropionate), 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis (2-hydroxymethyl propionitrile), and 2,2'-azobis [2- (2-imidazoline-2-yl) propane] etc. are mentioned. Examples of the organic peroxide include benzoyl peroxide, t-butylpabenzoate, cumene hydroperoxide, diisopropylpaoxydicarbonate, di-n-propylpaoxydicarbonate, di (2-ethoxyethyl) paoxydicarbonate and t-butyl Paoxyneodicanoate, t-butyl paoxy pibarate, (3,5,5-trimethylhexanoyl) paoxide, dipropionyl paoxide, diacetyl paoxide and the like. These polymerization initiators can be used individually or in combination of 2 or more types.

(Polymerization solvent)

In the case of solution polymerization, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, hexane, acetone, hexane, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate as a polymerization solvent. , Diethylene glycol dimethyl ether, diethylene glycol diethyl ether and the like are used, but are not particularly limited thereto. Although these polymerization solvent may be used in mixture of 2 or more types, it is preferable that it is a solvent used for an end use.

(Diisocyanate (B))

As a diisocyanate (B) which comprises a pigment dispersant, a conventionally well-known thing can be used, For example, aromatic diisocyanate (b1), aliphatic diisocyanate (b2), aromatic-aliphatic diisocyanate (b3), Alicyclic diisocyanate (b4) etc. are mentioned.

As aromatic diisocyanate (b1), xylene diisocyanate, 1, 3- phenylene diisocyanate, 4, 4'- diphenyl diisocyanate, 1, 4- phenylene diisocyanate, 4, 4'- diphenylmethane diisocyanate, 2, 4- tolylene diisocyanate, 2, 6- tolylene diisocyanate, 4, 4 -'- toluidine diisocyanate, naphthylene diisocyanate, 1, 3-bis (isocyanate methyl) benzene, etc. are mentioned.

Examples of the aliphatic diisocyanate (b2) include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1, 3-butylene diisocyanate, dodecamethylene diisocyanate, 2, 4, 4- trimethyl hexamethylene diisocyanate, etc. are mentioned.

As aromatic-aliphatic diisocyanate (b3), it is ω, ω'- diisocyanate-1,3-dimethylbenzene, ω, ω'- diisocyanate-1,4-dimethylbenzene, ω, ω'- diisocyanate-1 , 4-diethyl benzene, 1, 4- tetramethyl xylene diisocyanate, 1, 3- tetramethyl xylene diisocyanate, etc. are mentioned.

Examples of the alicyclic diisocyanate (b4) include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, and 1,4- Cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, etc. are mentioned.

The diisocyanate (B) enumerated above is not necessarily limited to these, It can also be used in combination of 2 or more types.

As diisocyanate (B), an aliphatic diisocyanate (b2), an aromatic aliphatic diisocyanate (b3), and an alicyclic diisocyanate (b4) are preferable from a viewpoint of egg yolk modification, Furthermore, alicyclic diisocyanate (b4) ), And most preferably 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (alias: isophorone diisocyanate, IPDI).

In addition to the diisocyanate, some polyisocyanates having three or more isocyanate groups in one molecule may be used within the range of not gelling at the time of producing the pigment dispersant. These include the isocyanurate body of the diisocyanate (B) enumerated above, the trimethylolpropane adduct type, and a biuret type, for example.

(Urethane Prepolymer (E))

Urethane prepolymer (E) means what can be obtained by making the hydroxyl group which is a vinyl polymer (A) which has two hydroxyl groups in one terminal area | region, and the isocyanate group of diisocyanate (B) react.

For example, when the number of moles of the vinyl polymer (A) is α and the number of moles of the diisocyanate (B) is β, when α / β = α / (α + 1), a urethane prepolymer having an isocyanate group at both ends is theoretically formed. You can get it. If α is a positive integer, the larger the α, the more the molecular weight.

In the synthesis | combination of a urethane prepolymer (E), a well-known synthetic catalyst can be used, For example, a tertiary amine compound, an organometallic compound, etc. are mentioned.

Examples of the tertiary amine compound include triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, diazabicycloundecene (DBU), and the like.

Examples of the organometallic compound include tin compounds and non-tin compounds.

As the tin compound, for example, dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaliate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, di Butyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloro Acetate, 2-ethylhexanoic acid tin, etc. are mentioned.

As the non-tin compound, for example,

Titanium series such as dibutyltitanium dichloride, tetrabutyl titanate, butoxytitanium trichloride, and lead oleate;

Lead systems such as lead 2-ethylhexanoate, lead benzoate and naphthenate;

Iron-based compounds such as iron 2-ethylhexanoate and iron acetylacetate;

Cobalt compounds such as cobalt benzoate and cobalt 2-ethylhexanoate;

Zinc-based compounds such as zinc naphthenate and zinc 2-ethylhexanoate; and

Zirconium system, such as zirconium naphthenate.

In the said catalyst, dibutyltin dilaurate (DBTDL), 2-ethylhexanoic acid tin, etc. are preferable at the point of reactivity or hygiene.

Although catalysts, such as the said tertiary amine compound and an organometallic compound, may be used independently as needed, they can also be used together.

The organometallic compound catalyst used in the synthesis of the urethane prepolymer (E) also significantly promotes the reaction even in the reaction with the amine described later.

In the synthesis of the urethane prepolymer (E), a known solvent is suitably used. The use of a solvent serves to facilitate reaction control.

Examples of the solvent used for this purpose include ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, hexane, acetone, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, and diethylene glycol. Monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether and the like are used, but are not particularly limited thereto.

The concentration in the urethane prepolymer reaction system in the case of using a solvent is, in terms of solid content concentration of the urethane prepolymer, preferably 30 to 95% by weight from the viewpoint of reaction control, and more preferably 40 from the viewpoint of viscosity control. 90 wt%. If it is 30% by weight or more, the reaction is fast and no unreacted material remains. When it is 95 weight% or less, reaction does not progress rapidly partly and control of molecular weight etc. is easy.

The urethanation reaction which makes the urethane prepolymer (E) by making the hydroxyl group of a vinyl polymer (A), and the isocyanate group of diisocyanate (B) react can be various methods. Although it is largely divided into the method of adding the whole amount and reacting, and 2) the vinyl polymer (A) and the solvent in the flask as needed, the diisocyanate (B) is dripped, and adding a catalyst as needed, but reaction is precisely 2) is preferable in the case of control.

As for the temperature of reaction which obtains a urethane prepolymer (E), 120 degrees C or less is preferable. More preferably, it is 50-110 degreeC. When the temperature is higher than 110 ° C, it becomes difficult to control the reaction rate, so that a urethane prepolymer having a predetermined molecular weight and structure cannot be obtained. It is preferable to perform a urethanation reaction at 50-110 degreeC for 1 to 20 hours in presence of a catalyst.

As for the compounding molar ratio of the diisocyanate (B) with respect to a vinyl polymer (A), 1.01-3.00 are preferable from a viewpoint of the productivity of a urethane prepolymer, and the design of the dispersing agent which is a final composite (balance of a pigment adsorption site and a solvent affinity site) 1.30-2.30 are more preferable at the point of a viewpoint, and 1.50-2.00 are the most preferable from a viewpoint of the dispersion stability of the pigment dispersion using the dispersing agent which is a final composite. When the said compounding molar ratio is too small, the dispersing agent which is a final product will have a high molecular weight, the viscosity of the pigment dispersion using it, and also the viscosity of the coating material and ink using it will become a practical problem. In addition, as mentioned above, when the said compounding molar ratio is larger than 3.00, the diisocyanate (B) which does not have a vinyl polymerization part derived from a vinyl polymer (A), and the urethane site | part derived from it increase, and the performance of the dispersing agent which is a final product deteriorates. There is.

(Polyamine (C))

As a polyamine (C) which comprises a pigment dispersant, it is a compound which has at least two primary and / or secondary amino groups, and is used in order to react with an isocyanate group and produce | generate a urea bond. As such an amine, a diamine (c1) can be mentioned first.

As diamine (c1), the diamine (c1-1) which has two primary amino groups, the diamine (c1-2) which has two secondary amino groups, and the diamine (c1-3) which has a primary and secondary amino group are mentioned. Can be.

As a diamine (c1-1) which has two primary amino groups, a well-known thing can be used, Specifically,

Ethylenediamine, propylenediamine [nickname: 1,2-diaminopropane or 1,2-propanediamine], trimethylenediamine [nickname: 1,3-diaminopropane or 1,3-propanediamine], tetramethylenediamine [ Alias: 1,4-diaminobutane], 2-methyl- 1,3-propanediamine, pentamethylenediamine [alias: 1,5-diaminopentane], hexamethylenediamine [alias: 1,6-diaminohexane ], Aliphatic diamines, such as 2, 2- dimethyl- 1, 3- propane diamine, 2, 2, 4- trimethyl hexamethylene diamine, and tolylene diamine;

Alicyclic diamines such as isophorone diamine and dicyclohexyl methane-4,4'-diamine; and

And aromatic diamines such as phenylenediamine and xylenediamine.

In addition, as a diamine (c1-2) which has two secondary amino groups, a well-known thing can be used, Specifically,

N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N'-di-tert- butylethylenediamine, etc. are mentioned.

In addition, as a diamine (c1-3) which has a primary and a secondary amino group, a well-known thing can be used, Specifically,

N-methylethylenediamine [nickname: methylaminoethylamine], N-ethylethylenediamine [nickname: ethylaminoethylamine], N-methyl-1,3-propanediamine [nickname: N-methyl-1,3-dia] Minopropane or methylaminopropylamine], N, 2-methyl- 1, 3- propanediamine, N-isopropylethylenediamine [alias: isopropylaminoethylamine], N-isopropyl- 1, 3- diamino propane [Nickname: N-isopropyl-1,3-propanediamine or isopropylaminopropylamine] and N-lauryl-1,3-propanediamine [nickname: N-lauryl-1,3-diaminopropane or la] Urylaminopropylamine], and the like.

The polyamine constituting the pigment dispersant is a compound having at least two primary and / or secondary amino groups, and this urea group, where primary and / or secondary amines react with isocyanate groups to form urea groups, becomes a pigment adsorption site, When the polyamine (C) is a compound having two primary and / or secondary amino groups at both ends and a secondary and / or tertiary amino group at both ends, the adsorption to the quinophthalone pigment is increased. , Especially preferred.

As such polyamine (C), the polyamine (c2) which has two primary and / or secondary amino groups at the both ends as follows, and has a secondary and / or tertiary amino group in addition to both ends is mentioned.

As polyamine (c2), the polyamine (c2-1) which has a secondary amino group other than both ends, and the polyamine (c2-2) which has a tertiary amino group other than both ends are mentioned.

As a polyamine (c2-1) which has a secondary amino group other than both ends, it is the iminobispropylamine [an alias N, N-bis (3-aminopropyl) amine], N, N'-bisaminopropyl-1, for example. And 3-propylene diamine and N, N'-bisaminopropyl-1,4-butylenediamine.

Examples of the polyamine (c2-2) having a tertiary amino group in addition to both ends thereof include methyliminobispropylamine (nickname N, N-bis (3-aminopropyl) methylamine) and lauryliminobispropylamine. N, N-bis (3-aminopropyl) laurylamine] etc. are mentioned.

As a polyamine (C) which comprises a pigment dispersant, the polymer (c3) which has two or more primary and / or secondary amino groups, and has a molecular weight distribution can also be used.

As a polymer (c3) which has a primary and / or secondary amino group, the homopolymer of an ethylenically unsaturated monomer which has a primary amino group, or an ethylenically unsaturated monomer which has a secondary amino group, for example, vinylamine or an arylamine (so-called Polyvinylamine or polyaryl amine) or copolymers of these and other ethylenically unsaturated monomers and ring-opening polymers of ethyleneimine, polycondensates of ethylene chloride and ethylenediamine, or ring-opening polymers of oxazolidone-2 (so-called polyethyleneimines Is preferably selected from.

Among the (c1), (c2) and (c3) exemplified as the polyamine (C), (c1) and (c2) are preferable in terms of synthesis control, and (c2) is more preferable in terms of dispersibility. Most preferably, it is polyamine (c2-1) which has a secondary amino group other than both ends.

As an amine compound which comprises a pigment dispersing agent, monoamine can also be used other than a polyamine (C). As a monoamine, it is a monoamine compound which has one primary amino group or a secondary amino group in a molecule | numerator, and a monoamine stops reaction for suppressing too high molecular weight in reaction of a diisocyanate (B) and a polyamine (C). Used as a zero. Monoamine may have a polar functional group other than a primary amino group or a secondary amino group in a molecule | numerator. As such a polar functional group, a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, a cyano group, a nitroxyl group, etc. are mentioned.

As a monoamine, a conventionally well-known thing can be used, Specifically,

Aminomethane, aminoethane, 1-aminopropane, 2-aminopropane, 1-aminobutane, 2-aminobutane, 1-aminopentane, 2-aminopentane, 3-aminopentane, isoamylamine, N-ethylisoa Milamine, 1-aminohexane, 1-aminoheptane, 2-aminoheptane, 2-octylamine, 1-aminononane, 1-aminodecane, 1-aminododecane, 1-aminotridecane, 1-aminohexa Decane, stearylamine, aminocyclopropane, aminocyclobutane, aminocyclopentane, aminocyclohexane, aminocyclododecane, 1-amino-2-ethylhexane, 1-amino-2-methylpropane, 2-amino-2 -Methyl propane, 3-amino-1-propene, 3-aminomethylheptane, 3-isopropoxypropylamine, 3-butoxypropylamine, 3-isobutoxypropylamine, 2-ethylhexoxypropylpropylamine, 3-decyoxypropylamine, 3-laurioxypropylamine, 3-myristyloxyloph Philamine, 2-aminomethyltetrahydrofuran, dimethylamine, diethyl amine, N-methylethylamine, N-methylisopropylamine, N-methylhexylamine, diisopropylamine, din-propylamine, din -Butylamine, disec-butylamine, N-ethyl- 1, 2- dimethylpropylamine, piperidine, 2-pipecoline, 3-pipecoline, 4-pipecoline, 2, 4- lupetidine, 2 6-Lupetidine, 3,5-Lupetidine, 3-piperidinemethanol, pipecolinic acid, isonifecotic acid, methyl isonipetate, ethyl isonipecatetate, 2-piperidinethanol, 4-piperidine ethanol, 4-piperidine butyrate, 4-piperidinol, pyrrolidine, 3-aminopyrrolidine, 3-pyrrolidinol, indolin, aniline, N-butylaniline, o- Aminotoluene, m-aminotoluene, p-aminotoluene, o-benzylaniline, p-benzylaniline, 1-anilinonaphthalene, 1-aminoanthraquinone, 2-aminoanthraquinone, 1-ami Anthracene, 2-aminoanthracene, 5-aminoisoquinoline, o-aminodiphenyl, 4-aminodiphenyl ether, β-aminoethylbenzene, 2-aminobenzophenone, 4-aminobenzophenone, o-aminoacephenone, m-aminoacetphenone, p-aminoacephenone, benzylamine, N-methylbenzylamine, 3-benzylaminopropionic acid ethyl ether, 4-benzylpiperidine, α-phenylethylamine, phenethylamine, p-methoxy Phenethylamine, furfurylamine, p-aminoazobenzene, m-aminophenol, p-aminophenol, arylamine, diphenylamine, and the like.

Especially, the monoamine compound which is an aliphatic amine which has no rigidity and has only a secondary amino group has good dispersibility and is preferable.

As an aliphatic monoamine compound which has only a secondary amino group,

Dimethylamine, diethylamine, N-methylethylamine, N-methylisopropylamine, N-methylhexylamine, diisopropylamine, din-propylamine, din-butylamine, disec-butylamine, N -Ethyl- 1, 2- dimethylpropylamine, piperidine, 2-pipecoline, 3-pipecoline, 4-pipecoline, 2, 4- lupetidine, 2, 6- lupetidine, 3, 5- Lufetidine, 3-piperidinmethanol, 2-piperidinethanol, 4-piperidinethanol, 4-piperidinol, pyrrolidine, 3-aminopyrrolidine, 3-pyrrolidinol, and the like. Can be.

In addition, since the tertiary amino group does not have active hydrogen reacting with the isocyanate group, the diamine having a primary or secondary amino group and a tertiary amino group can be used as a monoamine constituting the pigment dispersant, and at the polymer end of the dispersant A tertiary amino group having an effect of improving the pigment adsorption capacity can be introduced.

As a diamine which has a primary or secondary amino group and a tertiary amino group, it is N, N- dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dimethyl- 1, 3- propanediamine, and N, N, Diamine which has primary amino groups and tertiary amino groups, such as 2, 2- tetramethyl- 1, 3- propanediamine; And

The diamine which has secondary amino groups and tertiary amino groups, such as N, N, N'- trimethylethylenediamine, is mentioned.

You may use these monoamines in mixture of 1 type, or 2 or more types. Moreover, the active hydrogen of the urea bond after reaction of a primary amine group and an isocyanate group is low in reactivity, and it reacts with an isocyanate group more than the polymerization conditions of a dispersing agent, and molecular weight does not become large.

(Method of producing a pigment dispersant)

Pigment dispersants,

In the presence of the compound (a3) which has two hydroxyl groups and one thiol group in a molecule | numerator, one side formed by radically polymerizing the ethylenically unsaturated monomer (a1) and ethylenically unsaturated monomer (a2) shown by General formula (1) A first step of producing a vinyl polymer (A) having two hydroxyl groups in the end region,

A second step of producing a urethane prepolymer (E) having an isocyanate group at both ends formed by reacting a hydroxyl group of a vinyl polymer (A) having two hydroxyl groups in one end region with an isocyanate group of a diisocyanate (B); Fair,

It is preferable to manufacture by the 3rd process of making the isocyanate group of the urethane prepolymer (E) which has an isocyanate group at both ends, and the primary and / or secondary amino group of a polyamine (C) react.

The urea reaction for obtaining a urethane urea resin from a urethane prepolymer (E), a polyamine (C), or a polyurethane urea having a primary or secondary amino group at the end is as follows: 1) Putting a solution of the urethane prepolymer (E) into a flask and (C) It is largely divided into the method of dripping, and the method of 2) polyamine (C) and the solution which consists of a solvent as needed in the flask, and the solution of urethane prepolymer (E). Either method may be used, but method 2) is preferable in view of the dispersibility of the pigment dispersant synthesized.

As for the temperature of a urea reaction, 100 degrees C or less is preferable. More preferably, it is 70 degrees C or less. Even when the reaction rate is not fast and controlled even at 70 ° C, 50 ° C or less is more preferable. When it is higher than 100 ° C, it is difficult to control the reaction rate, and it is difficult to obtain a urethane urea resin having a predetermined molecular weight and structure.

In addition, the compounding ratio of a urethane prepolymer (E) and a polyamine (C) is not specifically limited, It selects arbitrarily according to the kind of pigment.

The end point of reaction can be judged by the loss of the isocyanate peak by the isocyanate% measurement by IR titration or IR measurement.

It is preferable that the polystyrene conversion weight average molecular weight (Mw) in the gel osmosis chromatography (GPC) of the pigment dispersant contained in the coloring composition for color filters is 1,000-100,000, More preferably, 1,500-50,000, Especially preferably, Is 1,500-20,000.

If the weight average molecular weight is 1,000 or more, the stability of the pigment composition is good, and if it is 100,000 or less, the interaction between resins becomes a good range, and the viscosity of the pigment composition does not increase. Moreover, it is preferable that the amine value of the obtained dispersing agent is 1-100 mgKOH / g, More preferably, it is 2-80 mgKOH / g, More preferably, it is 3-60 mgKOH / g. When the amine value is 1 mgKOH / g or more, the pigment and the functional groups adsorbed are sufficient, so that the dispersion of the pigment is good. When the amine value is 100 mgKOH / g or less, aggregation of the pigments does not occur and the effect of lowering the viscosity is sufficient and the appearance of the coating film is sufficient. Is good.

It is preferable to use 5 weight%-70 weight% with respect to a quinophthalone pigment, More preferably, it is 10 weight%-50 weight%. If it is 5 weight% or more, a favorable pigment dispersion effect can be acquired, and if it is 70 weight% or less, it will not adversely affect heat resistance etc. other than dispersibility, for example.

(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 alkylnaphthaline sulfonate, sodium alkyl diphenyl ether disulfonate, lauryl sulfate Anionic surfactants such as monoethanolamine, lauryl sulfate triethanolamine, lauryl ammonium sulfate, stearic acid monoethanolamine, monoethanolamine of styrene-acrylic acid copolymer, and polyoxyethylene alkyl ether phosphate ester; polyoxyethylene oleate ether Nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate; alkyl quaternary ammonium salts; Such as ethylene oxide adducts Cationic surfactants; Amphoteric surfactants, such as alkyl betaine, such as alkyl dimethylamino acetic acid betaine, and alkyl imidazoline, These can be used individually or in mixture of 2 or more types, It is necessarily limited to these It is not.

Content of surfactant is preferably 0.1-55 weight part, More preferably, it is 0.1-45 weight part with respect to 100 weight part of coloring agents. If content of a resinous dispersing agent is 0.1 weight part or more, the added effect can fully be acquired, and if content is 55 weight part or less, dispersion will be very favorable.

<Photopolymerizable monomer>

One embodiment of the coloring composition may contain a photopolymerizable monomer. The photopolymerizable monomer contains monomers or oligomers which are cured by ultraviolet rays, heat or the like to produce a transparent resin, and these may be used alone or in combination of two or more thereof. It is preferable that it is 5-400 weight part with respect to 100 weight part of coloring agents, and, as for content of a photopolymerizable monomer, it is more preferable that it is 10-300 weight part from a viewpoint of photocurability and developability.

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-hydroxy ethyl (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 -Hexane diol glycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, diphene Erythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, (meth) acrylic acid ester of methylolated melamine, epoxy (meth) acrylic Various acrylic esters and methacrylic acid esters, such as a rate and urethane acrylate, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide , N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile, EO modified bisphenol A di (meth) acrylate, 1, 4- butanediol di (meth) acrylate, diethylene glycol di ( Meta) acrylate, neopentyl glycol di (meth) acrylate, polyester (meth) acrylate, tris (acryloxyethyl) isocyanurate, tris (Methacryloxyethyl) isocyanurate, caprolactone modified dipentaerythritol hexaacrylate, ditrimethylol propane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, ω-carboxypolycaprolactone mono Acrylate, ω-carboxypolycaprolactone monomethacrylate, 2-acryloyloxyethyl amber acid, 2-methacryloyloxyethyl amber acid, 2-acryloyloxypropyl amber acid, 2-methacryloyloxypropyl Succinic acid, methoxy ethylene glycol acrylate, methoxy ethylene glycol methacrylate, methoxy diethylene glycol acrylate, methoxy diethylene glycol methacrylate, methoxy triethylene glycol acrylate, methoxy triethylene glycol methacrylate, meth Methoxy propylene glycol acrylate, methoxy propylene glycol methacrylate, methoxy dipropylene glycol 2-acryloyl hydroxyethyl amber acid (Acrylate, methoxy dipropylene glycol methacrylate, 2-hydroxy-3- phenoxypropyl acrylate, 2-hydroxy-3- phenoxypropyl methacrylate, or a commercial item) Although the brand name M-5300 may be mentioned, it is not necessarily limited to these.

<Photopolymerization initiator>

The coloring composition of this embodiment may contain a photoinitiator. When the said composition is hardened by ultraviolet irradiation and a filter segment is formed by the photolithographic method, a photoinitiator etc. can be added and it can be prepared in the form of a solvent developing type or an alkali developing type photosensitive coloring composition. It is preferable that content of a photoinitiator is 2-200 weight part with respect to 100 weight part of coloring agents, More preferably, from a viewpoint of photocurability and developability, for example, 3-150 weight part, 5-150 weight part, 5 200 parts by weight and 10 to 150 parts by weight may be taken.

As a photoinitiator, 4-phenoxydichloroacetphenone, 4-t-butyl dichloroacetphenone, diethoxy acetphenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 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 Acetphenone type compounds, such as these; Benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; Benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3 ', 4,4'-tetra ( benzophenone compounds such as t-butylpaoxycarbonyl) benzophenone; Thioxanthones such as thioxanthone, 2-chlorothioxanthone, 2-methyl thioxanthone, 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-tril) -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-benzoyl oxime)] or O- (acetyl) -N- (1-phenyl- 2-oxo- 2- (4'- methoxy- naphthyl) ethylidene) hydroxylamine, etc. Oxime Ester compounds; Phosphine compounds such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; Quinone compounds such as 9,10-phenanthrene quinone, camphor quinone and ethyl anthraquinone; Borate compounds; Carbazole compounds; Imidazole compound; or titanocene compound or the like is used. These photoinitiators can be used individually by 1 type or in mixture of 2 or more types in arbitrary ratio as needed.

<Sensitizer>

One embodiment of a coloring composition may contain a sensitizer.

Examples of the sensitizer include unsaturated ketones represented by calcon 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, acridine derivatives, azine derivatives such as xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, melocyanine derivatives and oxonol derivatives , Thiazine derivatives, oxazine derivatives, indolin derivatives, azulene derivatives, azulenium derivatives, scarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporpyrazine derivatives , Phthalocyanine derivatives, tetraazaporpyrazine derivatives, tetraquinoxaliloporpyrazine derivatives, naph Rocyanine derivatives, subphthalocyanine derivatives, pyryllium derivatives, thiopyryllium derivatives, tetraphylline derivatives, anarylene derivatives, spiroparan derivatives, spiroxazine derivatives, thiospyropyran derivatives, metal arene complexes, organic ruthenium complexes, Or Michler's ketone derivatives, biimidazole derivatives, α-acyloxyesters, acylphosphine oxides, methylphenylglyoxylates, benzyl, 9,10-phenanthrenequinones, camphorquinones, ethyl anthraquinones, 4,4'-di Ethyl isophthalophenone, 3,3 ', or 4,4'-tetra (t-butylpaoxycarbonyl) benzophenone, 4,4'-diethylaminobenzophenone, and the like.

More specifically, "The Pigment Handbook" by Makoto Okawara (Kodansha, 1986), "Chemicals of Functional Pigments" by Shiko Okawara (Siemshi, 1981), Ikemori Chuzabu Although the sensitizer described in "special functional material" compiled by Roh et al. (1986, SIEMC) is mentioned, It is not limited to these. In addition, a sensitizer which shows absorption with respect to the light from ultraviolet to a near infrared region can also be contained.

A sensitizer 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 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.

<Polyfunctional thiol>

One embodiment of a coloring composition may contain the polyfunctional thiol which functions as a chain transfer agent.

The polyfunctional thiol may be a compound having two or more thiol groups, for example, hexanedithiol, decandithiol, 1,4-butanediolbisthiopropionic acid, 1,4-butanediolbisthioglycolate, ethylene glycol bisthioglyco Ethylene glycol bisthiopropionic acid, trimethylol propane tristhioglycolate, trimethylol propane tristyopric acid, trimethylol propane tris (3-mercapto butyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakis Thiopropionic acid, 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 etc. are mentioned. 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 solid content before the coloring composition (100% by weight). If content of a polyfunctional thiol is 0.1 weight% or more, the addition effect of a polyfunctional thiol will fully be exhibited, and if it is 30 weight% or less, it will become a range with a favorable sensitivity, and resolution will increase.

<Antioxidant>

One embodiment of a coloring composition may contain antioxidant. Since antioxidant prevents the photoinitiator and thermosetting compound contained in a coloring composition from oxidizing and yellowing by the thermal process at the time of thermosetting or ITO annealing, the transmittance | permeability of a coating film can be made high. Therefore, by including the antioxidant, yellowing due to oxidation during the heating step can be prevented, and a high coating film transmittance can be obtained.

The "antioxidant" may be a compound having an ultraviolet absorption function, a radical supplement function, or a peroxide decomposition function, and specifically, as an antioxidant, an interference phenol type, an interference amine type, a phosphorus type, a sulfur type, a benzotriazole type, or a benzophenone type , A hydroxylamine-based compound, a salicylic acid ester-based compound, and a triazine-based compound may be mentioned, and known ultraviolet absorbers, antioxidants and the like can be used.

Among these antioxidants, interference phenol-based antioxidants, interference amine-based antioxidants, phosphorus-based antioxidants or sulfur-based antioxidants may be mentioned as preferable ones from the viewpoint of the transmittance, sensitivity and compatibility of the coating film. More preferably, they are interference phenolic antioxidants, interference amine antioxidants, or phosphorus antioxidants.

These antioxidant can be used individually by 1 type or in mixture of 2 or more types in arbitrary ratio as needed. Moreover, since content of antioxidant is 0.5-5.0 weight% based on solid content weight of a coloring composition as a reference | standard (100 weight%), since brightness and a sensitivity are favorable, it is more preferable.

<Amine compound>

One embodiment of the coloring composition can contain an amine compound having a function of reducing oxygen dissolved and present.

Examples of such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate and 2-dimethylaminoethyl benzoate. And 4-ethylamino benzoic acid 2-ethylhexyl, and N, N-dimethyl paratoluidine.

<Leveling agent>

In one embodiment of the coloring composition, in order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent. 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 Toe Dow Corning Co., Ltd. and BYK-333 by BIC Chem Corporation are mentioned. As a specific example of the dimethylsiloxane which has a polyester structure in a principal chain, BYK-310, BYK-370, etc. made by BIC Chem Corporation are mentioned. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain may be used in combination. It is preferable to use content of a leveling agent normally 0.003-0.5 weight% based on the total weight of a coloring composition (100 weight%).

As a leveling agent especially preferable, it is a kind of what is called surfactant which has a hydrophobic group and a hydrophilic group in a molecule | numerator. Specifically, while having a hydrophilic group, the solubility in water is low, and when added to a coloring composition, the surface tension lowering ability is low, and the wettability to the glass plate is good regardless of the low surface tension lowering ability. In addition, it is preferable that the charging property can be sufficiently suppressed in the amount of addition in which defects in the coating film due to foaming do not appear. As a leveling agent having such desirable properties, dimethylpolysiloxanes having polyalkylene oxide units are preferably used. As a polyalkylene oxide unit, there exist a polyethylene oxide unit and a polypropylene oxide unit, and dimethyl polysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

In addition, the binding form of the polyalkylene oxide unit with the dimethylpolysiloxane has a pendant form in which the polyalkylene oxide unit is bonded in a repeating unit of dimethylpolysiloxane, a terminal modified form bonded to the end of dimethylpolysiloxane, and alternately and repeatedly bonded to dimethylpolysiloxane. Any of linear block copolymer type may be used. Dimethyl polysiloxane which has a polyalkylene oxide unit is marketed from Toray Dow Corning Corporation, For example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-291, 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 auxiliary to the leveling agent. You may use surfactant in mixture of 2 or more types.

As anionic surfactant, Polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, the alkali salt of a styrene-acrylic acid copolymer, sodium alkylnaphthalin sulfonate, sodium alkyl diphenyl ether disulfonate, lauryl sulfate monoethanolamine, Lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of a styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate ester, etc. are mentioned.

Examples of the cationic surfactants include alkyl quaternary ammonium salts and their ethylene oxide adducts. As a nonionic surfactant, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate Such as; Amphoteric surfactants, such as alkylbetaines, such as alkyldimethylamino acetate acetate, and alkyl imidazoline, and a fluorine-type and silicone type surfactant are mentioned.

<Hardening agent, hardening accelerator>

One embodiment of a coloring composition may contain a hardening | curing agent, a hardening accelerator, etc. as needed in order to assist hardening of a thermosetting resin. Phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds, and the like are effective as the curing agent, but are not particularly limited to these, and any curing agent may be used as long as it can react with the thermosetting resin. You may also do it. Moreover, among these, the compound which has two or more phenolic hydroxyl groups in 1 molecule, and an amine hardening | curing agent are mentioned as a preferable thing. As the curing accelerator, for example, an amine compound (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine). , 4-methyl-N, N-dimethylbenzylamine, etc.), quaternary ammonium chloride compounds (for example, triethylbenzyl ammonium chloride, etc.), block isocyanate compounds (for example, dimethylamine, etc.), imidazole derivative bicyclic Amidine compounds and their salts (e.g., imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenyl) Midazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole and the like), phosphorus compound (for example, triphenylphosphine Etc.), guanamine compounds (for example, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (for example, 2,4-diamino-6) Methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, isocyanuric acid adduct, etc. can be used. These may be used individually by 1 type and may use 2 or more types together. As content of a hardening accelerator, 0.01-15 weight part is preferable with respect to 100 weight part of thermosetting resins.

<Other additive component>

One embodiment of a coloring composition may contain another additive component as needed. For example, storage stabilizers may be included to stabilize the viscosity over time of the composition. Moreover, in order to improve adhesiveness with a transparent substrate, you may contain adhesive improvers, such as a silane coupling agent.

As a storage stabilizer, For example, organic acids, such as quaternary ammonium chloride, such as benzyl trimethyl chloride and diethylhydroxyamine, lactic acid, and ethane diacid, its methyl ether, t-butyl pyrocatechol, tetraethylphosphine, tetraphenyl Organic phosphines, phosphites, such as phosphine, etc. are mentioned. A storage stabilizer can be used in the quantity of 0.1-10 weight part with respect to 100 weight part of coloring agents.

As an adhesion promoter, (meth) acrylsilanes, such as vinylsilanes, such as a vinyl tris ((beta) -methoxyethoxy) silane, vinylethoxysilane, and a vinyl trimethoxysilane, and (gamma) -methacryloxypropyl trimethoxysilane. , β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxy Epoxysilanes such as silane, β- (3,4-epoxycyclohexyl) methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and N-β ( Aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane and γ-aminopropyltri Toxysilane, (gamma) -aminopropyl trimethoxysilane, N-phenyl- (gamma) -aminopropyl trimethoxysilane, N- Amino carbonyl -γ- can be mentioned amino silanes such as the propyl triethoxysilane, γ- mercaptopropyltrimethoxysilane, γ- mercaptopropyl the tree with a silane coupling agent such as thio silanes such as silane. An adhesion improving agent can be used in the quantity of 0.01-10 weight part, Preferably it is 0.05-5 weight part with respect to 100 weight part of coloring agents in a coloring composition.

<Manufacturing method of a coloring composition>

In one embodiment of the coloring composition (hereinafter also referred to as a pigment dispersion), the colorant is added to a colorant carrier such as binder resin and / or a solvent, preferably a kneader, a two-stage roll mill, a three-stage roll mill, It can manufacture by disperse | distributing finely using various dispersion means, such as a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an atrito. Under the present circumstances, when 2 or more types of coloring agents are included, 2 or more types of coloring agents may be disperse | distributed simultaneously to a coloring agent support | carrier, and what disperse | distributed to the coloring agent support | carrier separately may be mixed. Moreover, when the solubility of a coloring agent is high, it is not necessary to disperse | distribute finely as mentioned above as long as the solubility to the solvent to be used is high, and it melt | dissolves by stirring and a foreign material is not confirmed.

When using as a photosensitive coloring composition (resist material) for color filters, it can prepare as a solvent developing type or an alkali developing type coloring composition. A solvent developing type or alkali developing type coloring composition can adjust and adjust the said pigment dispersion, a photopolymerizable monomer, and / or a photoinitiator, a solvent, other dispersing adjuvant, an additive, etc. as needed. A photoinitiator may be added at the stage of preparing a coloring composition, and may be added later to the prepared coloring composition.

<Removal of Coarse Particles>

One embodiment of the coloring composition is 5 μm or more coarse particles, preferably 1 μm or more coarse particles, more preferably 0.5 μm or more coarse particles and mixed dust by means of centrifugation, filtration by a sintered filter or membrane filter, or the like. It is preferable to remove. Thus, it is preferable that a coloring composition does not contain particle | grains 0.5 micrometer or more substantially. More preferably, it is 0.3 micrometer or less.

<Color filter>

Next, the color filter will be described. A color filter is provided with the filter segment formed using one Embodiment of a coloring composition. As a color filter, what has a red filter segment, a green filter segment, and a blue filter segment is mentioned. Further, the color filter may include a magenta filter segment, a cyan filter segment, and a yellow filter segment.

It is preferable that one embodiment of a coloring composition is used for formation of a red, green, or yellow filter segment, and it is especially preferable to be used for a green filter segment. The color filter should just be formed from the coloring composition which is at least 1 filter segment one embodiment of this invention, and the coloring agent used for formation of the filter segment of the other color which does not use the coloring composition which is one embodiment of this invention, A conventionally well-known thing can be used.

As a coloring agent used for a red filter segment, 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, And red pigments such as 254, 255, 264, 270, 272, 273, 274, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, or 287. Moreover, red dyes, such as xanthene type, azo type, disazo type, anthraquinone type, can also be used. Specifically, salt-forming compounds of xanthene-based acid dyes such as CI acid red 52, 87, 92, 289, 338, etc. may be mentioned.

In addition, an orange colorant and / or a yellow colorant can be used together in a red filter segment. For example, orange pigments such as CI Pigment Orange 38, 43, 71, or 73 and / or 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 Yellow pigments such as 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, or 221. Can be mentioned. Orange dyes and / or yellow dyes such as chinoline, azo, disazo and methine may also be used.

As a coloring agent used for a green filter segment, green pigments, such as CI pigment green 7, 36, 37, 58, are mentioned, for example. Moreover, blue pigments, such as an aluminum phthalocyanine pigment, can also be used. A yellow coloring agent can be used together in a green filter segment, and the yellow coloring agent mentioned by description of a red filter segment is mentioned specifically ,.

As a coloring agent used for a blue filter segment, CI pigment blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, Blue pigments, such as 22, 60, and 64, are mentioned. Moreover, purple pigment can be used together. As a purple pigment which can be used together, CI pigment violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 27, And purple pigments such as 29, 30, 31, 32, 37, 39, 40, 42, 44, 47, 49 and 50. Moreover, you may use the basic dye which shows blue or purple, and the salt-forming compound of an acid dye. In the case of using a dye, triarylmethane-based dyes or xanthene-based dyes are preferable in terms of lightness.

<Manufacturing method of color filter>

One embodiment of a color filter can be manufactured according to the printing method or the photolithography method.

Since formation of the filter segment by the printing method is patterned only by repeating printing and drying of the coloring composition prepared as a printing ink, it is low cost and excellent in mass productivity as a manufacturing method of a color filter. In addition, with the development of printing technology, it is possible to print fine patterns having a high degree of precision and smoothness. In order to print, it is preferable to set it as a composition which prevents ink from drying and solidifying 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 adjustment with a dispersing agent and a extender pigment can also be performed.

In the case of forming the filter segment by the photolithography method, the spray coating method, the spin coating method, the slit coating method, the roll coating method, or the like, on the transparent substrate, the coloring composition prepared as the solvent developing type or the alkali developing type coloring resist material is used. It apply | coats so that the thickness of a dry film may be 0.2-5 micrometers by the coating method of the. The film dried as needed is subjected to ultraviolet exposure through a mask having a predetermined pattern provided in contact or non-contact state with the film. Thereafter, the developer can be immersed in a solvent or an alkaline developer, or sprayed with a spray 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 a higher precision than the printing method can be produced.

As for the development, aqueous solutions such as sodium carbonate and sodium hydroxide are used as the alkaline developer, and organic alkalis such as dimethylbenzylamine and triethanolamine can also be used. A defoaming agent or a surfactant may be added to the developer.

In addition, in order to increase the ultraviolet exposure sensitivity, after coating and drying the colored resist, after coating and drying a water-soluble or alkali water-soluble resin, such as polyvinyl alcohol or water-soluble acrylic resin, and forming a film to prevent polymerization inhibition by oxygen Ultraviolet exposure can also be performed.

A color filter can be manufactured by the electrodeposition method, the transfer method, the inkjet method, etc. other than the said method. An electrodeposition method is a method of manufacturing a color filter by electrodepositing the filter segment of each color on the transparent conductive film by the electrophoresis of colloidal particle using the transparent conductive film formed on the board | substrate. In addition, the transfer method is a method of previously forming a filter segment on the surface of a peelable transfer base sheet, and transferring this filter segment to a desired board | substrate.

Before forming the filter segment of each color on a transparent substrate or a reflecting substrate, a black matrix can be formed previously. As the black matrix, inorganic films such as chromium, chromium / chromium oxide, inorganic films such as titanium nitride, and resin films in which light-shielding agents are dispersed are used, but not limited to these. In addition, a thin film transistor (TFT) may be previously formed on the transparent substrate or the reflective substrate, and then filter segments of each color may be formed. Moreover, on one Embodiment of a color filter, an overcoat film, a transparent conductive film, etc. are formed as needed.

The color filter is bonded together with the opposing substrate using a sealant, injects liquid crystal from an injection hole provided in the seal portion, and then closes the injection hole, and if necessary, a liquid crystal display panel is manufactured by adhering a polarizing film or a retardation film to the outside of the substrate.

Such liquid crystal display panels are twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), optically compensated bend ( It can be used in the liquid crystal display mode which colorizes using color filters, such as OCB).

Example

Hereinafter, although each embodiment I-VIII is demonstrated based on an Example, this invention is not limited by this. In the examples and reference examples, unless otherwise specified, "part" means "mass part" and "%" means "weight%". In addition, the measurement of an average primary particle diameter and identification of a compound were performed as follows.

<Average primary particle diameter of a coloring agent>

The average primary particle diameter of a coloring agent was measured by the method of directly measuring the size of a primary particle from an electron micrograph using a transmission type (TEM) electron microscope. Specifically, the diameter of the short axis and the length of the long axis of the primary particles of each colorant were measured, and the average was made into the primary particle diameter of the colorant. Next, with respect to 100 or more colorant particles, the volume (weight) of each particle was calculated | required nearest to the cube of the calculated | required particle diameter, and the volume average particle diameter was made into the average primary particle diameter.

<Identification of Compound>

Identification of the compound was carried out with the agreement of the molecular ion peak value of the mass spectrum obtained using the MALDI mass spectrometer autoflexIII (hereinafter referred to as TOF-MS) manufactured by Burka Dartonicus, and the number of masses obtained by calculation.

<< embodiment I >>

First, before the Example, the manufacturing method of the pigment derivative (1) and blue coloring agent 1 (B-1) used for a coloring composition is demonstrated.

(Production of Pigment Derivative 1)

The dye derivative (1) was obtained in accordance with the synthesis method described in Japanese Patent No. 4557581.

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(Production of Blue Colorant 1 (B-1))

In 1250 parts of n-amyl alcohol, 225 parts of phthalodinitriles and 78 parts of aluminum chloride anhydrides were added and stirred in reaction container. To this, 266 parts of DBU (1,8-Diazabicyclo [4.0.] Undec-7-ene) were added, the temperature was raised, and the mixture was refluxed at 136 ° C for 5 hours. The reaction solution cooled to 30 degreeC with stirring was stirred and inject | poured in 5000 parts of methanol, and the mixed solvent of 10000 parts of water, and the blue suspension was obtained. The suspension was filtered, washed with 2000 parts of methanol and 4000 parts of water in a mixed solvent, and dried to obtain 135 parts of chloro aluminum phthalocyanine (AlPc-Cl). Furthermore, 100 parts of chloro aluminum phthalocyanine was slowly added to 1200 parts of concentrated sulfuric acid at room temperature in reaction container. It stirred at 40 degreeC for 3 hours, and poured sulfuric acid solution into 24000 parts of 3 degreeC cold waters. The blue precipitate was filtered, washed with water and dried to obtain 102 parts of hydroxyaluminum phthalocyanine (AlPc-OH).

Subsequently, 100 parts of hydroxyaluminum phthalocyanine (AlPc-OH), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were put into a stainless 1 gallon kneader (manufactured by Inoue Sesakujo Co., Ltd.), and kneaded at 60 ° C for 6 hours. The kneaded product was poured into 3000 parts of warm water, stirred for 1 hour while heating to 70 ° C, and the mixture was stirred. Repeated filtration and washing to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 ° C to give a blue colorant ( B-1) 98 parts were obtained. The average primary particle diameter was 31.2 nm.

Example 1

(Production of Yellow Colorant 1 (Y-1))

Compound (1) was obtained according to the synthesis method disclosed in Japanese Patent Laid-Open No. 2008-81566.

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To 300 parts of methyl benzoate, 100 parts of compound (1), 70 parts of 2,3-naphthalenedicarboxylic acid anhydride and 143 parts of benzoic acid were added, and it heated at 180 degreeC and made it react for 4 hours. By TOF-MS, the production | generation of a quinophthalone compound (a) and the loss | disappearance of the compound (1) which are raw materials were confirmed. Furthermore, after cooling to room temperature, the reaction mixture was poured into 3130 parts of acetone and stirred at room temperature for 1 hour. The product was filtered off, and the mixture was washed with methanol and dried to obtain 120 parts of quinophthalone compound (a). It identified that it was a quinophthalone compound (a) as a result of the mass spectrometry by TOF-MS.

Next, 100 parts of the quinophthalone compound (a), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a stainless 1 gallon kneader (manufactured by Inoue Sesakujo Co., Ltd.), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. . The resultant kneaded product was poured into 3 liters of warm water, stirred for 1 hour while heating to 70 ° C to obtain a suspension, filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 ° C for 98 parts. Yellow colorant 1 (Y-1) was obtained. The average primary particle diameter was 31.3 nm.

[Example 2]

(Production of Yellow Colorant 2 (Y-2))

70 parts of quinophthalone compound (a), 30 parts of CI pigment yellow 138 ("Pariotol yellow -K0960-HD" made by BASF Corporation), 1200 parts of sodium chloride, and 120 parts of diethylene glycol (made by Inoue Sesakujo) ) Was kneaded at 60 ° C. for 8 hours. Next, the kneaded product was poured into warm water, stirred for 1 hour while heated to about 70 ° C, brought to a suspension state, filtered, washed with water repeatedly to remove sodium chloride and diethylene glycol, and dried overnight at 80 ° C to give yellow color. 97 parts of coloring agents 2 (Y-2) were obtained. The average primary particle diameter was 30.4 nm.

[Example 3]

(Production of Yellow Colorant 3 (Y-3))

70 parts of quinophthalone compound (a) and 30 parts of CI pigment yellow 138 ("Pariotol yellow -K0960-HD" made by BASF Corporation) 50 parts of quinophthalone compound (a) and CI pigment yellow 138 (made by BASF Corporation " Except having changed into 50 parts of pariotol yellow-K0960-HD ", it carried out similarly to manufacture of the yellow coloring agent 2 (Y-2), and obtained the yellow coloring agent 3 (Y-3). The average primary particle diameter was 29.6 nm.

Example 4

(Production of Yellow Colorant 4 (Y-4))

70 parts of quinophthalone compound (a) and 30 parts of CI pigment yellow 138 ("Pariotol yellow -K0960-HD" made by BASF Corporation) 20 parts of quinophthalone compound (a) and CI pigment yellow 138 (made by BASF Corporation " The yellow coloring agent 4 (Y-4) was obtained like manufacture of the yellow coloring agent 2 (Y-2) except having changed to 80 parts of pariotol yellow-K0960-HD ". The average primary particle diameter was 31.8 nm.

[Example 5]

(Production of Yellow Colorant 5 (Y-5))

It carried out similarly to manufacture of a yellow coloring agent (Y-1) except changing 70 parts of 2, 3- naphthalenedicarboxylic acid anhydrides with a mixture of 42 parts of 2, 3- naphthalenedicarboxylic acid anhydrides and 60 parts of tetrachloro phthalic anhydride, and Yellow colorant 5 (Y-5) consisting of a mixture of nophthalone compound (a) and pigment yellow 138 was obtained. The average primary particle diameter was 28.0 nm. As a result of TOF-MS measurement, the composition ratio of the quinophthalone compound (a) and the pigment yellow 138 in the yellow coloring agent 5 was 5: 5.

[Example 6]

(Production of Yellow Colorant 6 (Y-6))

To 200 parts of methyl benzoate, 35 parts of 8-aminoquinaldine, 33 parts of 2,3-naphthalenedicarboxylic acid anhydride, 47 parts of tetrachlorophthalic anhydride and 154 parts of benzoic acid were added, and it heated at 180 degreeC, and stirred for 2 hours. Then, 95 parts of tetrachloro phthalic anhydride and 50 parts of benzoic acid were added, and it stirred at 180 degreeC for 3 hours. Furthermore, after cooling to room temperature, the reaction mixture was poured into 6140 parts of acetone and stirred at room temperature for 1 hour. The product was filtered off, and the mixture was washed with methanol and dried to obtain 125 parts of a quinophthalone compound. As a result of the TOF-MS measurement, the yellow coloring agent 6 confirmed that the main component consists of a composition ratio of a quinophthalone compound (a) and pigment yellow 138 about 5: 5. In addition, since very few molecular ion peaks corresponding to the mass number of the quinophthalone compound (c) were observed, it was suggested that trace amounts of the quinophthalone compound (c) were also contained.

Subsequently, 100 parts of the obtained quinophthalone compound, 1200 parts of sodium chloride, and 120 parts of diethylene glycol were put into the stainless 1 gallon kneader (made by Inoue Sesakujo Co., Ltd.), and it knead | mixed at 60 degreeC for 8 hours. Next, the kneaded product was poured into warm water, stirred for 1 hour while heated to 70 ° C, and then in suspension, filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 ° C to give a yellow colorant. 98 parts of 6 (Y-6) were obtained. The average primary particle diameter was 29.0 nm.

[Example 7]

(Production of Yellow Colorant 7 (Y-7))

To 200 parts of methyl benzoate, 40 parts of 8-aminoquinaldine, 150 parts of 2,3-naphthalenedicarboxylic acid anhydride and 154 parts of benzoic acid were added, it heated at 180 degreeC, and stirred for 4 hours. Furthermore, after cooling to room temperature, the reaction mixture was poured into 5440 parts of acetone and stirred at room temperature for 1 hour. The product was filtered off, and the mixture was washed with methanol and dried to obtain 116 parts of quinophthalone compound (c). It identified that it was a quinophthalone compound (c) as a result of the mass spectrometry by TOF-MS.

Subsequently, 100 parts of the obtained quinophthalone compound (c), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were put into the stainless 1 gallon kneader (made by Inoue Sesakujo Co., Ltd.), and kneaded at 60 degreeC for 8 hours. Next, the kneaded product was poured into warm water, stirred for 1 hour while heating to about 70 ° C. to a suspension state, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight and yellowed. 97 parts of coloring agents 7 (Y-7) were obtained. The average primary particle diameter was 34.1 nm.

[Example 8]

(Production of Yellow Colorant 8 (Y-8))

The compound (2) was obtained by the method similar to the synthesis | combination of a compound (1) according to the synthesis | combining method of Unexamined-Japanese-Patent No. 2008-81566 using a quinophthalone compound (c) as a raw material.

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100 parts of compounds (2), 108 parts of tetrachlorophthalic anhydride, and 143 parts of benzoic acid were added to 300 parts of methyl benzoate, it heated at 180 degreeC, and was made to react for 4 hours. The production | generation of a quinophthalone compound (b) and the loss | disappearance of the compound (2) which are raw materials were confirmed by TOF-MS. Furthermore, after cooling to room temperature, the reaction mixture was poured into 3510 parts of acetone and stirred at room temperature for 1 hour. The product was filtered off, and the mixture was washed with methanol and dried to obtain 120 parts of the quinophthalone compound (b). It identified that it was a quinophthalone compound (b) as a result of the mass spectrometry by TOF-MS.

Subsequently, 100 parts of obtained quinophthalone compound (b), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were put into the stainless 1 gallon kneader (made by Inoue Sesakujo Co., Ltd.), and it knead | mixed at 60 degreeC for 8 hours. Next, the kneaded product was poured into warm water and stirred for 1 hour while heating to about 70 DEG C, followed by filtration and washing to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 DEG C, to give a yellow colorant. 98 parts of 8 (Y-8) were obtained. The average primary particle diameter was 31.1 nm.

[Example 9]

(Production of Yellow Colorant 9 (Y-9))

Except having replaced 50 parts of quinophthalone compounds (a) with 50 parts of quinophthalone compounds (b), it carried out similarly to manufacture of yellow coloring agent 3 (Y-3), and obtained the yellow coloring agent 9 (Y-9). The average primary particle diameter was 30.2 nm.

[Example 10]

(Production of Yellow Colorant 10 (Y-10))

A yellow colorant which is the same as the preparation of the yellow colorant 1 (Y-1), except that 70 parts of 2,3-naphthalenedicarboxylic acid anhydride is changed to 70 parts of 1,2-naphthalenedicarboxylic acid anhydride. 10 (Y-10) was obtained. The average primary particle diameter was 31.6 nm.

[Example 11]

(Production of Yellow Colorant 11 (Y-11))

100 parts of compounds (2), 176 parts of tetrabromo phthalic anhydride, and 143 parts of benzoic acid were added to 300 parts of methyl benzoate, it heated at 180 degreeC, and was made to react for 6 hours. By TOF-MS, the production | generation of a quinophthalone compound (h) and the loss | disappearance of the compound (2) which are raw materials were confirmed. Furthermore, after cooling to room temperature, the reaction mixture was poured into 7190 parts of acetone and stirred at room temperature for 1 hour. The product was filtered off, and the mixture was washed with methanol and dried to obtain 138 parts of quinophthalone compound (h). It identified that it was a quinophthalone compound (h) as a result of the mass spectrometry by TOF-MS.

Subsequently, 100 parts of obtained quinophthalone compound (h), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were put into the stainless 1 gallon kneader (made by Inoue Sesakujo Co., Ltd.), and it knead | mixed at 60 degreeC for 8 hours. Next, the kneaded product was poured into warm water, stirred for 1 hour while heating to about 70 ° C. to a suspension state, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight and yellowed. 97 parts of coloring agents 11 (Y-11) were obtained. The average primary particle diameter was 28.3 nm.

[Example 12]

(Production of Yellow Colorant 12 (Y-12))

52 parts of quinophthalone compounds (a) were melt | dissolved in 428 parts of 98% sulfuric acid, and 472 parts of 25% fuming sulfuric acid, and it stirred at 85 degreeC for 2 hours, and performed the sulfonation reaction. Subsequently, this reaction solution was added dropwise into 6000 parts of ice water, and the precipitated quinophthalone compound was separated by filtration and washed with water to obtain the paste. The obtained paste was redispersed in 8000 parts of water, and stirred at room temperature for 1 hour. After filtration, the resultant was separated, washed with water, and dried overnight at 80 ° C. to obtain 54 parts of the quinophthalone compound (k). It identified that it was a quinophthalone compound (k) as a result of the mass spectrometry by TOF-MS.

Subsequently, 50 parts of the obtained quinophthalone compound (k) and 50 parts of CI pigment yellow 138 ("Pariotol yellow-K0960-HD" made by BASF Corporation), 1200 parts of sodium chloride, and 120 parts of diethylene glycol (1 gallon kneader made of stainless steel) It was made into Inoue Sesakujo Co., Ltd., and kneaded at 60 degreeC for 8 hours. Next, the kneaded product was poured into warm water, stirred for 1 hour while heating to about 70 ° C. to a suspension state, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight and yellowed. 95 parts of coloring agents 12 (Y-12) were obtained. The average primary particle diameter was 36.8 nm.

[Example 13]

(Production of Yellow Colorant 13 (Y-13))

44 parts of quinophthalone compounds (b) were dissolved in 540 parts of 95% sulfuric acid, 38 parts of N-hydroxymethylphthalimido were added, and it stirred at 85 degreeC for 7 hours. After cooling, the reaction solution was added dropwise to 3600 parts of ice water, and the precipitated quinophthalone compound was separated by filtration, washed with water to obtain the paste. The obtained paste was redispersed in 5000 parts of water and stirred at room temperature for 1 hour. After filtration, the resultant was separated, washed with water, and dried overnight at 80 ° C. to obtain 53 parts of quinophthalone compound (r). It identified that it was a quinophthalone compound (r) as a result of the mass spectrometry by TOF-MS.

Subsequently, 50 parts of obtained quinophthalone compound (r) and 50 parts of CI pigment yellow 138 ("Pariotol yellow-K0960-HD" by BASF Corporation), 1200 parts of sodium chloride, and 120 parts of diethylene glycol (1 gallon kneader) It was made into Inoue Sesakujo Co., Ltd., and kneaded at 60 degreeC for 8 hours. Next, the kneaded product was poured into warm water, stirred for 1 hour while heating to about 70 ° C. to a suspension state, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight and yellowed. 98 parts of coloring agents 13 (Y-13) were obtained. The average primary particle diameter was 35.4 nm.

[Example 14]

(Production of Yellow Colorant 14 (Y-14))

With the manufacture of yellow colorant 3 (Y-3) except changing 50 parts of CI pigment yellow 138 ("Pariotol yellow -K0960-HD" made by BASF Corporation) to 50 parts of CI pigment yellow 150 ("E4GN" made by Lanxess company) It carried out similarly and obtained yellow coloring agent 14 (Y-14). The average primary particle diameter was 36.5 nm.

[Referential Example 1]

(Production of Yellow Colorant 15 (Y-15))

100 parts of CI pigment yellow 138 ("Pariotol yellow -K0960-HD" made by BASF Corporation), 1200 parts of sodium chloride, and 120 parts of diethylene glycol are put in stainless steel 1 gallon kneader (made by Inoue Sesakujo Co., Ltd.), and it is 60 hours at 60 degreeC Kneaded. Next, the kneaded product was poured into warm water, stirred for 1 hour while heating to about 70 ° C. to a suspension state, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight and yellowed. 98 parts of coloring agents 15 (Y-15) were obtained. The average primary particle diameter was 35.8 nm.

[Reference Example 2]

(Production of Yellow Colorant 16 (Y-16))

With the manufacture of yellow colorant 15 (Y-15) except changing 100 parts of CI pigment yellow 138 ("Pariotol yellow -K0960-HD" made by BASF Corporation) to 100 parts of CI pigment yellow 150 ("E4GN" made by Lanxess company) It carried out similarly and obtained yellow coloring agent 16 (Y-16). The average primary particle diameter was 36.5 nm.

[Referential Example 3]

(Production of Yellow Colorant 17 (Y-17))

100 parts of CI pigment yellow 138 ("Pariotol yellow -K0960-HD" made by BASF company) 50 parts of CI pigment yellow 138 ("Pariotol yellow -K0960-HD" made by BASF company) and CI pigment yellow 150 (product made by Lanxess company Except having changed into the mixture of 50 parts of "E4GN", it carried out similarly to manufacture of yellow coloring agent 15 (Y-15), and obtained yellow coloring agent 17 (Y-17). The average primary particle diameter was 37.2 nm.

Table 1 shows the contents of the prepared yellow colorants 1 to 17 (Y-1 to 17). "PY138" and "PY150" described in Table 1 mean CI Pigment Yellow 138 and CI Pigment Yellow 150, respectively.

<Method for producing binder resin solution>

(Preparation of acrylic resin solution 1)

196 parts of cyclohexanone were put into a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube, and a stirring device in a separable four-necked flask, the temperature was raised to 80 ° C., and the inside of the reaction vessel was replaced with nitrogen. 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylates, 12.0 parts of methacrylic acid, paracumyl phenol ethylene oxide modified acrylate ("Aronix M110" made by Toagosei Co., Ltd.) from a dripping pipe A mixture of 20.7 parts and 1.1 parts of 2,2'-azobisisobutylonitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain a solution of acrylic resin. After cooling to room temperature, about 2 parts of the resin solution was sampled, dried by heating at 180 ° C. for 20 minutes to measure the nonvolatile content, and methoxypropyl acetate was added to the synthesized resin solution so that the nonvolatile content was 20% by mass. Solution 1 was prepared. The weight average molecular weight (Mw) was 26000.

(Preparation of acrylic resin solution 2)

207 parts of cyclohexanone were placed in a separable four-necked flask with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube, and a stirring device, and the temperature was raised to 80 ° C., and the nitrogen was replaced in the reaction vessel. 20 parts of methacrylic acid, 20 parts of paracumyl phenol ethylene oxide modified acrylates (Aronix M110 made by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2, from a dripping pipe A mixture of 1.33 parts of 2'-azobisisobutylonitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain a copolymer resin solution. Next, after stopping nitrogen gas and stirring dry air for 1 hour with respect to the obtained copolymer solution whole quantity, after cooling to room temperature, 2-methacryloyl oxyethyl isocyanate (Carenz MOI by Showa Denko Corporation) ) A mixture of 6.5 parts, dibutyltin laurate 0.08 parts, and 26 parts of cyclohexanone was added dropwise at 70 ° C. over 3 hours. After completion of the dropwise addition, the reaction was continued for 1 hour to obtain a solution of an acrylic resin. After cooling to room temperature, about 2 parts of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the synthesized resin solution so that the nonvolatile content was 20% by mass. 2 was prepared. The weight average molecular weight (Mw) was 18000.

(Weight Average Molecular Weight of Binder Resin)

The weight average molecular weight of an acrylic resin is the weight average molecular weight of polystyrene conversion measured by GPC (gel osmosis chromatography).

<Production of Yellow Coloring Composition>

[Example 15]

(Production of Yellow Coloring Composition 1 (YP-1))

After stirring and mixing the mixture which consists of the following components so that it may become uniform, it disperse | distributes with Eiger-mill ("Mini Model M-250 MKII" by Eiger Japan company) using 0.5 mm diameter zirconium oxide beads, and Filtration with a 5 micrometers filter produced the yellow coloring composition 1 (YP-1).

Yellow colorant 1 (Y-1) 9.5 parts

Pigment derivative (1) 0.5 part

Resin-type dispersant ("PB821" made by Ajinomoto Fine Techno Co., Ltd.) 1.0 part

Acrylic resin solution 1-45.0 parts

Propylene glycol monomethyl ether acetate 44.0 parts

[Examples 16-28, Reference Examples 4-6]

(Production of yellow coloring composition 2-14, 20-22 (YP-2-14, 20-22))

Except having changed the yellow coloring agent 1 (Y-1) into the yellow coloring agent of Table 2, it carried out similarly to the yellow coloring composition 1 (YP-1), and yellow coloring composition 2-14, 20-22 (YP-2-14, 20-22) was produced.

[Example 29]

(Production of Yellow Coloring Composition 15 (YP-15))

After stirring and mixing the mixture which consists of the following components uniformly, after disperse | distributing with Eiger-mill ("Mini Model M-250 MKII" by Eiger Japan company) using zirconium oxide beads of 0.5 mm in diameter, It filtered by the filter of 5 micrometers, and produced the yellow coloring composition 15 (YP-15).

Yellow colorant 1 (Y-1) 10.0 parts

Resin-type dispersant (PB821 made by Ajinomoto Fine Techno Co., Ltd.) 2.0part

Acrylic resin solution 1 40.0part

Propylene glycol monomethyl ether acetate 40.0 parts

[Examples 30-33, Reference Examples 7-9]

(Production of yellow coloring composition 16-19, 23-25 (YP-16-19, 23-25))

Except having changed the yellow coloring agent 1 (Y-1) into the yellow coloring agent of Table 2, it carried out similarly to the yellow coloring composition 15 (YP-15), and yellow coloring composition 16-19, 23-25 (YP-16-19, 23-25) was produced.

<Evaluation of Yellow Coloring Composition>

Evaluation of a yellow coloring composition evaluated the coating film using the yellow coloring composition, and measured the brightness, the thickness of a film, and contrast ratio. The evaluation method is shown below.

(Brightness evaluation)

The yellow coloring composition was apply | coated using the spin coater on the glass substrate of 100 mm x 100 mm and 1.1 mm thickness, and the coating film was obtained by heating at 230 degreeC for 20 minutes. At this time, the thickness of the coating film was applied after timely changing the coating conditions (number of revolutions of the spin coater, time) so that the thickness of the coating film was x = 0.440 in the C light source. The obtained coating film was measured for brightness (Y) using a microscopic spectrophotometer (Olymps Kogaku Co., Ltd. "OSP-SP100"), and was determined according to the following criteria.

○ ： 89.0 or more

△: 89.5 or more and less than 89.0

× ： Less than 87.5

(Color evaluation)

Using the same coating film as the lightness evaluation, the thickness of the film when the chromaticity of x (C) = 0.440 was measured and determined according to the following criteria. The smaller the thickness of the film imparting a chromaticity of x (C) = 0.440, the greater the coloring power, which is excellent.

○: less than 2.0 [μm]

Δ: 2.0 or more and less than 3.0 [μm]

×: 3.0 or more [μm]

(Contrast Ratio Evaluation)

Light emitted from the backlight unit for liquid crystal display is polarized through the polarizing plate, passes through the coating film of the coloring composition applied on the glass substrate, and reaches the other polarizing plate. At this time, when the polarizing plate and the polarizing plane of the polarizing plate are parallel, the light passes through the polarizing plate, but when the polarizing plane is orthogonal, the light is blocked by the polarizing plate. However, when light polarized by the polarizing plate passes through the coating film of the coloring composition, scattering or the like occurs due to colorant particles, and when a deviation occurs in a part of the polarizing plane, when the polarizing plates are parallel, the amount of light transmitted decreases, and the polarizing plate is When orthogonal, some light is transmitted. This transmitted light was measured as the brightness | luminance on a polarizing plate, and the ratio of the brightness | luminance when orthogonal to the brightness | luminance when a polarizing plate is parallel was computed as contrast ratio.

(Contrast ratio) = (Brightness in parallel) / (Brightness in orthogonal)

Therefore, when scattering is caused by the colorant in the coating film, the brightness at the same time decreases and the brightness at the orthogonal angle 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 Nippon Denko Corporation) were used as the polarizing plate. When measuring, it measured through the black mask which made the hole of 1 cm square in the measurement part. It judged according to the following criteria using the same coating film as when the brightness evaluation was performed.

○: 3000 or more

△: 2000 or more and less than 3000

×: Less than 2000

The evaluation results are shown in Table 2 with the kind of the yellow coloring agent used in the yellow coloring composition with respect to the yellow coloring composition prepared in the Example and the reference example.

From Table 2, it became clear that the yellow coloring composition of Examples 15-33 which used the quinophthalone compound represented by General formula (1) as a coloring agent was excellent in brightness and contrast ratio, and showed high coloring power. On the other hand, the yellow coloring composition of Reference Examples 4-9 using the yellow coloring agent used conventionally is inferior to any one of brightness, contrast ratio, and coloring power, and simultaneously obtains the result which satisfy | fills all brightness, contrast ratio, and coloring power simultaneously. It became clear that I could not.

When the yellow coloring composition of Examples 16-18 was compared, the difference in brightness, contrast ratio, and coloring power was confirmed by changing the ratio of a quinophthalone compound (a) and CI pigment yellow 138. The larger the ratio of the quinophthalone compound (a) was, the higher the brightness and the coloring power tended to be, but the contrast ratio was about the yellow coloring composition of Example 17 (Kinophthalone compound (a) / CI pigment yellow 138 = 5/5). ) Showed the best results.

When the yellow coloring composition of Examples 17, 19, and 20 was compared, the quinophthalone compound (a) and CI pigment yellow 138 were synthesize | combined separately, and the coloring agent obtained by mixing at the time of salt milling process, and by the cosynthesis method In the yellow coloring composition using the obtained coloring agent, it became clear that almost equivalent results can be obtained.

When comparing Example 15, Example 29, Example 16, Example 30, Example 17, Example 31, Example 18, Example 32, Example 23, and Example 33, a pigment derivative is added to the yellow coloring composition. When (1) was contained, it became clear that both brightness and contrast ratio became favorable.

<Production of Green and Blue Coloring Compositions>

(Production of Green Coloring Composition 1 (GP-1))

After stirring and mixing the mixture which consists of the following components uniformly, after disperse | distributing with Eiger-mill ("Mini Model M-250 MKII" by Eiger Japan company) using zirconium oxide beads of 0.5 mm in diameter, Filtration with a 5 micrometers filter produced the green coloring composition 1 (GP-1).

Green colorant 1 (C.I. Pigment Green 58) 10.0 parts

Resin type dispersant ("EFKA4300" made by Chiba Japan Corporation) 1.0part

Acrylic resin solution 1 45.0 parts

Propylene glycol monomethyl ether acetate 44.0 parts

(Production of Blue Coloring Composition 1 (BP-1))

After stirring and mixing the following mixture to make it uniform, it was made to disperse | distribute with Eiger-Mill ("Mini Model M-250 MKII" made by Eiger Japan Co., Ltd.) for 5 hours using the zirconium oxide beads of diameter 0.5mm, and then filter of 5 micrometers It filtered with and produced the green coloring composition 2 (GP-2).

Blue colorant 1 (B-1) 10.0 parts

Resin-type dispersant ("EFKA4300" made by Chiba Japan Corporation) 1.0 part

Acrylic resin solution 1-45.0 parts

Propylene glycol monomethyl ether acetate 44.0 parts

<Preparation of the photosensitive coloring composition>

[Example 34]

(Production of Photosensitive Coloring Composition 1 (GR-1))

The mixture of the following composition was stirred and mixed so that it might become uniform, and it filtered with the 1 micrometer filter and produced the photosensitive coloring composition 1 (GR-1).

Yellow coloring composition 1 (YP-1) # 18.4 parts

Green coloring composition 1 (GP-1) 26.6 parts

Acrylic resin solution 2 4.5 parts

Photopolymerizable monomer ("Aronix M402" made by Toagosei Corporation) 3.6 parts

Photopolymerization initiator ("irgacure 907" made by Chiba Japan Corporation) 1.3 parts

Sensitizer (Hadoya Kagaku Kogyo "EAB-F") 0.2 part

Ethylene glycol monomethyl ether acetate 45.4 parts

[Examples 35-43, Reference Examples 10-15]

(Production of Photosensitive Coloring Compositions 2-16 (GR-2-16))

In addition to using the yellow coloring composition shown in Table 3, a green coloring composition, or a blue coloring composition, at the time of coating evaluation, a yellow coloring composition and a green coloring composition, or blue coloring are suitable for chromaticity of x = 0.290 and y = 0.600 in C light source. Photosensitive coloring compositions 2-16 (GR-2-16) were produced like photosensitive coloring composition 1 (GR-1) except having changed the ratio of a composition (change ratio so that whole quantity of a coloring composition may be 45 parts).

<Coating film evaluation of the photosensitive coloring composition>

Evaluation of the lightness, film thickness, and contrast ratio of the coating film produced using obtained photosensitive coloring composition 1-16 (GR-1-16) was performed by the following method.

(Brightness evaluation)

The photosensitive coloring composition was applied on a 100 mm × 100 mm, 1.1 mm thick glass substrate with a spin coater, then dried at 70 ° C. for 20 minutes, and subjected to ultraviolet exposure at 300 mJ / cm ² using an ultrahigh pressure mercury lamp, The development was carried out with an alkali developer at 23 ° C. As alkaline developing solution, what consists of 1.5 weight% of sodium carbonate, 0.5 weight% of sodium bicarbonate, 8.0 weight% of anionic surfactants ("Perilex NBL" by Kao Corporation), and 90 weight% of water were used. Moreover, the coating film was obtained by heating at 230 degreeC for 30 minutes. The brightness (Y) of the coating film obtained using the brown-light spectrophotometer ("OSP-SP100" by Olympus optical company) was measured, and it determined according to the following reference | standard. In addition, the produced coating film was made to be the chromaticity (C light source) shown in Table 3 after heat processing at 230 degreeC.

○: 59.5 or more

△: 58.0 or more ~ less than 59.5

×: Less than 58.0

(Color evaluation)

Using the coating film which evaluated brightness, the thickness of the film at the time of showing chromaticity of x (C) = 0.290 and y (C) = 0.600 was measured, and it determined according to the following reference | standard. The thinner the thickness of the film giving the chromaticity of x (C) = 0.290 and y (C) = 0.600, the greater the coloring power.

○: less than 2.5 [μm]

△: 2.5 or more-less than 3.0 [μm]

×: 3.0 or more [μm]

(Contrast Ratio Evaluation)

About the measuring method of coating-contrast ratio, it measured by the method similar to the contrast ratio measurement of the yellow coloring composition of Examples 15-33 and Reference Examples 4-9. The contrast ratio was computed using the coating film similar to the brightness evaluation, and it determined according to the following criteria.

○: 3500 or more

△: 3000 or more and less than 3500

×: Less than 3000

Table 3 shows the evaluation results of the photosensitive coloring composition prepared in Examples and Reference Examples.

From the result of Table 3, in the color filter formation, the Example using the photosensitive coloring composition containing the quinophthalone compound represented by General formula (1) simultaneously satisfies all brightness, contrast ratio, and coloring power more than a reference example. It became clear that it was possible to obtain, especially the brightness was excellent.

<Production of color filter>

The red photosensitive coloring composition 1 and blue photosensitive coloring composition 1 which were used for preparation of a color filter were produced. In addition, the photosensitive coloring composition 6 (GR-6) was used about green.

(Production of Red Coloring Composition 1 (RP-1))

The mixture of the compounding compositions shown below was uniformly stirred and mixed, dispersed for 8 hours in a pico mill using zirconium oxide beads having a diameter of 0.1 mm, and then filtered through a 5 μm filter to obtain a red coloring composition 1 (RP−). 1) was produced.

Red colorant 1 (C.I. Pigment Red 254) 8.5 parts

Red colorant 2 (C.I. Pigment Red 177) 3.5 parts

Resin-type dispersant ("EFKA4300" made by Chiba Japan Corporation) 1.0 part

Acrylic resin solution 1-35.0 parts

Propylene glycol monomethyl ether acetate 52.0 parts

(Preparation of red photosensitive coloring composition 1 (RR-1))

The mixture of the following composition was stirred and mixed so that it might become uniform, and it filtered with the 1 micrometer filter and produced the red photosensitive coloring composition 1 (RR-1).

Red coloring composition 1 (RP-1) 42.0 parts

Acrylic resin solution 2 13.2parts

Photopolymerizable monomer ("Aronix M400" made by Toagosei Co., Ltd.) 2.8 parts

Photopolymerization initiator ("Iruga cua 907" made by Chiba Japan Corporation) 2.0 parts

Sensitizer ("EAB-F" made by Hodogaya Kagaku Kogyo Kogyo) 0.4 part

Ethylene glycol monomethyl ether acetate 39.6 parts

(Preparation of blue coloring composition 2 (BP-2))

The mixture of the compounding compositions shown below was uniformly stirred and mixed, dispersed for 8 hours in a picomill using zirconium oxide beads having a diameter of 0.1 mm, and filtered through a 5 μm filter to prepare a blue colored composition 2 (BP-2). .

7.2 parts of blue colorants 2 (C.I. pigment blue 15: 6)

Purple Colorant 1 (C.I. Pigment Violet 23) 4.8parts

Resin type dispersant ("EFKA4300" made by Chiba Japan Corporation) 1.0 parts

Acrylic resin solution 1 33.5 parts

Propylene glycol monomethyl ether acetate 52.0 parts

(Preparation of blue photosensitive coloring composition 1 (BR-1))

The mixture of the following composition was stirred and mixed so that it might be uniform, and it filtered with the 1 micrometer filter and produced the blue photosensitive coloring composition 1 (BR-1).

Blue coloring composition 2 (BP-2) '34.0 parts

Acrylic resin solution 2-15.2 parts

Photopolymerizable monomer ("Aronix M400" made by Toagosei Co., Ltd.) 3.3 parts

Photopolymerization initiator ("Iruga cua 907" made by Chiba Japan Corporation) 2.0 parts

Sensitizer (Hadoya Kagaku Kogyo "EAB-F") 0.4 part

Ethylene glycol monomethyl ether acetate 45.1 parts

The black matrix was pattern-processed on the glass substrate, and the red photosensitive coloring composition 1 (RR-1) was apply | coated to the thickness of the film which becomes x = 0.640 and y = 0.330 with a spin coater on the said board | substrate, and the colored film was formed. . A photomask was passed through the film, and ultraviolet rays of 300 mJ / cm ² were irradiated with an ultrahigh pressure mercury lamp. Subsequently, spray development was carried out with an alkaline developer composed of 0.2% by weight aqueous sodium carbonate solution to remove unexposed portions, and then washed with ion-exchanged water, and the substrate was heated at 230 ° C. for 20 minutes to form a red filter segment. By the same method, x = 0.150, y using the green photosensitive coloring composition 1 (BR-1) in the thickness of the film | membrane which turns green photosensitive coloring composition 6 (GR-6) into x = 0.290 and y = 0.600. It apply | coated to the thickness of the film | membrane which becomes = 0.060, respectively, and formed the green filter segment and the blue filter segment, and obtained the color filter.

By using the photosensitive coloring composition 6 (GR-6), it was possible to produce the color filter which is high brightness, high contrast, and excellent coloring power.

<< embodiment II >>

"PGMAC" means propylene glycol monomethyl ether acetate.

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

The weight average molecular weight (Mw) of the resin is HLC-8220 GPC (manufactured by Tosoh Corp.) as an apparatus, TSK-GEL SUPER HZM-N is used in series as a column, and THF is used as a solvent. It is a polystyrene conversion molecular weight measured by.

First, the manufacturing method of the binder resin solution, the dye derivative, the coloring agent, the yellow coloring composition, and the blue coloring composition used by the Example and the reference example is demonstrated.

<Method for producing binder resin solution>

(Preparation of acrylic resin solution 1)

196 parts of cyclohexanone was added to a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube, and a stirring device in a separable four-necked flask, the temperature was raised to 80 ° C, and the reaction vessel was replaced with nitrogen. 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylates, 12.0 parts of methacrylic acid, paracumyl phenol ethylene oxide modified acrylate ("Aronix M110" made by Toagosei Co., Ltd.) from a dripping pipe A mixture of 20.7 parts and 1.1 parts of 2,2'-azobisisobutylonitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of a resin solution was sampled, and it heat-dried at 180 degreeC for 20 minutes, measured a non volatile matter, and added methoxypropyl acetate to the non-volatile content 20 mass% to the synthesized resin solution first, and acryl Resin solution 1 was prepared. The weight average molecular weight (Mw) was 26000.

(Preparation of acrylic resin solution 2)

207 parts of cyclohexanone were placed in a separable four-necked flask with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube, and a stirring device, and the temperature was raised to 80 ° C., and the nitrogen was replaced in the reaction vessel. 20 parts of methacrylic acid, 20 parts of paracumyl phenol ethylene oxide modified acrylates (Aronix M110 made by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2, from a dripping pipe A mixture of 1.33 parts of 2'-azobisisobutylonitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain a copolymer resin solution. Next, nitrogen gas was stopped with respect to the entire amount of the obtained copolymer solution, stirred while injecting dry air for 1 hour, and then cooled to room temperature, followed by 2-methacryloyloxyethyl isocyanate (Carenz MOI manufactured by Showa Denko Co., Ltd.). The mixture of 6.5 parts, dibutyltin laurate 0.08 parts, and 26 parts of cyclohexanone was dripped at 70 degreeC over 3 hours. After completion of the dropwise addition, the reaction was continued for 1 hour to obtain a solution of an acrylic resin. After cooling to room temperature, about 2 parts of the resin solution was sampled, dried by heating at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the synthesized resin solution so that the nonvolatile content was 20% by mass. 2 was prepared. The weight average molecular weight (Mw) was 18000.

<Production of Pigment Derivative (1)>

According to the synthesis | combining method as described in patent 4585781, the pigment derivative (1) was obtained.

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<Manufacturing method of a coloring agent>

(Production of Yellow Colorant 1 (PY-1))

Compound (1) was obtained according to the synthesis method disclosed in Japanese Patent Laid-Open No. 2008-81566.

[Formula 29]

To 300 parts of methyl benzoate, 100 parts of compound (1), 70 parts of 2,3-naphthalenedicarboxylic acid anhydride and 143 parts of benzoic acid were added, and it heated at 180 degreeC and made it react for 4 hours. By TOF-MS, the production | generation of the quinophthalone compound (a) shown by following formula (50) and the loss | disappearance of the compound (1) which are raw materials were confirmed. Furthermore, after cooling to room temperature, the reaction mixture was poured into 3130 parts of acetone and stirred at room temperature for 1 hour. The product was filtered off, and the mixture was washed with methanol and dried to obtain 120 parts of a quinophthalone compound (a). It identified that it was a quinophthalone compound (a) as a result of the mass spectrometry by TOF-MS.

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Next, 100 parts of the quinophthalone compound (a), 1200 parts of sodium chloride and 120 parts of diethylene glycol were placed in a stainless 1 gallon kneader (manufactured by Inoue Sesakujo Co., Ltd.), and kneaded at 60 ° C for 6 hours to perform salt milling. . The resultant kneaded product was poured into 3 liters of warm water, stirred for 1 hour while heating to 70 ° C to obtain a suspension, filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 ° C for 98 parts. Yellow colorant 1 (PY-1) was obtained. The average primary particle diameter was 31.3 nm.

(Production of Yellow Colorant 2 (PY-2))

20 parts of quinophthalone compounds (a) obtained by manufacture of the yellow coloring agent 1 (PY-1), 80 parts of CI pigment yellow 138 ("Pariotol yellow-K0960-HD" by BASF Corporation), 1200 parts of sodium chloride, and diethylene glycol 120 parts were put into the stainless 1 gallon kneader (made by Inoue Sesakujo Co., Ltd.), it knead | mixed at 60 degreeC for 6 hours, and the salt milling process was carried out. The resultant kneaded product was poured into 3 liters of warm water, stirred for 1 hour while heating to 70 ° C to obtain a suspension, filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 ° C for 98 parts. Yellow colorant 2 (PY-2) was obtained. The average primary particle diameter was 31.3 nm.

(Production of Yellow Colorant 3 (PY-3))

Using the quinophthalone compound (c) as a raw material, the compound (2) was obtained by the method similar to the synthesis of compound (1) according to the synthesis method as described in Unexamined-Japanese-Patent No. 2008-81566.

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100 parts of compounds (2), 108 parts of tetrachlorophthalic anhydride, and 143 parts of benzoic acid were added to 300 parts of methyl benzoate, it heated at 180 degreeC, and was made to react for 4 hours. The production | generation of a quinophthalone compound (b) and the loss | disappearance of the compound (2) which are raw materials were confirmed by TOF-MS. Furthermore, after cooling to room temperature, the reaction mixture was poured into 3510 parts of acetone and stirred at room temperature for 1 hour. The product was filtered off, and the mixture was washed with methanol and dried to obtain 120 parts of the quinophthalone compound (b) represented by the following formula (51). It identified that it was a quinophthalone compound (b) as a result of the mass spectrometry by TOF-MS.

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Subsequently, 40 parts of the obtained quinophthalone compound (b), 60 parts of CI pigment yellow 138 ("Pariotol yellow-K0960-HD" by BASF Corporation), 1200 parts of sodium chloride, and 120 parts of diethylene glycol (1 gallon kneader made of stainless steel) It was made into Inoue Sesakujo Co., Ltd., and kneaded at 60 degreeC for 8 hours. Subsequently, this kneaded product was poured into warm water, stirred for 1 hour while heating to about 70 ° C. to a suspension state, filtered, washed with water repeatedly to remove sodium chloride and diethylene glycol, and dried overnight at 80 ° C. to give a yellow colorant. 97 parts of 3 (PY-3) were obtained. The average primary particle diameter was 36.8 nm.

(Production of Yellow Colorant 4 (PY-4))

To 200 parts of methyl benzoate, 40 parts of 8-aminoquinaldine, 150 parts of 2,3-naphthalenedicarboxylic acid anhydride and 154 parts of benzoic acid were added, it heated at 180 degreeC, and stirred for 4 hours. Furthermore, after cooling to room temperature, the reaction mixture was poured into 5440 parts of acetone and stirred at room temperature for 1 hour. The product was filtered off, and the mixture was washed with methanol and dried to obtain 116 parts of a quinophthalone compound (c) represented by the following Formula (52). It identified that it was a quinophthalone compound (c) as a result of the mass spectrometry by TOF-MS.

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Subsequently, 20 parts of the obtained quinophthalone compound (c), 80 parts of CI pigment yellow 138 ("Pariotol yellow-K0960-HD" by BASF Corporation), 1200 parts of sodium chloride, and 120 parts of diethylene glycol (1 gallon kneader made of stainless steel) It was made into Inoue Sesakujo Co., Ltd., and kneaded at 60 degreeC for 8 hours. Subsequently, this kneaded product was poured into warm water, stirred for 1 hour while heating to about 70 ° C. to a suspension state, filtered, washed with water repeatedly to remove sodium chloride and diethylene glycol, and dried overnight at 80 ° C. to give a yellow colorant. 97 parts of 4 (PY-4) were obtained. The average primary particle diameter was 34.1 nm.

(Production of Yellow Colorant (PY-5))

100 parts of CI pigment yellow 138 (trade name Pariotol Yellow-K0961HD manufactured by BASF Corporation), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a stainless 1 gallon kneader (manufactured by Inoue Sesakujo), and kneaded at 70 ° C for 6 hours. The kneaded product was poured into 3000 parts of warm water, stirred for 1 hour while heating to 70 ° C, and the mixture was stirred. Repeated filtration and washing to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 ° C. PY-5) 98 parts was obtained. The average primary particle diameter was 35.5 nm.

(Production of Blue Colorant (PB-1))

In 1250 parts of n-amyl alcohol, 225 parts of phthalodinitriles and 78 parts of aluminum chloride anhydrides were added and stirred in reaction container. To this, 266 parts of DBU (1,8-Diazabicyclo [4.0.] Undec-7-ene) were added, the temperature was raised, and the mixture was refluxed at 136 ° C for 5 hours. The reaction solution cooled to 30 degreeC with stirring was poured in 5000 parts of methanol, and the mixed solvent of 10000 parts of water under stirring, and the blue suspension was obtained. The suspension was filtered, washed with 2000 parts of methanol and 4000 parts of water mixed solvent, and dried to obtain 135 parts of chloro aluminum phthalocyanine. Furthermore, 100 parts of chloro aluminum phthalocyanine was slowly added to 1200 parts of concentrated sulfuric acid in room temperature at room temperature. It stirred at 40 degreeC for 3 hours, and poured sulfuric acid solution into 24000 parts of 3 degreeC cold waters. The blue precipitate was filtered, washed with water and dried to obtain 102 parts of an aluminum phthalocyanine pigment represented by the following formula (53).

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Subsequently, 100 parts of aluminum phthalocyanine pigment, 1200 parts of sodium chloride, and 120 parts of diethylene glycol which were represented by Formula (53) were put into the stainless 1 gallon kneader (made by Inoue Sesakujo), and it knead | mixed at 70 degreeC for 6 hours. The kneaded product was poured into 3000 parts of warm water, stirred for 1 hour while heating to 70 ° C, and the mixture was stirred. Repeated filtration and washing to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 ° C to give a blue colorant ( PB-1) was obtained. The average primary particle diameter was 30.4 nm.

(Production of Blue Coloring Agent (PB-2))

100 parts of aluminum phthalocyanine pigment and 49.5 parts of diphenyl phosphate which were represented by Formula (53) were added to 1000 parts of methanol in the reaction container, and it heated at 40 degreeC, and made it react for 8 hours. After cooling this to room temperature, the product was filtered, and after wash | cleaning with methanol, it dried and obtained 114 parts of aluminum phthalocyanine pigments shown by following formula (54).

(35)

The blue coloring agent (PB-2) was obtained for the aluminum phthalocyanine pigment represented by obtained Formula (54) by the salt milling method similar to a blue coloring agent (PB-1). The average primary particle diameter was 31.2 nm.

(Production of Blue Colorant (PB-3))

In a reaction vessel, 100 parts of aluminum phthalocyanine pigment and 43.2 parts of diphenylphosphinic acid represented by Formula (53) were added to 1000 parts of methanol, heated to 40 ° C, and reacted for 8 hours. After cooling this to room temperature, the product was filtered, and after wash | cleaning with methanol, it dried and obtained 112 parts of aluminum phthalocyanine pigments represented by following formula (55).

The blue coloring agent (PB-3) was obtained for the aluminum phthalocyanine pigment represented by obtained Formula (55) by the salt milling method similar to a blue coloring agent (PB-1). The average primary particle diameter was 29.5 nm.

(36)

(Production of Blue Colorant (PB-4))

According to the synthesis method as described in Unexamined-Japanese-Patent No. 2010-79247, the aluminum phthalocyanine pigment represented by following formula (56) was obtained.

[Formula 37]

The blue coloring agent (PB-4) was obtained for the aluminum phthalocyanine pigment represented by obtained Formula (56) by the salt milling method similar to a blue coloring agent (PB-1). The average primary particle diameter was 33.0 nm.

(Production of Blue Colorant (PB-5))

200 parts of pyridine, 800 parts of xylene, and 54.6 parts of phenylphosphonic acid were added to 100 parts of aluminum phthalocyanine pigments represented by Formula (53), and heating and refluxing were continued for 8 hours. After filtering and washing | cleaning with methanol, it dried and obtained the aluminum phthalocyanine pigment shown by following formula (57) of 110 parts.

(38)

Then, the salt milling process was performed by the method similar to a blue coloring agent (PB-1), and the blue coloring agent (PB-5) was manufactured. The volume average primary particle diameter of the obtained coloring agent was 37 nm.

<Manufacturing method of a coloring composition>

(Production of Yellow Coloring Composition (DY-1))

After stirring and mixing the mixture of the following composition to make it uniform, it was 4 hours using the Eiger-Mill ("Mini Model M-250 MKII" by Eiger Japan company) as a media type | mold wet dispersion machine using 0.5 mm diameter zirconium oxide beads. After dispersion | distribution, it filtered with the filter of 5 micrometers and produced the yellow coloring composition (DY-1).

Yellow colorant (PY-1) 9.5 parts

Pigment derivative (1) 0.5 part

Resin Dispersant

(PJ821 made by Ajinomoto Fine Techno Co., Ltd.) 2.0 copy

Acrylic resin solution 1-40.0 parts

PGMAC Part 48.0

(Production of Yellow Coloring Composition (DY-2))

In preparation of the said yellow coloring composition (DY-1), the yellow coloring composition (DY-2) was produced similarly except having changed the yellow coloring agent (PY-1) into the yellow coloring agent (PY-2).

(Production of Yellow Coloring Composition (DY-3))

In the preparation of the yellow coloring composition (DY-1), a yellow coloring composition (DY-3) was produced in the same manner except that the yellow coloring agent (PY-1) was changed to a yellow coloring agent (PY-3).

(Production of Yellow Coloring Composition (DY-4))

In the preparation of the yellow coloring composition (DY-1), a yellow coloring composition (DY-4) was produced in the same manner except that the yellow coloring agent (PY-1) was changed to a yellow coloring agent (PY-4).

(Production of Yellow Coloring Composition (DY-5))

In the preparation of the yellow coloring composition (DY-1), a yellow coloring composition (DY-5) was produced in the same manner except that the yellow coloring agent (PY-1) was changed to a yellow coloring agent (PY-5).

(Production of Blue Coloring Composition (DB-1))

After the mixture of the following composition was stirred and mixed so that it might become uniform, it used 4, using Eiger-Mill ("Mini Model M-250 MKII" by Eiger Japan) as a media type | mold wet disperser using the zirconium oxide beads of diameter 0.5mm. After disperse | distributing time, it filtered with the filter of 5 micrometers and produced the blue coloring composition (DB-1).

Blue coloring agent (PB-1) 10.0 parts

Resin Dispersant

("BYK-LPN6919" made by Big Chemistry Corporation) 8.3 copies

Acrylic resin solution 1-25.0 parts

PGMAC Part 56.7

(Production of Blue Coloring Composition (DB-2))

In the preparation of the blue coloring composition (DB-1), a blue coloring composition (DB-2) was produced in the same manner except that the blue coloring agent (PB-1) was changed to a blue coloring agent (PB-2).

(Production of Blue Coloring Composition (DB-3))

In preparation of the said blue coloring composition (DB-1), the blue coloring composition (DB-3) was produced similarly except having changed the blue coloring agent (PB-1) into the blue coloring agent (PB-3).

(Production of Blue Coloring Composition (DB-4))

In the preparation of the blue coloring composition (DB-1), a blue coloring composition (DB-4) was produced in the same manner except that the blue coloring agent (PB-1) was changed to a blue coloring agent (PB-4).

(Production of Blue Coloring Composition (DB-5))

In the preparation of the blue coloring composition (DB-1), a blue coloring composition (DB-5) was produced in the same manner except that the blue coloring agent (PB-1) was changed to a blue coloring agent (PB-5).

Example 1

(Green Coloring Composition (DG-1))

The green coloring composition (DG-1) was produced by stirring-mixing with the following composition using the yellow coloring composition (DY-1) and blue coloring composition (DB-1).

Yellow coloring composition (DY-1) 81.0 parts

19.0 parts of blue coloring compositions (DB-1)

Subsequently, the obtained green coloring composition (DG-1) was apply | coated using a spin coater on the glass substrate of 100 mm x 100 mm and 1.1 mm thickness, it dried for 20 minutes at 70 degreeC, and then heated and cooled at 230 degreeC for 1 hour. The coating film substrate was produced by carrying out. The chromaticity of the obtained coating film was measured using the microscopic spectrophotometer (Olympus Kogaku Co., Ltd. "OSP-SP100"), and it confirmed that the chromaticity of the board | substrate became x = 0.290 and y = 0.600 in C light source.

[Examples 2 to 17 and Reference Examples 1 to 5]

(Green coloring composition (DG-2-22))

When it changed into the yellow coloring composition and blue coloring composition shown in Table 1, and it was set as the coating substrate in the same manner as green coloring composition (DG-1), it stirred stirring at the compounding ratio which becomes x = 0.290 and y = 0.600 in C light source. By this, the green coloring composition (DG-2-22) was produced. In addition, the total content of a green coloring composition is all 100.0 parts.

<Evaluation of Green Coloring Composition>

About the obtained green coloring composition (DG-1-22), the test regarding the viscosity of a dispersion and coloring power was performed by the following method. The results are shown in Table 2.

(Viscosity evaluation)

The viscosity of the coloring composition measured the viscosity in rotation speed of 20 rpm using the E-type viscosity meter ("ELD type viscometer" by Toki-san Corporation) at 25 degreeC on the adjustment day. The results were judged by the following criteria.

○: less than 10.0 [mPa · s]

Δ: 10.0 or more and less than 13.0 [mPa · s]

X: 13.0 or more [mPa · s]

(Color evaluation)

The coloring power was evaluated by the thickness measurement of a coating film. The thickness measurement of the obtained coating film was measured using the surface shape measuring apparatus "Dektak8 (made by Veeco)". The result was judged according to the following criteria. The smaller the thickness of the film | membrane which gives the target chromaticity, the larger the coloring power is, and it can be said that it is excellent.

◎: Less than 1.2 [μm]

○: 1.2 or more and less than 1.6 [μm]

Δ: 1.6 or more and less than 2.0 [μm]

X: 2.0 or more [μm]

From the result of Table 2, it is clear that the coloring composition of the Example containing the quinophthalone compound and aluminum phthalocyanine pigment which have a specific structure can obtain the result which is a viscosity and coloring power more favorable than a reference example.

<Preparation of the photosensitive coloring composition>

[Example 18]

(Green Photosensitive Coloring Composition (RG-1))

After stirring and mixing the following composition mixture uniformly, it filtered with the 1 micrometer filter and produced the photosensitive green coloring composition (RG-1).

Green coloring composition (DG-1) 45.0 parts

Acrylic resin solution 2 4.5 parts

Photopolymerizable monomer 3.6 parts

(`` Aronix M402 '' made by Toago Seisha)

Photoinitiator (Irugacua 907, manufactured by Chiba Japan) 1.3

Sensitizer ("EAB-F" made by Hodogaya Kagaku Corporation) 0.2 copy

Cyclohexanone 45.4 parts

[Examples 18-34, Reference Examples 6-10]

Production of (RG-2-20)

With the composition shown in Table 3, the green photosensitive coloring composition (RG-2-22) was produced like green photosensitive coloring composition (RG-1).

<Evaluation of Green Photosensitive Coloring Composition>

About the obtained green photosensitive coloring composition (RG-1-22), the test regarding brightness, contrast ratio, and coloring power was performed by the following method. The results are shown in Table 4.

(Brightness evaluation)

The green photosensitive coloring composition (RG-1 to 22) was applied onto a glass substrate 100 mm × 100 mm, 1.1 mm thick using a spin coater, dried at 70 ° C. for 20 minutes, and accumulated light amount 150 mJ / using an ultra-high pressure mercury lamp. Ultraviolet exposure was performed at cm ² , and development was carried out with an alkali developer at 23 ° C. to obtain a coating film substrate. Next, the coating film substrate was produced by heating and cooling at 230 degreeC for 1 hour. The chromaticity of the obtained coating film was measured using a microscopic spectrophotometer (Olympus Kogaku Corporation "OSP-SP100"), and the brightness when the chromaticity of the substrate became x = 0.290 and y = 0.600 in the C light source: Measured. In addition, as an alkaline developing solution, what consists of 8.0 weight% of sodium 1.5 weight% sodium hydrogencarbonate 0.5 weight% anionic surfactant ("Perryex NBL" by Kao Corporation), and 90 weight% of water was used. Judgment criteria are as follows.

○: 59.5 or more

△: 58.0 or more and less than 58.5

×: Less than 58.0

(Contrast Ratio Evaluation)

The light from the backlight unit for liquid crystal display is polarized through the polarizing plate, passes through the coating film of the coloring composition applied on the glass substrate, and reaches the other polarizing plate. At this time, if the polarizing plate and the polarizing plane of the polarizing plate is parallel, the light is transmitted through the polarizing plate, but when the polarizing plane is orthogonal, the light is blocked by the polarizing plate. However, when light polarized by the polarizing plate passes through the coating film of the coloring composition, scattering or the like occurs due to the colorant particles, and when a deviation occurs in a part of the polarizing plane, the amount of light transmitted decreases when the polarizing plates are in parallel, When it is orthogonal, some light transmits. This transmitted light was measured as the brightness | luminance on a polarizing plate, and ratio of the brightness | luminance at the time of orthogonal to the brightness | luminance when a polarizing plate is parallel was computed as contrast ratio.

(Contrast ratio) = (Brightness in parallel) / (Brightness in orthogonal)

Therefore, when scattering is caused by the colorant 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. On the measurement, it measured through the black mask which made the hole of 1 cm square through the measurement part. It determined according to the following criteria using the same coating film as the brightness evaluation.

○: More than 4000

△: 3500 or more and less than 4000

× ： Less than 3500

(Color evaluation)

The coloring power was evaluated by measuring the thickness of a coating film using the coating film which performed brightness evaluation. The thickness measurement of the obtained coating film measured using the surface shape measuring apparatus "Dektak8 (made by Veeco)". The result was judged according to the following criteria. The thinner the thickness of the film imparting the desired chromaticity, the greater the coloring power.

◎: Less than 2.0 [μm]

○: 2.0 or more and less than 2.5 [μm]

Δ: 2.5 or more and less than 3.0 [μm]

×: 3.0 or more [μm]

<Production of color filter>

First, the red photosensitive coloring composition and blue photosensitive coloring composition used for preparation of a color filter were produced. In addition, (RG-6) was used as a green photosensitive coloring composition.

(Production of Red Photosensitive Coloring Composition (RR-1))

After stirring and mixing the mixture of the following composition to make it uniform, it disperse | distributed with Eiger-Mill ("Mini Model M-250 MKII" by Eiger Japan company) using 0.5 mm of zirconium oxide beads, and it was 5.0 micrometers of Filtration with a filter produced the red coloring composition (DR-1).

Red Pigment (C.I. Pigment Red 254)

Red Pigment (C.I. Pigment Red 177) # 2.4

Resin type dispersant ("EFKA4300" made by Chiba Japan Corporation) 1.0 parts

Acrylic resin solution 1-35.0 parts

Propylene glycol monomethyl ether acetate 52.0 parts

Subsequently, the mixture of the following composition was stirred and mixed so that it might become uniform, and it filtered with 1.0 micrometer filter and produced the red photosensitive coloring composition (RR-1).

Red coloring composition (DR-1) 42.0 parts

Acrylic resin solution 2 13.2part

Photopolymerizable monomer ("Aronix M400" made by Toagosei Corporation) 2.8 parts

Photopolymerization initiator ("Iruga cua 907" made by Chiba Japan Corporation) 2.0 parts

Sensitizer (Hodogaya Kagaku Kogyo "EAB-F") 0.4 copy

Ethylene glycol monomethyl ether acetate 39.6 parts

(Production of Blue Photosensitive Coloring Composition (RB-1))

After stirring and mixing the mixture of the following composition to make it uniform, it disperse | distributed with Eiger-Mill ("Mini Model M-250 MKII" by Eiger Japan company) using 0.5 mm of zirconium oxide beads, and it was 5.0 micrometers of It filtered by the filter and produced blue coloring composition (DB-6).

Blue pigment (C.I. pigment blue 15: 6) 7.2 part

Purple Pigment (C.I. Pigment Violet 23) 4.8

Resin type dispersant ("EFKA4300" made by Chiba Japan Corporation) 1.0 parts

Acrylic resin solution 1-35.0 parts

Propylene glycol monomethyl ether acetate 52.0 parts

Then, the mixture of the following composition was stirred and mixed so that it might become uniform, and it filtered with 1.0 micrometer filter, and produced the blue photosensitive coloring composition (RB-1).

Blue coloring composition (DB-6) # 34.0 parts

Acrylic resin solution 2 5.215.2parts

Photopolymerizable monomer ("Aronix M400" made by Toagosei Co., Ltd.) 3.3 parts

2.0 parts of photoinitiators ("irgacua 907" made by Chiba Japan Corporation)

Sensitizer ("EAB-F" made by Hodogaya Kagaku Senior High School)

Ethylene glycol monomethyl ether acetate 45.1 parts

(Production of color filter)

The black matrix was pattern-processed on the glass substrate, and the red photosensitive coloring composition (RR-1) was apply | coated with the spin coater on the said board | substrate, and the coloring film was formed. A photomask was passed through the film, and ultraviolet rays of 150 mJ / cm ² were irradiated with an ultrahigh pressure mercury lamp. Subsequently, after spray development with an alkaline developer consisting of 0.2% by weight aqueous sodium carbonate solution to remove unexposed portions, the substrate was washed with ion-exchanged water and heated at 220 ° C. for 20 minutes to give a C light source (hereinafter, green and blue). Red filter segment was formed, such that x = 0.640 and y = 0.330. By the same method, green so that it may become x = 0.290 and y = 0.060 using a blue photosensitive coloring composition (RB-1) so that it may become x = 0.290 and y = 0.600 using a green photosensitive coloring composition (RG-6). A filter segment and a blue filter segment were formed to obtain a color filter.

By using the photosensitive coloring composition (RG-6), it was possible to produce the color filter which was high brightness, was high contrast, and was excellent also in coloring power.

<< embodiment III >>

Hereinafter, the weight average molecular weight (Mw) is a polystyrene conversion molecular weight when using DSK as a developing solvent with GPC (made by Tosoh, HLC-8320GPC) equipped with a RI detector using a TSKgel column (manufactured by Tosoh Corporation).

First, the yellow coloring agent and dye derivative used for the coloring composition of this embodiment are demonstrated.

<Production of a yellow colorant>

(Production of Yellow Colorant 1 (Y-1))

100 parts of quinophthalone type yellow pigment CI pigment yellow 138 ("Pariotol yellow -K0960-HD" made by BASF Corporation), 1200 parts of sodium chloride, and 120 parts of diethylene glycol are put in a 1 gallon kneader (made by Inoue Sesakujo) made of stainless steel, It knead | mixed at 60 degreeC for 6 hours. Subsequently, this kneaded product was poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to a suspension state, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 98 parts of yellow colorants 1 (Y-1) were obtained. The average primary particle diameter was 30.1 nm.

(Production of Yellow Colorant 2 (Y-2))

Compound (1) was obtained according to the synthesis method disclosed in Japanese Patent Laid-Open No. 2008-81566.

[Chemical Formula 39]

100 parts of compounds (1), 70 parts of 2, 3- naphthalenedicarboxylic acid anhydrides, and 143 parts of benzoic acid were added to 300 parts of methyl benzoate, and it heated at 180 degreeC, and made it react for 4 hours. The production | generation of a quinophthalone compound (a) and the loss | disappearance of the compound (1) which are raw materials were confirmed by TOF-MS. Furthermore, after cooling to room temperature, the reaction mixture was poured into 3130 parts of acetone and stirred at room temperature for 1 hour. The product was filtered off, and the mixture was washed with methanol and dried to obtain 120 parts of quinophthalone compound (a). It identified that it was a quinophthalone compound (a) as a result of the mass spectrometry by TOF-MS.

Next, 100 parts of the quinophthalone compound (a), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a stainless 1 gallon kneader (manufactured by Inoue Sesakujo Co., Ltd.), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. . The resultant kneaded product was poured into 3 liters of warm water, stirred for 1 hour while heating to 70 ° C to obtain a suspension, filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 ° C for 98 parts. Yellow colorant 2 (Y-2) was obtained. The average primary particle diameter was 31.3 nm.

(Production of Yellow Colorant 3 (Y-3))

70 parts of quinophthalone compound (a), 30 parts of CI pigment yellow 138 ("Pariotol yellow -K0960-HD" made by BASF Corporation), 1200 parts of sodium chloride, and 120 parts of diethylene glycol (made by Inoue Sesakujo) ) Was kneaded at 60 ° C. for 8 hours. Subsequently, this kneaded product was poured into warm water, stirred for 1 hour while heating to about 70 ° C. to a suspension state, filtered, washed with water repeatedly to remove sodium chloride and diethylene glycol, and dried overnight at 80 ° C. to give a yellow colorant. 97 parts of 3 (Y-3) were obtained. The average primary particle diameter was 30.4 nm.

(Production of Yellow Colorant 4 (Y-4))

70 parts of quinophthalone compound (a) and 30 parts of CI pigment yellow 138 ("Pariotol yellow -K0960-HD" made by BASF Corporation) 50 parts of quinophthalone compound (a) and CI pigment yellow 138 (made by BASF Corporation " The yellow coloring agent 4 (Y-4) was obtained like manufacture of the yellow coloring agent 2 (Y-2) except having changed to 50 parts of pariotol yellow-K0960-HD ". The average primary particle diameter was 29.6 nm.

(Production of Yellow Colorant 5 (Y-5))

70 parts of quinophthalone compound (a) and 30 parts of CI pigment yellow 138 ("Pariotol yellow -K0960-HD" made by BASF Corporation) 20 parts of quinophthalone compound (a) and CI pigment yellow 138 (made by BASF Corporation " The yellow coloring agent 5 (Y-5) was obtained like manufacture of the yellow coloring agent 2 (Y-2) except having changed to 80 parts of pariotol yellow-K0960-HD ". The average primary particle diameter was 31.8 nm.

(Production of Yellow Colorant 6 (Y-6))

40 parts of 8-aminoquinaldine, 150 parts of 2, 3- naphthalenedicarboxylic anhydrides, and 154 parts of benzoic acid were added to 200 parts of methyl benzoate, and it heated at 180 degreeC, and stirred for 4 hours. Furthermore, after cooling to room temperature, the reaction mixture was poured into 5440 parts of acetone and stirred at room temperature for 1 hour. The product was filtered off, and the mixture was washed with methanol and dried to obtain 116 parts of quinophthalone compound (c). It identified that it was a quinophthalone compound (c) as a result of the mass spectrometry by TOF-MS.

Subsequently, 100 parts of the obtained quinophthalone compound (c), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were put into the stainless 1 gallon kneader (made by Inoue Sesakujo Co., Ltd.), and kneaded at 60 degreeC for 8 hours. Subsequently, this kneaded product was poured into warm water, stirred for 1 hour while heating to about 70 ° C. to a suspension state, filtered, washed with water repeatedly to remove sodium chloride and diethylene glycol, and dried overnight at 80 ° C. to give a yellow colorant. 97 parts of 6 (Y-6) were obtained. The average primary particle diameter was 34.1 nm.

(Production of Yellow Colorant 7 (Y-7))

Compound (2) was obtained by the same method as the synthesis of compound (1), according to the synthesis method described in Japanese Patent Application Laid-Open No. 2008-81566, using the quinophthalone compound (c) as a raw material.

[Formula 40]

100 parts of compounds (2), 108 parts of tetrachlorophthalic anhydride, and 143 parts of benzoic acid were added to 300 parts of methyl benzoate, it heated at 180 degreeC, and was made to react for 4 hours. The production | generation of a quinophthalone compound (b) and the loss | disappearance of the compound (2) which are raw materials were confirmed by TOF-MS. Furthermore, after cooling to room temperature, the reaction mixture was poured into 3510 parts of acetone and stirred at room temperature for 1 hour. The product was filtered off, and the mixture was washed with methanol and dried to obtain 120 parts of the quinophthalone compound (b). It identified that it was a quinophthalone compound (b) as a result of the mass spectrometry by TOF-MS.

Subsequently, 100 parts of obtained quinophthalone compound (b), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were put into the stainless 1 gallon kneader (made by Inoue Sesakujo Co., Ltd.), and it knead | mixed at 60 degreeC for 8 hours. Subsequently, this kneaded product was poured into warm water, stirred for 1 hour while heating to about 70 ° C. to a suspension state, filtered, washed with water repeatedly to remove sodium chloride and diethylene glycol, and dried overnight at 80 ° C. to give a yellow colorant. 98 parts of 7 (Y-7) were obtained. The average primary particle diameter was 31.1 nm.

(Production of Yellow Colorant 8 (Y-8))

Yellow, which is the quinophthalone compound (d), was carried out in the same manner as in the preparation of the yellow colorant 1 (Y-1), except that 70 parts of 2,3-naphthalenedicarboxylic acid anhydride was changed to 70 parts of 1,2-naphthalenedicarboxylic acid anhydride. Colorant 8 (Y-8) was obtained. The average primary particle diameter was 31.6 nm.

(Production of Yellow Colorant 9 (Y-9))

100 parts of compounds (2), 176 parts of tetrabromo phthalic anhydride, and 143 parts of benzoic acid were added to 300 parts of methyl benzoate, it heated at 180 degreeC, and was made to react for 6 hours. By TOF-MS, the production | generation of a quinophthalone compound (g) and the loss | disappearance of the compound (2) which are raw materials were confirmed. Furthermore, after cooling to room temperature, the reaction mixture was poured into 7190 parts of acetone and stirred at room temperature for 1 hour. The product was filtered off, and the mixture was washed with methanol and dried to obtain 138 parts of quinophthalone compound (h). It identified that it was a quinophthalone compound (h) as a result of the mass spectrometry by TOF-MS.

Subsequently, 100 parts of obtained quinophthalone compound (h), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were put into the stainless 1 gallon kneader (made by Inoue Sesakujo Co., Ltd.), and it knead | mixed at 60 degreeC for 8 hours. Subsequently, this kneaded product was poured into warm water, stirred for 1 hour while heating to about 70 ° C. to a suspension state, filtered, washed with water repeatedly to remove sodium chloride and diethylene glycol, and dried overnight at 80 ° C. to give a yellow colorant. 97 parts of 9 (Y-9) were obtained. The average primary particle diameter was 28.3 nm.

(Production of Yellow Colorant 10 (Y-10))

52 parts of quinophthalone compounds (a) were melt | dissolved in 428 parts of 98% sulfuric acid, and 472 parts of 25% fuming sulfuric acid, and it stirred at 85 degreeC for 2 hours, and performed the sulfonation reaction. Subsequently, this reaction solution was dripped in 6000 parts of ice-water, and the precipitated quinophthalone compound was filtered, and it distinguished and washed with water, and the paste was obtained. The obtained paste was redispersed in 8000 parts of water, and stirred at room temperature for 1 hour. After filtration, the reaction mixture was washed with water, and dried overnight at 80 ° C. to obtain 54 parts of the quinophthalone compound (k). It identified that it was a quinophthalone compound (k) as a result of the mass spectrometry by TOF-MS.

Subsequently, 50 parts of the obtained quinophthalone compound (k) and 50 parts of CI pigment yellow 138 ("Pariotol yellow-K0960-HD" made by BASF Corporation), 1200 parts of sodium chloride, and 120 parts of diethylene glycol (1 gallon kneader made of stainless steel) It was made into Inoue Sesakujo Co., Ltd., and kneaded at 60 degreeC for 8 hours. Subsequently, this kneaded product was poured into warm water, stirred for 1 hour while heating to about 70 ° C. to a suspension state, filtered, washed with water repeatedly to remove sodium chloride and diethylene glycol, and dried overnight at 80 ° C. to give a yellow colorant. 95 parts of 10 (Y-10) were obtained. The average primary particle diameter was 36.8 nm.

(Production of Yellow Colorant 11 (Y-11))

44 parts of quinophthalone compounds (b) were melt | dissolved in 540 parts of 95% sulfuric acid, 38 parts N-hydroxymethyl phthalimide was added here, and it stirred at 85 degreeC for 7 hours. After cooling, the reaction solution was added dropwise to 3600 parts of ice water, and the precipitated quinophthalone compound was separated by filtration, washed with water to obtain the paste. The obtained paste was redispersed in 5000 parts of water and stirred at room temperature for 1 hour. After filtration, the residue was separated, washed with water, and dried overnight at 80 ° C. to obtain 53 parts of quinophthalone compound (r). It identified that it was a quinophthalone compound (r) as a result of the mass spectrometry by TOF-MS.

Subsequently, 50 parts of obtained quinophthalone compound (r) and 50 parts of CI pigment yellow 138 ("Pariotol yellow-K0960-HD" by BASF Corporation), 1200 parts of sodium chloride, and 120 parts of diethylene glycol (1 gallon kneader) It was made into Inoue Sesakujo Co., Ltd., and kneaded at 60 degreeC for 8 hours. Subsequently, this kneaded product was poured into warm water, stirred for 1 hour while heating to about 70 ° C. to a suspension state, filtered, washed with water repeatedly to remove sodium chloride and diethylene glycol, and dried overnight at 80 ° C. to give a yellow colorant. 98 parts of 11 (Y-11) were obtained. The average primary particle diameter was 35.4 nm.

(Production of Yellow Colorant 12 (Y-12))

To 500 parts of isoindolin series yellow pigment CI pigment yellow 139 ("Irgafoa yellow 2R-CF" made by Chiba Japan company), 500 parts of sodium chloride and 250 parts of diethylene glycol to stainless 1 gallon kneader (product made in Inoue Sesakujo) It put and knead | mixed at 120 degreeC for 8 hours. Subsequently, this kneaded product was poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to a suspension state, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 490 parts of yellow coloring agents 12 (Y-12) were obtained. The average primary particle diameter was 34.2 nm.

(Production of Yellow Colorant 13 (Y-13))

200 parts of nickel complex yellow pigment CI pigment yellow 150 ("E-4GN" made by Lanxess Corporation), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were put in a stainless gallon kneader (made by Inoue Sesakujo), and it is 80 degreeC 6 hours kneading. Subsequently, this kneaded product was poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to a suspension state, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of yellow coloring agents 13 (Y-13) were obtained. The average primary particle diameter was 31.9 nm.

<Color derivatives (1), (2)>

According to the synthesis | combining method as described in patent 4585781, the pigment derivatives (1) and (2) were obtained.

(41)

(42)

Next, the pigment dispersant of this embodiment is demonstrated.

<Production of pigment dispersant>

(Production of Vinyl Polymer (A-1))

In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser and a stirrer, 100 parts of methyl methacrylate, 200 parts of butyl acrylate, diethylene glycol monomethyl ether methacrylate (Brenma PME-100 manufactured by Nippon Oil Holding Co., Ltd.) 200 parts, 28 parts of 1-thioglycerols, and 226 parts of propylene glycol monomethyl ether acetate were put, and it substituted by nitrogen gas. The reaction vessel was heated to 90 ° C., 0.5 parts of AIBN was added, and then reacted for 8 hours. After confirming that 95% reacted by non-volatile content measurement, it cooled to room temperature and 70% of non volatile matters of the vinyl polymer (A-1) which have two advantageous hydroxyl groups in one terminal area of about 3,500 weight average molecular weight. A solution was obtained.

(Manufacture of vinyl polymer (A-2)-(A-15), comparative vinyl polymer (A'-1)-(A'-3))

Synthesis was carried out in the same manner as in the vinyl polymer (A-1), except that the raw materials and amounts to be put in Table 1 were used, and vinyl polymers (A-2) to (A) having two free hydroxyl groups in one end region. -15) and the non-volatile matter 70 weight% solution of the comparative vinyl polymer (A'-1)-(A'-3) were obtained.

Abbreviated-name in Table 1 is as showing below.

(Production of Pigment Dispersant (B-1))

In a reaction vessel 1 equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 100 parts of a 70% nonvolatile matter solution of the vinyl polymer (A-1), 15.3 parts of isophorone diisocyanate, 26.8 parts of propylene glycol monomethyl ether acetate, and a catalyst 0.027 parts of dibutyltin dilaurate was added and replaced with nitrogen gas. The reaction vessel was heated to 100 ° C, reacted for 4 hours, cooled to 40 ° C, and a prepolymer solution having an isocyanate group was obtained. 6.08 parts of iminobispropylamine and 156.3 parts of propylene glycol monomethyl ether acetate were put into the reaction container 2 equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, and it heated at 60 degreeC. The said prepolymer solution was dripped there over 30 minutes, and after making it react for 30 more minutes, it cooled to room temperature and complete | finished reaction. Propylene glycol monomethyl ether acetate was added here, and the 30% non-volatile matter solution of the pigment dispersant (B-1) was obtained. The weight average molecular weight was about 10,000 and the theoretical amine value was 47 mgKOH / g.

(Manufacture of pigment dispersant (B-2)-(B-18), comparative pigment dispersant (B'-1)-(B'-3))

Except having used the raw material and the quantity to put in Table 3, it synthesize | combined like the said pigment dispersant (B-1), and (B-2)-(B-18), (B-1)-(B VII-3) A non-volatile content 30% solution of various pigment dispersants was obtained.

Abbreviated-name of Table 3 is as showing below. IPDI: isophorone diisocyanate HDI: hexamethylene diisocyanate DBTDL: dibutyltin dilaurate IBPA: iminobispropylamine [nickname N, N-bis (3-aminopropyl) amine] MIBPA: methyl iminobispropylamine [nickname N, N-bis (3-aminopropyl) methylamine]

(Comparative Pigment Dispersant B'-4)

Ajinomoto fine techno company: Aji spa -PB-711 (for 40% of nonvolatile matters)

(Comparative Pigment Dispersant B'-5)

Cationic comb graft polymer having a basic polymer equivalent of 48 mgKOH / g in which the stem polymer portion is made of dimethylaminomethylated glycidyl methacrylate acrylate esterified glycidyl methacrylate copolymer, and the branched polymer portion is made of methyl polymethacrylate. Non volatile matter 40% propylene glycol monomethyl ether acetate solution (Patent No. 9-176511: pigment dispersant described in Example 6)

<Production of binder resin>

(Manufacture of binder resin (C-1))

Into the reaction vessel, 98.4 parts of propylene glycol monomethyl ether acetate are heated to 110 DEG C while injecting nitrogen gas into the container, and 12.3 parts of methacrylic acid, 20 parts of butyl acrylate, 29.2 parts of benzyl methacrylate, and paracumyl A mixture of 24.2 parts of phenolethylene oxide-modified acrylate ("Aronix M-110" manufactured by Toagosei Co., Ltd.), 14.3 parts of 4-hydroxybutyl acrylate and 1.65 parts of AIBN was added dropwise over 2 hours to conduct a polymerization reaction. After completion of the dropwise addition, the reaction was continued for 3 hours at 110 ° C, then cooled to room temperature and the reaction was completed. Propylene glycol monomethyl ether acetate was added here, and the 20% solution of the non volatile matter of binder resin (C-1) was obtained. The weight average molecular weight of the binder resin was about 30,000, and in theory, Tg was 2.1 占 폚.

(Production of binder resin (C-2)-(C-4))

Synthesis was carried out in the same manner as in the binder resin (C-1), except that the raw materials listed in Table 4 and the amounts used were added, and propylene glycol monomethyl ether acetate was added to the binder resins (C-2) to (C-4). A nonvolatile content of 20% solution was obtained.

Abbreviated-name of Table 4 is as showing below. MMA: Methyl methacrylate nBA: Butyl acrylate BzMA: Benzyl methacrylate M-110: Toagosei Co., Ltd. Paracumyl phenol ethylene oxide modified acrylate 4HBA: 4-hydroxybutyl acrylate HEMA: 2-hydroxy Ethyl methacrylate PME-400: Nippon Oil Co., Ltd. methoxy polyethylene glycol methacrylate AIBN: 2,2'- azobis (isobutylonitrile)

<Production of Yellow Coloring Composition>

Example 1

(Production of Yellow Coloring Composition 1 (YP-1))

After stirring and mixing the mixture which consists of the following components uniformly, it disperse | distributed with Eiger-Mill ("Mini Model M-250 'MKII" made from Eiger Japan company) for 5 hours using the zirconium oxide beads of diameter 0.5mm, and 5 micrometers It filtered with the filter of and produced the yellow coloring composition 1 (YP-1).

Yellow colorant 1 (Y-1) 9.5 parts

Pigment derivative (1) 부 0.5part

Pigment dispersant (B-1) 6.7 parts

Binder Resin (C-1) 40.0 parts

Propylene glycol monomethyl ether acetate 43.3 parts

[Examples 2 to 33 and Reference Examples 1 to 10]

(Production of Yellow Coloring Composition 2 to 43 (YP-2 to 43))

Except having changed into the material of Table 5, it carried out similarly to the yellow coloring composition 1 (YP-1), and produced the yellow coloring compositions 2-43 (YP-2-43).

About the obtained yellow coloring composition (YP-1-43), the viscosity characteristic, the brightness, and contrast ratio were measured with the following method. The evaluation results are shown in Table 5.

(Viscosity characteristic)

Rotation speed in 25 degreeC using the E-type viscosity meter ("ELD-type viscometer" made by Tokisan Co., Ltd.) the viscosity of the day after preparing the yellow coloring composition (YP-1-43) is described. It measured on the condition of 20 rpm. In addition, by measuring the viscosity promoted over time for one week at 40 ° C. (hereinafter referred to as viscosity over time), the rate of change of viscosity over time is calculated by the following equation, and the stability over time is evaluated in the following four steps. It was.

[Time-viscosity change rate (%)] = [Time-viscosity viscosity] / [initial viscosity] x 100

◎: The change over time is less than ~ 105%

(Circle): Time-lapse change rate is more than -105% and less than 130%

(Triangle | delta): Time-lapse change rate-130% or more, less than 150%

X: Change rate over time is -150% or more

(brightness)

The yellow coloring composition (YP-1-43) was apply | coated using the spin coater on the glass substrate of 100 mm x 100 mm, 1.1 mm thickness, and the coating film was obtained by heating at 230 degreeC for 20 minutes. At this time, the thickness of the coating film was applied after the heat treatment at 230 ° C. by changing the application conditions (the number of revolutions of the spin coater and time) in a timely manner so as to be x = 0.440 in the C light source. The obtained coating film was measured for brightness (Y) using a microspectrophotometer (Olympus Kogaku Co., Ltd. "OSP-SP100"), and was determined according to the following criteria.

○ ： 89.0 or more

△: 89.5 or more and less than 89.0

×: Less than 87.5

(Contrast ratio)

Light emitted from the backlight unit for liquid crystal display is polarized through the polarizing plate, passes through the coating film of the coloring composition applied on the glass substrate, and reaches the other polarizing plate. At this time, if the polarizing plane of the polarizing plate and the polarizing plate is parallel, light passes through the polarizing plate, but when the polarizing plane is orthogonal, the light is blocked by the polarizing plate. However, when light polarized by the polarizing plate passes through the coating film of the coloring composition, scattering or the like occurs due to colorant particles, and when a deviation occurs in a part of the polarizing plane, when the polarizing plates are parallel, the amount of light transmitted decreases. In this orthogonal part, some light is transmitted. This transmitted light was measured as the brightness | luminance on a polarizing plate, and ratio of the brightness | luminance at the time of orthogonal to the brightness | luminance when a polarizing plate is parallel was computed as contrast ratio.

(Contrast ratio) = (Brightness in parallel) / (Brightness in orthogonal)

Therefore, when scattering is caused by the colorant in the coating film, the brightness at the same time decreases and the brightness at the orthogonal rate 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. On the basis of the measurement, the measurement was performed by passing a black mask having a hole of 1 cm angle through the measurement portion using the same coating film as the brightness evaluation, and determined according to the following criteria.

○: 3500 or more

△: 3000 or more and less than 3500

×: Less than 3000

As is evident from the evaluation results in Table 5, an embodiment using a pigment dispersant comprising a vinyl polymer comprising, in the copolymerization composition, an ethylenically unsaturated monomer having at least one of a quinophthalone pigment and an ethylene oxide chain or a propylene oxide chain, which is the present embodiment. The coloring compositions of Examples 1-33 were the low initial viscosity and the low viscosity change rate with time, and showed favorable stability. In addition, all resulted in high brightness and high contrast, and were found to be excellent as a coloring composition for color filters. In contrast, the coloring compositions of Reference Examples 1 to 3 and 6 to 8 using the pigment dispersant consisting of a vinyl polymer having no ethylene oxide chain or propylene oxide chain, Reference Example 1 had a low initial viscosity but a high rate of change in viscosity over time It was also low contrast. In addition, the reference examples 2, 3, 6-8 were all high in initial viscosity and the viscosity change with time, and were low brightness and low contrast. In addition, the reference examples 4 and 5 using the pigment dispersant with a different structure were also the same. The coloring compositions of Reference Examples 9 and 10 using a pigment dispersant consisting of a vinyl polymer comprising a non-kinophthalone pigment and an ethylenically unsaturated monomer having at least one of an ethylene oxide chain or a propylene oxide chain in the copolymerization composition are satisfactory in contrast. Although it was possible value, it was inferior to the coloring composition part of an Example in brightness.

<Preparation of the photosensitive coloring composition>

Next, the green coloring composition used for the photosensitive coloring composition of this embodiment is demonstrated.

<Production of Green Coloring Composition>

(Production of Green Coloring Composition (GP-1))

After stirring and mixing the mixture which consists of the following components uniformly, it disperse | distributed with Eiger-mill ("mini-model M-250 'MKII" made from Eiger Japan company) for 5 hours using the zirconium oxide beads of diameter 0.5mm, It filtered by the filter and produced the green coloring composition (GP-1).

Green colorant (C.I. Pigment Green 58) 부 10.0 parts

Resin type dispersant ("EFKA4300" made by Chiba Japan Corporation) 1.0part

Binder resin (C-4) 45.0 parts

Propylene glycol monomethyl ether acetate 44.0 parts

[Example 34]

(Production of Photosensitive Coloring Composition 1 (GR-1))

The mixture of the following composition was stirred and mixed so that it might become uniform, and it filtered with the 1 micrometer filter and produced the photosensitive coloring composition 1 (GR-1). In addition, the ratio of a yellow coloring composition and a green coloring composition is a ratio according to chromaticity of x = 0.290 and y = 0.600 in C light source.

Yellow coloring composition 1 (YP-1) # 18.4 parts

Green coloring composition (GP-1) # 26.6 parts

Binder Resin (C-4) 4.5 parts

Photopolymerizable monomer ("Aronix M402" made by Toagosei Corporation) 3.6 parts

Photopolymerization initiator ("irgacure 907" made by Chiba Japan Corporation) 1.3 parts

Sensitizer (Hadoya Kagaku Kogyo "EAB-F") 0.2 part

Ethylene glycol monomethyl ether acetate 45.4 parts

[Examples 35-66, Reference Examples 11-20]

(Production of Photosensitive Coloring Compositions 2 to 43 (GR-2 to 43))

Except having changed into the combination of the coloring composition shown in Table 6, and also changing the ratio of a yellow coloring composition and a green coloring composition, it carried out similarly to the photosensitive coloring composition 1 (GR-1), and the photosensitive coloring compositions 2-43 (GR-2) 43). In addition, as for the ratio of a yellow coloring composition and a green coloring composition, the ratio was selected so that it might match with chromaticity of x = 0.290 and y = 0.600 in C light source, when both produced the coating substrate. In addition, the sum total content of a yellow coloring composition and a green coloring composition is 45.0 parts.

About each obtained photosensitive coloring composition, the brightness and contrast ratio were measured with the following method. (Brightness) The photosensitive coloring composition (GR1-43) was apply | coated using a spin coater on the glass substrate of 100 mm x 100 mm, 1.1 mm thickness, dried at 70 degreeC for 20 minutes, and accumulated light quantity 150mJ / using an ultrahigh pressure mercury lamp. Ultraviolet exposure was performed at cm ² , and development was carried out with an alkali developer at 23 ° C. to obtain a coating film substrate. Next, it heated at 220 degreeC for 30 minutes, and produced the coating film board | substrate by standing to cool. At this time, the thickness of the coating film was applied after the heat treatment at 230 ° C. by changing the coating conditions (the number of revolutions of the spin coater, time) in a time so that y = 0.600 in the C light source. The obtained coating film was measured for brightness (Y) using a microspectrophotometer (Olymps Kogaku Co., Ltd. "OSP-SP100"), and was determined according to the following criteria.

○: 59.5 or more

△: 58.0 or more ~ less than 59.5

×: Less than 58.0

(Contrast ratio)

About the measuring method of the contrast ratio of a coating film, the contrast ratio was computed by measuring by the same method as the contrast ratio measurement of the yellow coloring composition mentioned above using the coating film which evaluated brightness, and determined according to the following reference | standard.

○: 3500 or more

△: 3000 or more and less than 3500

×: Less than 3000

As is evident from the evaluation results in Table 6, yellow using a pigment dispersant consisting of a vinyl polymer comprising an ethylenically unsaturated monomer having at least one of a quinophthalone pigment and an ethylene oxide chain or a propylene oxide chain in the present embodiment. The photosensitive coloring composition of Examples 34-66 to which the coloring agent was added was a favorable result in lightness and contrast, and showed that it was excellent as a coloring composition for color filters. On the other hand, the photosensitive coloring composition of Reference Examples 11-20 using the pigment dispersing agent which consists of a vinyl polymer which does not have an ethylene oxide chain or a propylene oxide chain is behind the photosensitive coloring composition of an Example in both brightness, contrast, or either. The result was a fall.

<Production of color filter>

Next, the red photosensitive coloring composition and blue photosensitive coloring composition used for the color filter of this embodiment are demonstrated. In addition, the photosensitive coloring composition 1 (GR-1) of this embodiment was used about the green photosensitive coloring composition.

<Red photosensitive coloring composition>

(Production of Red Coloring Composition (RP-1))

After stirring the mixture of the compounding composition shown below uniformly, and disperse | distributing with Eiger-mill ("mini-model M-250 'MKII" made from Eiger Japan company) for 5 hours using the zirconium oxide beads of diameter 0.5mm, 5 micrometers It filtered with the filter of and produced the red coloring composition (RP-1).

Red colorant (C.I. Pigment Red 254) 8.5 parts

Red colorant (C.I. Pigment Red 177) 3.5 parts

Resin type dispersant ("EFKA4300" made by Chiba Japan Corporation) 1.0 parts

Binder Resin (C-4) 35.0 parts

Propylene glycol monomethyl ether acetate 52.0 parts

(Preparation of red photosensitive coloring composition (RR-1))

The mixture of the following composition was stirred and mixed so that it might become uniform, and it filtered with the 1 micrometer filter and produced the red photosensitive coloring composition (RR-1).

Red coloring composition (RP-1) 42.0 parts

Binder Resin (C-4) 13.2Part

Photopolymerizable monomer ("Aronix M400" made by Toagosei Corporation) 2.8 parts

Photopolymerization initiator ("Iruga cua 907" made by Chiba Japan Corporation) 2.0 parts

Sensitizer ("EAB-F" made by Hodogaya Kagaku Kogyo Kogyo) 0.4 part

Ethylene glycol monomethyl ether acetate 39.6 parts

(Preparation of blue coloring composition (BP-1))

After stirring the mixture of the compounding composition shown below uniformly, and disperse | distributing with Eiger-mill ("mini-model M-250 'MKII" made from Eiger Japan company) for 5 hours using the zirconium oxide beads of diameter 0.1mm, 5 micrometers It filtered with the filter of and produced the blue coloring composition (BP-1).

Blue colorant (C.I. pigment blue 15: 6) 7.2 parts

Purple Colorant (C.I. Pigment Violet 23) 4.8 parts

Resin type dispersant ("EFKA4300" made by Chiba Japan Corporation) 1.0 parts

Binder Resin (C-4) 35.0 parts

Propylene glycol monomethyl ether acetate 52.0 parts

(Preparation of blue photosensitive coloring composition (BR-1))

The mixture of the following compositions was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare a blue photosensitive coloring composition (BR-1).

Blue coloring composition (BP-1) '34.0 parts

Binder Resin (C-4) 5.215.2 parts

Photopolymerizable monomer ("Aronix M400" made by Toagosei Corporation) 3.3 parts

Photopolymerization initiator ("Iruga cua 907" made by Chiba Japan Corporation) 2.0 parts

Sensitizer ("EAB-F" made by Hodogaya Kagaku Kogyo Kogyo) 0.4 part

Ethylene glycol monomethyl ether acetate 45.1 parts

The black matrix was pattern-processed on the glass substrate, and the red photosensitive coloring composition (RR-1) was apply | coated to the thickness of the film which becomes x = 0.640 and y = 0.330 with a spin coater on the said board | substrate, and the coloring film was formed. A photomask was passed through the film, and ultraviolet rays of 300mJ / cm ² were irradiated with an ultrahigh pressure mercury lamp. Subsequently, spray development was carried out with an alkaline developer consisting of 0.2% aqueous sodium carbonate solution, and the unexposed portions were removed, washed with ion exchanged water, and the substrate was heated at 230 ° C. for 20 minutes to form a red filter segment. In the same manner, the green photosensitive coloring composition 1 (GR-1) is x = 0.290 and y = 0.600, and x = 0.150 and y = 0.060 using the blue photosensitive coloring composition (BR-1). It apply | coated to the thickness of the film | membrane which became like each, and formed the green filter segment and the blue filter segment, and obtained the color filter.

By using the photosensitive coloring composition 1 (GR-1), it was possible to produce a high-contrast and high contrast color filter.

<< embodiment IV >>

The measuring method of the weight average molecular weight (Mw) of resin is as follows.

(Measurement method of weight average molecular weight (Mw) of the resin)

The weight average molecular weight (Mw) of resin was the weight of the polystyrene conversion measured using THF in the developing solvent by GPC (made by Tosoh, HLC-8120 GPC) equipped with RI detector using TSKgel column (made by Tosoh Corporation). Average molecular weight (Mw).

Then, the manufacturing method of the binder resin solution, the dye derivative, the coloring agent, the green coloring composition, and the blue coloring composition used for the Example and the reference example is demonstrated.

<Method for producing binder resin solution>

(Preparation of acrylic resin solution 1)

196 parts of cyclohexanone were added to a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube, and a stirring device in a separable four-necked flask, the temperature was raised to 80 ° C., and the inside of the reaction vessel was replaced with nitrogen. 37.2 parts of n-butyl methacrylates, 12.9 parts of 2-hydroxyethyl methacrylates, 12.0 parts of methacrylic acid, paracumyl phenol ethylene oxide modified acrylate ("Aronix M110" by Toagosei Co., Ltd.) A mixture of 20.7 parts and 1.1 parts of 2,2'-azobisisobutylonitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain a solution of acrylic resin. After cooling to room temperature, about 2 parts of a resin solution was sampled, and it heat-dried at 180 degreeC for 20 minutes, and measured the non volatile matter, The methoxypropyl acetate was added to the synthetic resin solution so that a non volatile matter might be 20 mass%, and an acrylic resin Solution 1 was prepared. The weight average molecular weight (Mw) was 26000.

(Preparation of acrylic resin solution 2)

207 parts of cyclohexanone were placed in a separable four-necked flask with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube, and a stirring device, and the temperature was raised to 80 ° C., and the nitrogen was replaced in the reaction vessel. 20 parts of methacrylic acid, 20 parts of paracumyl phenol ethylene oxide modified acrylates (Aronix M110 made by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2, from a dripping pipe A mixture of 1.33 parts of 2'-azobisisobutylonitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain a copolymer resin solution. Subsequently, the nitrogen gas was stopped and stirred while injecting dry air for 1 hour with respect to the entire amount of the obtained copolymer solution, and then cooled to room temperature, followed by 2-methacryloyloxyethyl isocyanate (Carenz MOI manufactured by Showa Denko Co., Ltd.). ) A mixture of 6.5 parts, dibutyltin laurate 0.08 parts, and 26 parts of cyclohexanone was added dropwise at 70 ° C. over 3 hours. After completion of the dropwise addition, the reaction was continued for 1 hour to obtain a solution of an acrylic resin. After cooling to room temperature, about 2 parts of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Then, cyclohexanone was added to the synthesized resin solution so that the nonvolatile content was 20% by mass, and the acrylic resin solution was added. 2 was prepared. The weight average molecular weight (Mw) was 18000.

<Manufacturing method of a pigment derivative>

(Production of Pigment Derivative 1)

According to the synthesis | combining method described in patent 4585781, the pigment derivative (1) was obtained.

Pigment derivatives (1)

(43)

<Manufacturing method of a coloring agent>

(Production of Kinophthalone Compound (1))

According to the synthesis method described in Unexamined-Japanese-Patent No. 2008-81566, the quinophthalone compound (1) was obtained. It identified that it was a quinophthalone compound (1) as a result of the mass spectrometry by TOF-MS.

(44)

(Production of a quinophthalone compound (2))

40 parts of 8-aminoquinaldine, 150 parts of 2, 3- naphthalenedicarboxylic anhydrides, and 154 parts of benzoic acid were added to 200 parts of methyl benzoate, and it heated at 180 degreeC, and stirred for 4 hours. Furthermore, after cooling to room temperature, the reaction mixture was poured into 5440 parts of acetone and stirred at room temperature for 1 hour. The product was filtered off, and the mixture was washed with methanol, dried, and 116 parts of specific quinophthalone pigments represented by formula (A-3) were obtained. It identified that it was a quinophthalone pigment of a formula (A-3) as a result of the mass spectrometry by TOF-MS.

Subsequently, according to the synthesis method of Unexamined-Japanese-Patent No. 2008-81566, using the quinophthalone pigment of Formula (A-3) as a raw material, a quinophthalone compound (2 ) It identified that it was a quinophthalone compound (2) as a result of the mass spectrometry by TOF-MS.

[Chemical Formula 45]

(Production of Kinophthalone Compound (3))

20 parts of 8-hydroxy-2-methylquinoline, 25 parts of naphthalenedicarboxylic acid anhydrides, and 300 parts of benzoic acid were mixed, and it stirred at 200 degreeC for 7 hours. After cooling, 1000 parts of methanol was added, followed by stirring for 1 hour. And the solid precipitated was collected by suction filtration. Furthermore, the solid was put into 2000 parts of methanol, stirred for 1 hour, and the solid was collected by suction filtration. It dried with the vacuum dryer (40 degreeC) overnight, and obtained 37 parts of quinophthalone compounds (3). It identified that it was a quinophthalone compound (3) as a result of the mass spectrometry by TOF-MS.

(46)

(Production of Yellow Colorant (YA-1))

100 parts of quinophthalone compound (1), 70 parts of 2, 3- naphthalenedicarboxylic anhydrides, and 143 parts of benzoic acid were added to 300 parts of methyl benzoate, and it heated at 180 degreeC and made it react for 4 hours. By TOF-MS, the production | generation of the specific quinophthalone pigment represented by Formula (A-1) and the disappearance of the quinophthalone compound (1) which are raw materials were confirmed. Furthermore, after cooling to room temperature, the reaction mixture was poured into 3130 parts of acetone and stirred at room temperature for 1 hour. The product was filtered, and then separated, washed with methanol and dried to obtain 120 parts of specific quinophthalone pigments represented by formula (A-1). It identified that it was a quinophthalone pigment of a formula (A-1) as a result of the mass spectrometry by TOF-MS.

[Formula 47]

Subsequently, 100 parts of the quinophthalone pigments of formula (A-1), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were put in a stainless 1 gallon kneader (manufactured by Inoue Sesakujo Co., Ltd.), and kneaded at 60 ° C for 6 hours. The resultant kneaded product was poured into 3 liters of warm water, stirred for 1 hour while heating to 70 占 폚, and then in suspension, filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 占 폚 to give 98 parts of yellow color. A coloring agent (YA-1) was obtained. The average primary particle diameter was 31.3 nm.

(Production of Yellow Colorant (YA-2))

50 parts of quinophthalone pigment of formula (A-1), 50 parts of CI pigment yellow 138 ("Pariotol yellow -K0960-HD" made by BASF Corporation), 1200 parts of sodium chloride, and 120 parts of diethylene glycol (1 gallon kneader (made of stainless steel) It was made into Inoue Sesakujo Co., Ltd., and kneaded at 60 degreeC for 8 hours. Subsequently, this kneaded product was poured into warm water, stirred for 1 hour while heating to about 70 ° C. to a suspension state, filtered, washed with water repeatedly to remove sodium chloride and diethylene glycol, and dried overnight at 80 ° C. to give a yellow colorant. 97 parts (YA-2) were obtained. The average primary particle diameter was 30.2 nm.

(Production of Yellow Colorant (YA-3))

100 parts of quinophthalone compound (2), 108 parts of tetrachloro phthalic anhydride, and 143 parts of benzoic acid were added to 300 parts of methyl benzoate, it heated at 180 degreeC, and was made to react for 4 hours. Furthermore, after cooling to room temperature, the reaction mixture was poured into 3510 parts of acetone and stirred at room temperature for 1 hour. The product was filtered off, and the mixture was washed with methanol and dried to obtain 118 parts of the specific quinophthalone pigment represented by Formula (A-2). It identified that it was the quinophthalone pigment of a formula (A-2) as a result of the mass spectrometry by TOF-MS.

(48)

Subsequently, 100 parts of the quinophthalone pigments of formula (A-2), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were put in a stainless 1 gallon kneader (manufactured by Inoue Sesakujo Co., Ltd.), and kneaded at 60 ° C for 6 hours. The resultant kneaded product was poured into 3 liters of warm water, stirred for 1 hour while heating to 70 ° C to obtain a suspension, filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 ° C for 98 parts. A yellow coloring agent (YA-3) was obtained. The average primary particle diameter was 31.1 nm.

(Production of Yellow Colorant (YA-4))

50 parts of quinophthalone pigment of formula (A-2), 50 parts of CI pigment yellow 138 ("Pariotol yellow -K0960-HD" made by BASF Corporation), 1200 parts of sodium chloride, and 120 parts of diethylene glycol (1 gallon kneader made of stainless steel) It was made into Inoue Sesakujo Co., Ltd., and kneaded at 60 degreeC for 8 hours. Subsequently, this kneaded product was poured into warm water, stirred for 1 hour while heating to about 70 ° C. to a suspension state, filtered, washed with water repeatedly to remove sodium chloride and diethylene glycol, and dried overnight at 80 ° C. to give a yellow colorant. 97 parts (YA-4) were obtained. The average primary particle diameter was 30.2 nm.

(Production of Yellow Colorant (YA-5))

20 parts of quinophthalone pigment of formula (A-2), 80 parts of CI pigment yellow 138 ("Pariotol yellow -K0960-HD" made by BASF Corporation), 1200 parts of sodium chloride, and 120 parts of diethylene glycol (1 gallon kneader made of stainless steel) It was made into Inoue Sesakujo Co., Ltd., and kneaded at 60 degreeC for 8 hours. Subsequently, this kneaded product was poured into warm water, stirred for 1 hour while heating to about 70 ° C. to a suspension state, filtered, washed with water repeatedly to remove sodium chloride and diethylene glycol, and dried overnight at 80 ° C. to give a yellow colorant. (YA-5) 96 parts was obtained. The average primary particle diameter was 29.7 nm.

(Production of Yellow Colorant (YA-6))

100 parts of the quinophthalone pigment of formula (A-3), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were put into the stainless 1 gallon kneader (made by Inoue Sesakujo Co., Ltd.), and it knead | mixed at 60 degreeC for 8 hours. Subsequently, this kneaded product was poured into warm water, stirred for 1 hour while heating to about 70 ° C. to a suspension state, filtered, washed with water repeatedly to remove sodium chloride and diethylene glycol, and dried overnight at 80 ° C. to give a yellow colorant. 97 parts (YA-6) were obtained. The average primary particle diameter was 34.1 nm.

(49)

(Production of Yellow Colorant (YA-7))

100 parts of quinophthalone compound (2), 176 parts of tetrabromo phthalic anhydride, and 143 parts of benzoic acid were added, and it heated at 180 degreeC and made it react for 300 hours for methyl benzoate. Furthermore, after cooling to room temperature, the reaction mixture was poured into 7190 parts of acetone and stirred at room temperature for 1 hour. The product was filtered and then separated, washed with methanol, and dried to obtain 138 parts of specific quinophthalone pigments represented by formula (A-5). It identified that it was the quinophthalone pigment of a formula (A-5) as a result of the mass spectrometry by TOF-MS.

(50)

Subsequently, 100 parts of the quinophthalone pigments of formula (A-5), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were put in a stainless 1 gallon kneader (manufactured by Inoue Sesakujo Co., Ltd.), and kneaded at 60 ° C for 8 hours. The resultant kneaded product was poured into 3 liters of warm water, stirred for 1 hour while heating to 70 ° C to obtain a suspension, filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by overnight drying at 80 ° C to obtain 97 parts of the mixture. A yellow coloring agent (YA-7) was obtained. The average primary particle diameter was 28.3 nm.

(Production of Yellow Colorant (YA-8))

50 parts of quinophthalone pigment of formula (A-5), 50 parts of CI pigment yellow 138 ("Pariotol yellow -K0960-HD" made by BASF Corporation), 1200 parts of sodium chloride, and 120 parts of diethylene glycol (1 gallon kneader made of stainless steel) It was made into Inoue Sesakujo Co., Ltd., and kneaded at 60 degreeC for 8 hours. Subsequently, this kneaded product was poured into warm water, stirred for 1 hour while heating to about 70 ° C. to a suspension state, filtered, washed with water repeatedly to remove sodium chloride and diethylene glycol, and dried overnight at 80 ° C. to give a yellow colorant. 98 parts (YA-8) were obtained. The average primary particle diameter was 28.1 nm.

(Production of Yellow Colorant (YB-1))

29 parts of 6-hexyl-2-methylquinoline, 25 parts of naphthalenedicarboxylic acid anhydrides, and 300 parts of benzoic acid were mixed, and it stirred at 200 degreeC for 7 hours. After cooling, 1000 parts of methanol was added, followed by stirring for 1 hour. And the solid precipitated was collected by suction filtration. Furthermore, the solid was put into 2000 parts of methanol, stirred for 1 hour, and the solid was collected by suction filtration. 42 parts of specific quinophthalone dyes (yellow coloring agent (YB-1)) which dry with a vacuum dryer (40 degreeC) overnight, and are represented by Formula (B-1) were obtained. It identified that it was the quinophthalone dye of a formula (B-1) as a result of the mass spectrometry by TOF-MS.

(51)

(Production of Yellow Colorant (YB-2))

34 parts of 8- (2-ethylhexyloxy) -2-methylquinoline, 25 parts of naphthalenedicarboxylic acid anhydrides, and 300 parts of benzoic acid were mixed, and it stirred at 200 degreeC for 7 hours. After cooling, 1000 parts of methanol was added, followed by stirring for 1 hour. And the solid precipitated was collected by suction filtration. Furthermore, the solid was put into 2000 parts of methanol, stirred for 1 hour, and the solid was collected by suction filtration. It dried with the vacuum dryer (40 degreeC) overnight, and 50 parts of specific quinophthalone dyes (yellow coloring agent (YB-2)) shown by Formula (B-5) were obtained. It identified that it was the quinophthalone dye of a formula (B-5) as a result of the mass spectrometry by TOF-MS.

(52)

(Production of Yellow Colorant (YB-3))

44 parts of 8- (2-ethylhexyloxy) -5-phenyl- 2-methylquinoline, 25 parts of naphthalenedicarboxylic anhydrides, and 300 parts of benzoic acid were mixed, and it stirred at 200 degreeC for 7 hours. After cooling, 1000 parts of methanol was added, followed by stirring for 1 hour. And the solid precipitated was collected by suction filtration. Furthermore, the solid was put into 2000 parts of methanol, stirred for 1 hour, and the solid was collected by suction filtration. It dried with the vacuum dryer (40 degreeC) overnight, and obtained 57 parts of specific quinophthalone dyes (yellow coloring agent (YB-3)) shown by Formula (B-6). It identified that it was the quinophthalone dye of a formula (B-6) as a result of the mass spectrometry by TOF-MS.

(53)

(Production of Yellow Colorant (YB-4))

46 parts of 8-dodecaoxy-5-bromo-2-methylquinoline, 25 parts of naphthalenedicarboxylic acid anhydrides, and 300 parts of benzoic acid were mixed, and it stirred at 200 degreeC for 7 hours. After cooling, 1000 parts of methanol was added, followed by stirring for 1 hour. And the solid precipitated was collected by suction filtration. In addition, the solid was poured into 2000 parts of methanol, stirred for 1 hour, and the solid was collected by suction filtration. It dried with the vacuum dryer (40 degreeC) overnight, and obtained 46 parts of specific quinophthalone dyes (yellow coloring agent (YB-4)) shown by Formula (B-8). It identified that it was the quinophthalone dye of a formula (B-8) as a result of the mass spectrometry by TOF-MS.

[Formula 54]

(Production of Yellow Colorant (YB-5))

34 parts of 6- (2-ethylhexyloxy) -2-methylquinoline, 25 parts of naphthalenedicarboxylic acid anhydrides, and 300 parts of benzoic acid were mixed, and it stirred at 200 degreeC for 7 hours. After cooling, 1000 parts of methanol was added, followed by stirring for 1 hour. And the solid precipitated was collected by suction filtration. Furthermore, the solid was put into 2000 parts of methanol, and it stirred for 1 hour, and collected the solid by suction filtration. It dried with the vacuum dryer (40 degreeC) overnight, and 43 parts of specific quinophthalone dyes (yellow coloring agent (YB-5)) shown by Formula (B-10) were obtained. It identified that it was the quinophthalone dye of a formula (B-10) as a result of the mass spectrometry by TOF-MS.

(55)

(Production of Yellow Colorant (YB-6))

29 parts of 6- (2-ethoxyethoxy) -2-methylquinoline, 25 parts of naphthalenedicarboxylic anhydrides, and 300 parts of benzoic acid were mixed, and it stirred at 200 degreeC for 7 hours. After cooling, 1000 parts of methanol was added, followed by stirring for 1 hour. And the solid precipitated was collected by suction filtration. In addition, the solid was poured into 2000 parts of methanol, stirred for 1 hour, and the solid was collected by suction filtration. It dried with the vacuum dryer (40 degreeC) overnight, and obtained 39 parts of specific quinophthalone dyes (yellow coloring agent (YB-6)) shown by Formula (B-11). It identified that it was the quinophthalone dye of a formula (B-11) as a result of the mass spectrometry by TOF-MS.

(56)

(Production of Yellow Colorant (YB-7))

34 parts of 6- (2- (1,3- dioxane-2-yl) ethoxy) -2-methylquinoline, 25 parts of naphthalenedicarboxylic anhydrides, and 300 parts of benzoic acid were mixed, and it stirred at 200 degreeC for 7 hours. After cooling, 1000 parts of methanol was added, followed by stirring for 1 hour. And the solid precipitated was collected by suction filtration. In addition, the solid was poured into 2000 parts of methanol, stirred for 1 hour, and the solid was collected by suction filtration. It dried with the vacuum dryer (40 degreeC) overnight, and obtained 33 parts of specific quinophthalone dyes (yellow coloring agent (YB-7)) shown by Formula (B-12). It identified that it was the quinophthalone dye of a formula (B-12) as a result of the mass spectrometry by TOF-MS.

(57)

(Production of Yellow Colorant (YB-8))

34 parts of 4- (2-ethylhexyloxy) -2-methylquinoline, 25 parts of naphthalenedicarboxylic acid anhydrides, and 300 parts of benzoic acid were mixed, and it stirred at 200 degreeC for 7 hours. After cooling, 1000 parts of methanol was added, followed by stirring for 1 hour. And the solid precipitated was collected by suction filtration. In addition, the solid was poured into 2000 parts of methanol, stirred for 1 hour, and the solid was collected by suction filtration. It dried with the vacuum dryer (40 degreeC) overnight, and obtained 42 parts of specific quinophthalone dyes (yellow coloring agent (YB-8)) shown by Formula (B-13). It identified that it was the quinophthalone dye of a formula (B-13) as a result of the mass spectrometry by TOF-MS.

(58)

(Production of Yellow Colorant (YB-9))

20 parts of quinophthalone compounds (3) are mixed with 200 parts of N, N- dimethylacetamides, 3 parts of sodium hydroxide and 18 parts of 2-ethylhexyl 4-bromo butyric acid are further mixed, and it is 90 hours at 90 degreeC. Stirred. After cooling, 1000 parts of methanol and 1000 parts of water were added, followed by stirring for 1 hour. And the solid precipitated was collected by suction filtration. In addition, the solid was poured into 1000 parts of methanol, stirred for 1 hour, and the solid was collected by suction filtration. It dried with the vacuum dryer (40 degreeC) overnight, and 16 parts of specific quinophthalone dyes (yellow coloring agent (YB-9)) shown by Formula (B-27) were obtained. It identified that it was the quinophthalone dye of a formula (B-27) as a result of the mass spectrometry by TOF-MS.

[Chemical Formula 59]

(Production of Yellow Colorant (YB-10))

20 parts of quinophthalone compounds (3) are mixed with 200 parts of N, N- dimethylacetamides, and 3 parts of sodium hydroxide and 19 parts of 2-ethylhexyl 5-bromo-gilic acid are further mixed, and it is 1 hour at 90 degreeC. Stirred. After cooling, 1000 parts of methanol and 1000 parts of water were added, followed by stirring for 1 hour. And the solid precipitated was collected by suction filtration. In addition, the solid was poured into 1000 parts of methanol, stirred for 1 hour, and the solid was collected by suction filtration. It dried with the vacuum dryer (40 degreeC) overnight, and obtained 20 parts of specific quinophthalone dyes (yellow coloring agent (YB-10)) shown by Formula (B-28). It identified that it was the quinophthalone dye of a formula (B-28) as a result of the mass spectrometry by TOF-MS.

(60)

(Production of Yellow Colorant (YB-11))

20 parts of commercially available CI disperse yellow 160 are mixed with 200 parts of N, N-dimethylacetamide, and 3 parts of sodium hydroxide and 18 parts of 2-ethylhexyl-4-bromonoic acid are further mixed and stirred at 90 ° C for 1 hour. It was. After cooling, 1000 parts of methanol and 1000 parts of water were added, followed by stirring for 1 hour. And the solid precipitated was collected by suction filtration. In addition, the solid was poured into 1000 parts of methanol, stirred for 1 hour, and the solid was collected by suction filtration. It dried with the vacuum dryer (40 degreeC) overnight, and obtained 20 parts of specific quinophthalone dyes (yellow coloring agent (YB-11)) shown by Formula (B-30). It identified that it was the quinophthalone dye of a formula (B-30) as a result of the mass spectrometry by TOF-MS.

(61)

(Production of Yellow Colorant (YC-1))

100 parts of CI Pigment Yellow 138 (trade name Pariotol Yellow-K0961HD manufactured by BASF Corporation), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a stainless 1 gallon kneader (manufactured by Inoue Sesakujo), and kneaded at 70 ° C for 6 hours. The kneaded product was poured into warm water, stirred for 1 hour while heating to 70 占 폚, and then in suspension, filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 占 폚 to give a yellow colorant (YC- 1) 98 parts were obtained. The average primary particle diameter was 35.5 nm.

(Production of Green Colorant (GC-1))

100 parts of CI pigment green 58 ("FASTGEN GREEN A110" by DIC Corporation), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were put into the stainless 1 gallon kneader (made by Inoue Sesakujo), and it knead | mixed at 70 degreeC for 6 hours. The kneaded product was poured into warm water, stirred for 1 hour while heating to 70 占 폚, and then in suspension, filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 占 폚 to give a green colorant (GC- 1) 97 parts were obtained. The average primary particle diameter was 28.2 nm.

(Production of Blue Colorant (BC-1))

In 1250 parts of n-amyl alcohol, 225 parts of phthalodinitriles and 78 parts of aluminum chloride anhydrides were added and stirred in reaction container. To this, 266 parts of DBU (1,8-Diazabicyclo [4.0]] undec-7-ene) were added, the temperature was raised, and the mixture was refluxed at 136 ° C for 5 hours. The reaction solution cooled to 30 degreeC with stirring was poured into the mixed solvent of 5000 parts of methanol and 10000 parts of water under stirring, and the blue suspension was obtained. This suspension was filtered, washed with 2000 parts of methanol and 4000 parts of water mixed solvent, and dried to obtain 135 parts of chloro aluminum phthalocyanine. Further, 100 parts of chloro aluminum phthalocyanine was slowly added to 1200 parts of concentrated sulfuric acid at room temperature in the reaction vessel. It stirred at 40 degreeC for 3 hours, and poured sulfuric acid solution into 24000 parts of 3 degreeC cold waters. The blue precipitate was filtered, washed with water and dried to obtain 102 parts of aluminum phthalocyanine (1).

(62)

Subsequently, 100 parts of aluminum phthalocyanine (1) and 49.5 parts of diphenyl phosphate were added to 1000 parts of methanol in methanol, and it heated at 40 degreeC, and made it react for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol, and dried to obtain 114 parts of aluminum phthalocyanine (2).

(63)

In addition, salt milling treatment was performed. 100 parts of aluminum phthalocyanine (2), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were put into the stainless 1 gallon kneader (made by Inoue Sesakujo), and it knead | mixed at 70 degreeC for 6 hours. The kneaded product was poured into warm water, stirred for 1 hour while heating to 70 占 폚, a suspension state was added, and filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 占 폚 to give a blue colorant (BC- 1) 98 parts were obtained. The average primary particle diameter was 31.2 nm.

<Method for Producing Green and Blue Coloring Composition>

(Production of Green Coloring Composition (DG-1))

After stirring and mixing the mixture of the following composition to make it uniform, it uses the zirconium oxide beads of diameter 0.5mm, and uses Eiger-Mill ("Mini Model M-250 'MKII" by Eiger-Japan Corporation) as a media type | mold wet disperser. After disperse | distributing time, it filtered with the filter of 5 micrometers and produced the green coloring composition (DG-1).

Green colorant (GC-1) 10.0 parts

Resin-type dispersant ("EFKA4300" made by Chiba Japan Corporation) 2.0 parts

Acrylic resin solution 1 40.0part

Propylene glycol monomethyl ether acetate 48.0 parts

(Production of Blue Coloring Composition (DB-1))

After stirring and mixing the mixture of the following composition to make it uniform, it uses the zirconium oxide beads of diameter 0.5mm, and uses Eiger-Mill ("Mini Model M-250 'MKII" by Eiger-Japan Corporation) as a media type | mold wet disperser. After disperse | distributing time, it filtered with the filter of 5 micrometers and produced the blue coloring composition (DB-1).

Blue coloring agent (BC-1) 10.0 parts

Resin-type dispersant ("BYK-LPN6919" made by BIG Chemi Corporation) 5.0 parts

Acrylic resin solution 1 33.5 parts

Propylene glycol monomethyl ether acetate 50.0 parts

<The manufacturing method of a yellow coloring composition>

Example 1

(Production of Yellow Coloring Composition (DY-1))

After stirring and mixing the mixture of the following composition to make it uniform, it uses the zirconium oxide beads of diameter 0.5mm, and uses Eiger-Mill ("Mini Model M-250 'MKII" by Eiger-Japan Corporation) as a media type | mold wet disperser. After disperse | distributing time, it filtered by the 5 micrometer filter and produced the yellow coloring composition (DY-1).

Yellow colorant (YA-1) 4.8 parts

Yellow colorant (YB-1) 4.8 parts

Pigment derivative (1) 0.4 part

Resin-type dispersant (PB821 made by Ajinomoto Fine Techno Co., Ltd.) 부 2.0 parts

Acrylic resin solution 1-40.0 parts

Cyclohexanone # 24.0

Propylene glycol monomethyl ether acetate 24.0 parts

[Examples 2 to 33 and Reference Examples 1 to 5]

(Yellow coloring composition (DY-2-38))

Except having changed the kind and compounding quantity of a yellow coloring agent as shown in Table 1, it carried out similarly to the yellow coloring composition (DY-1) of Example 1, and obtained the yellow coloring composition (DY-2 ~ 38). In addition, the total content of a yellow coloring agent is all 9.6 parts.

Yellow coloring agent (YC-2); C.I. which is a commercial item. Dispause Yellow 54

Yellow colorant (YC-3); CI dispose yellow 64 which is a commercial item

<Evaluation of Yellow Coloring Composition>

Evaluation of the spectral transmittance, contrast ratio, coloring power, heat resistance, and light resistance of the yellow coating film produced using the obtained yellow coloring composition (DY-1-38) was performed by the following method. Table 2 shows the results of the evaluation.

Spectral transmittance evaluation

A yellow coloring composition (DY-1 to 38) was applied onto a glass substrate 100 mm × 100 mm, 1.1 mm thick using a spin coater, then dried at 70 ° C. for 20 minutes, and then heated and cooled at 220 ° C. for 20 minutes. Thereby, the coating film substrate was produced. After the heat treatment at 220 degreeC, the produced coating film board | substrate measured the spectral transmittances of 500 nm and 550 nm using the microspectrophotometer (OLYMPOS Cogaku Corporation "OSP-SP100") so that the transmittance of 450 nm might be 5%. The higher the transmittance of 500 nm and 550 nm, the better the brightness. The spectral transmittances of 500 nm and 550 nm were determined according to the following criteria.

○: 99% or more

△: 97 or more, less than 99%

× ： Less than 97%

(Contrast Ratio Evaluation)

Light emitted from the backlight unit for liquid crystal display is polarized through the polarizing plate, passes through the coating film of the coloring composition applied on the glass substrate, and reaches the other polarizing plate. At this time, when the polarizing plate and the polarizing plane of the polarizing plate are parallel, light passes through the polarizing plate, but when the polarizing plane is orthogonal, the light is blocked by the polarizing plate. However, when light polarized by the polarizing plate passes through the coating film of the coloring composition, scattering or the like occurs due to the colorant particles, and when a deviation occurs in a part of the polarizing plane, the amount of light transmitted decreases when the polarizing plates are in parallel, When it is orthogonal, some light transmits. This transmitted light was measured as the brightness | luminance on a polarizing plate, and the ratio of the brightness | luminance at the time of orthogonal to the brightness | luminance when a polarizing plate is parallel was computed as contrast ratio.

(Contrast ratio) = (Brightness in parallel) / (Brightness in orthogonal)

Therefore, when scattering is caused by the colorant in the coating film, the brightness at the same time decreases and the brightness at the orthogonal angle 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. On the occasion of measurement, it measured through the black mask which made the hole of 1 cm square through the measurement part.

In addition, the coating film substrate used for contrast ratio evaluation apply | coats a yellow coloring composition (DY-1 ~ 38) using a spin coater on a glass substrate 100 mm x 100 mm, 1.1 mm thick, and then it drys at 70 degreeC for 20 minutes, Subsequently, it produced by heating and standing to cool at 220 degreeC for 20 minutes. The produced coating film was made to match chromaticity of x = 0.440 in C light source after heat processing at 220 degreeC. Contrast ratio was determined according to the following criteria.

○: 3000 or more

△: 2000 or more, less than 3000

×: Less than 2000

(Color evaluation)

Using the same coating film used for contrast ratio evaluation, the film thickness when the chromaticity of x (C) = 0.440 was measured, and it determined according to the following criteria. The thinner the thickness of the film imparting a chromaticity of x (C) = 0.440, the greater the coloring power, and the more excellent it can be said.

○: less than 2.0 [μm]

Δ: 2.0 or more and less than 3.0 [μm]

×: 3.0 or more [μm]

(Heat resistance evaluation)

A yellow coloring composition (DY-1 to 38) was applied onto a glass substrate 100 mm × 100 mm, 1.1 mm thick using a spin coater, then dried at 70 ° C. for 20 minutes, and then heated at 220 ° C. for 20 minutes, By allowing to cool, a coating film substrate was produced. The produced coating film board | substrate was made to match chromaticity of x = 0.440 in C light source after the heat processing at 220 degreeC. The chromaticity ([L * (1), a * (1), b * (1)]) in the C light source of the obtained coating film was measured using the microspectrophotometer (Olymps Kogaku Co., Ltd. "OSP-SP100"). Then, it heats at 230 degreeC for 1 hour as a heat resistance test, the chromaticity ([L * (2), a * (2), b * (2)]) in C light source is measured, and color difference (DELTA) Eab according to the following formula. * Was obtained and evaluated in the following three steps.

ΔEab * = √ ((L * (2)-L * (1)) ² + (a * (2)-a * (1)) ² + (b * (2)-b * (1)) ² )

○: ΔEab * is less than 5.0

Δ: ΔEab * is 5.0 or more but less than 10.0

X: ΔEab * is 10.0 or more

(Evaluation of light resistance)

A coating film substrate was produced in the same manner as in the evaluation of heat resistance, and the chromaticity ([L * (1), a * (1), b * (1)]) at the C light source was measured by a microscopic spectrophotometer (Olympus Kogaku Co., Ltd. -SP100 "). Subsequently, a UV blocking filter (“COLORED OPTICAL GLASS L38” manufactured by Hoya Corporation) was attached to the substrate and irradiated with ultraviolet rays for 100 hours using a 470 W / m ² xenon lamp, and then the chromaticity of the C light source ([L * ( 2), a * (2), b * (2)]) were measured, and the color difference ΔEab * was calculated by the above formula, and evaluated on the same basis as the heat resistance.

As shown in Table 2, the yellow coloring composition of the Example containing the quinophthalone pigment represented by General formula (1) and the quinophthalone dye represented by General formula (6) as a coloring agent which is a characteristic of this embodiment has a spectral transmittance. It was excellent in contrast ratio and coloring power, and the heat resistance and light resistance of the coating film were also the result without a problem.

On the other hand, the yellow coloring composition (DY-34-36) of the reference examples 1-3 was the result with low brightness. The yellow coloring composition (DY-37, 38) of the reference examples 4 and 5 which used specific quinophthalone dye alone and used together with CI pigment yellow 138 was a result with the favorable brightness but low contrast ratio. Moreover, the yellow coloring composition (DY-34) of the reference example 1 which used CI pigment yellow 138 which is an existing pigment independently had a problem that coloring power was low besides the point of low brightness. The yellow coloring composition (DY-35, 36) of the reference examples 2 and 3 which used CI dispase yellow 54 and CI dispase yellow 64 other than the quinophthalone dye [B] was a result with a bad contrast ratio, heat resistance, and light resistance.

<The manufacturing method of a green photosensitive coloring composition>

[Example 34]

(Green Photosensitive Coloring Composition (RG-1))

After stirring and mixing the mixture of the following composition uniformly, it filtered with 1.0 micrometer filter and obtained the green photosensitive coloring composition (RG-1).

Green coloring composition (DG-1) 23.5 parts

Yellow coloring composition (DY-1) # 21.5 parts

Acrylic resin solution 2 2.0part

Photopolymerizable monomer ("Aronix M402" made by Toagosei Corporation) 4.4 parts

Photopolymerization initiator ("Iruga cua OXE02" made by Chiba Japan Corporation) 1.2 parts

Cyclohexanone 20.0 parts

Propylene glycol monomethyl ether acetate 27.4 parts

[Examples 35-70, Reference Examples 6-15]

(Production of Green Photosensitive Coloring Composition (RG-2 to 47))

In addition to using the yellow coloring composition, green coloring composition, or blue coloring composition shown in Table 3, a yellow coloring composition, a green coloring composition, or a blue coloring composition to match chromaticity of x = 0.290, y = 0.600 in C light source at the time of coating film evaluation. The photosensitive coloring composition (RG-2-47) was produced by the method similar to the photosensitive coloring composition (RG-1) except changing the ratio of (to change the ratio so that whole quantity of a coloring composition may be 45 parts).

<Evaluation of Green Photosensitive Coloring Composition>

Evaluation of the brightness, contrast ratio, coloring power, heat resistance, light resistance, and the sensitivity of the green coating film produced using the obtained green photosensitive coloring composition (RG-1 to 47) was performed by the following method. Table 4 shows the evaluation results.

(Brightness evaluation)

The green photosensitive coloring composition (RG-1 to 47) was applied onto a glass substrate 100 mm × 100 mm, 1.1 mm thick by using a spin coater, and then dried at 70 ° C. for 20 minutes, and accumulated light amount was 150 mJ using an ultrahigh pressure mercury lamp. Ultraviolet exposure was performed at / cm ² , and developed with an alkali developer at 23 ° C to obtain a coating film substrate. Then, after heating and cooling at 220 degreeC for 20 minutes, the brightness Y (C) of the obtained coating film board | substrate was measured using the microspectrophotometer (Olymps Kogaku Corporation "OSP-SP100"). The produced coating film board | substrate was made to match chromaticity of x = 0.290 and y = 0.600 in C light source after the heat processing at 220 degreeC. As alkaline developing solution, what consists of 8.0 mass% of sodium carbonate 1.5 mass% sodium hydrogencarbonate 0.5 mass% anionic surfactant ("Perryex NBL" by Kao Corporation), and 90 mass% of water was used. Furthermore, the value of the brightness was determined according to the following criteria.

○: 60.5 or more

△: 58.5 or more, less than 60.5

×: Less than 58.5

(Contrast Ratio Evaluation)

About the measuring method of coating-contrast ratio, it measured by the method similar to the contrast ratio measurement of a yellow coloring composition. The contrast ratio was computed using the coating film similar to the brightness evaluation, and it determined according to the following criteria.

○: 3500 or more

△: 3000 or more and less than 3500

×: Less than 3000

(Color evaluation)

Using the coating film which evaluated brightness, the thickness of the film at the time of showing chromaticity of x (C) = 0.290 and y (C) = 0.600 was measured, and it determined according to the following reference | standard. The thinner the thickness of the film giving the chromaticity of x (C) = 0.290 and y (C) = 0.600, the greater the coloring power.

○: less than 2.5 [μm]

Δ: 2.5 or more and less than 3.0 [μm]

×: 3.0 or more [μm]

(Heat resistance evaluation)

The green photosensitive coloring composition (RG-1 to 47) was applied onto a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater, dried at 70 ° C. for 20 minutes, and accumulated in light using an ultrahigh pressure mercury lamp. Ultraviolet exposure was performed at 150 mJ / cm ² , and developed with an alkali developer at 23 ° C. Subsequently, after coating and heating at 220 degreeC for 20 minutes, the coating film substrate was obtained. The produced coating film board | substrate was made to match chromaticity of x = 0.290 and y = 0.600 in C light source after the heat processing at 220 degreeC. The chromaticity ([L * (1), a * (1), b * (1)]) in the C light source of the obtained coating film was measured using the microspectrophotometer (Olymps Kogaku Co., Ltd. "OSP-SP100"). Furthermore, after that, it heated at 230 degreeC for 1 hour as a heat resistance test, and measured the chromaticity ([L * (2), a * (2), b * (2)]) in C light source, according to the following formula. The color difference ΔEab * was determined and evaluated in the following three steps.

ΔEab * = √ ((L * (2) -L * (1)) ² + (a * (2) -a * (1)) ² + (b * (2) -b * (1)) ² )

○: ΔEab * is less than 5.0

Δ: ΔEab * is 5.0 or more but less than 10.0

X: ΔEab * is 10.0 or more

(Evaluation of light resistance)

A coating film substrate was produced in the same manner as in the evaluation of heat resistance, and the chromaticity ([L * (1), a * (1), b * (1)]) at the C light source was measured by a microscopic spectrophotometer (Olympus Kogaku Co., Ltd. "OSP"). -SP100 "). Subsequently, a UV blocking filter (“COLORED OPTICAL GLASS L38” manufactured by Hoya Corporation) was attached to the substrate and irradiated with ultraviolet rays for 100 hours using a 470 W / m ² xenon lamp, and then the chromaticity of the C light source ([L * ( 2), a * (2), b * (2)]) were measured, and the color difference ΔEab * was calculated according to the above formula and evaluated on the same basis as the heat resistance.

(Sensitivity evaluation)

After coating the green photosensitive coloring composition (RG-1-47) to the glass substrate of 10 cm x 10 cm by the spin coat method, it heated at 70 degreeC for 15 minutes in the clean oven, removed the solvent, and obtained the coating film of about 2 micrometers. Subsequently, after cooling this board | substrate to room temperature, the ultraviolet-ray was exposed through the photomask of a 100 micrometer width (200 micrometer peak) and a 25 micrometer width (50 micrometer peak) stripe pattern using an ultrahigh pressure mercury lamp. Thereafter, the substrate was spray-developed using an aqueous 23 ° C. sodium carbonate solution, washed with ion-exchanged water, dried by wind, and heated at 220 ° C. for 20 minutes in a clean oven. The thickness of the film of the pattern in the 100 micrometer photomask part of the filter segment formed by the said method was measured, and the minimum exposure amount which becomes 90% or more with respect to the film thickness after coating was determined according to the following reference | standard. The smaller the minimum exposure amount, the higher the sensitivity and the better the photosensitive coloring composition.

○: Less than 50mJ / cm ²

△: 50mJ / cm ² or more, less than 100 mJ / cm ²

× ： 100 mJ / cm ² or more

As shown in Table 4, the green photosensitive coloring composition of the Example containing the quinophthalone pigment represented by General formula (1) and the quinophthalone dye represented by General formula (6) as a coloring agent which is a characteristic of this embodiment is lightness, contrast ratio And it was excellent in coloring power, and the heat resistance and light resistance of a coating film were also the result without a problem. Moreover, the sensitivity was also a good result even though it contained dye.

On the other hand, the green photosensitive coloring composition (RG-38, 43) of the reference examples 6 and 11 which used CI pigment yellow 138 which is an existing pigment independently as a yellow coloring agent was a result with low coloring power. The green photosensitive coloring composition (RG-41, 42, 46, 47) of the reference examples 9, 10, 14, and 15 which used specific quinophthalone dye alone as a yellow coloring agent and used together with CI pigment yellow 138, has good brightness. But low contrast and poor sensitivity. Green photosensitive coloring composition (RG-39, 40, 44, 45) of the reference examples 7, 8, 12, 13 which used CI dispase yellow 54 and CI dispase yellow 64 other than a quinophthalone dye [B] as a yellow coloring agent. Was a bad result for all characteristics.

<Production of color filter>

First, the red photosensitive coloring composition and blue photosensitive coloring composition used for preparation of a color filter were produced.

(Production of Red Photosensitive Coloring Composition (RR-1))

After stirring and mixing the mixture of the following composition uniformly, it disperse | distributed with Eiger-Mill ("Mini Model M-250 'MKII" made from Eiger Japan Co., Ltd.) for 5 hours using the zirconium oxide beads of diameter 0.5mm, and then 5.0 micrometers It filtered with the filter of and produced the red coloring composition (DR-1).

Red Pigment (C.I. Pigment Red 254)

Red Pigment (C.I. Pigment Red 177) # 2.4

Resin-type dispersant ("EFKA4300" made by Chiba Japan Corporation) 1.0 part

Acrylic resin solution 1-35.0 parts

Propylene glycol monomethyl ether acetate 52.0 parts

Subsequently, the mixture of the following composition was stirred and mixed so that it might become uniform, and it filtered with 1.0 micrometer filter and produced the red photosensitive coloring composition (RR-1).

Red coloring composition (DR-1) 42.0 parts

Acrylic resin solution 2 13.2parts

Photopolymerizable monomer ("Aronix M400" made by Toagosei Co., Ltd.) 2.8 parts

Photopolymerization initiator ("Iruga cua 907" made by Chiba Japan Corporation) 2.0 parts

Sensitizer (Hodogaya Kagaku Kogyo "EAB-F") 0.4 copy

Ethylene glycol monomethyl ether acetate 39.6 parts

(Production of Blue Photosensitive Coloring Composition (RB-1))

After stirring and mixing the mixture of the following composition uniformly, it disperse | distributed with Eiger-Mill ("Mini Model M-250 'MKII" made from Eiger Japan Co., Ltd.) for 5 hours using the zirconium oxide beads of diameter 0.5mm, and then 5.0 micrometers It filtered with the filter of and produced the blue coloring composition (DB-1).

7.2 parts of blue pigments (C.I. pigment blue 15: 6)

Purple Pigment (C.I. Pigment Violet 23) 4.8

Resin-type dispersant ("EFKA4300" made by Chiba Japan Corporation) 1.0 part

Acrylic resin solution 1 33.5 parts

Propylene glycol monomethyl ether acetate 52.0 parts

Then, the mixture of the following composition was stirred and mixed so that it might become uniform, and it filtered with 1.0 micrometer filter and produced the blue photosensitive coloring composition (RB-1).

Blue coloring composition (DB-1) '34.0 parts

Acrylic resin solution 2-15.2 parts

Photopolymerizable monomer ("Aronix M400" made by Toagosei Co., Ltd.) 3.3 parts

Photopolymerization initiator ("Iruga cua 907" made by Chiba Japan Corporation) 2.0 parts

Sensitizer (Hadoya Kagaku Kogyo "EAB-F") 0.4 part

Ethylene glycol monomethyl ether acetate 45.1 parts

(Production of color filter)

The black matrix was pattern-processed on the glass substrate, and the red photosensitive coloring composition (RR-1) was apply | coated with the spin coater on the said board | substrate, and the coloring film was formed. A photomask was passed through the film, and ultraviolet rays of 150 mJ / cm ² were irradiated with an ultrahigh pressure mercury lamp. Next, spray development was carried out with an alkaline developer consisting of 0.2% by weight aqueous sodium carbonate solution, and the unexposed portions were removed, washed with ion-exchanged water, and the substrate was heated at 220 ° C. for 20 minutes to form a red filter segment. Here, the red filter segment was made to match chromaticity of x = 0.640 and y = 0.330 in C light source (it also uses green and blue hereafter) after heat processing at 220 degreeC. In addition, by the same method, a green filter segment is made to match chromaticity of x = 0.290 and y = 0.600 using a green photosensitive coloring composition (RG-19), and a blue filter segment is a blue photosensitive coloring composition (RB-1). Each filter segment was formed so that it might match with chromaticity of x = 0.150 and y = 0.060, and the color filter was obtained.

By using a green photosensitive coloring composition (RG-19), high brightness and high contrast of a color filter were attained, and other physical properties could be used suitably without a problem.

<< embodiment V >>

<Manufacturing method of a quinophthalone pigment | dye>

&Lt; EMI ID =

2.9 parts of 6-hexyl-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. After standing to cool, 100 parts of methanol was added, followed by stirring for 1 hour. And the solid precipitated was collected by suction filtration. Further, the solid was poured into 200 parts of methanol, stirred for 1 hour, and then collected by suction filtration. It dried with the vacuum dryer (40 degreeC) overnight, and obtained the product of 4.2 parts. Yield 82%. The compound was identified by the mass spectrometer (TOF-MS: autoflexII by Burka Dartonikus company). It confirmed that it was a target object in m / z = 408 (molecular weight 407.5).

(65)

2.3 parts of 6-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. After cooling, 100 parts of methanol was added, followed by stirring for 1 hour. And the solid precipitated was collected by suction filtration. Further, the solid was poured into 200 parts of methanol, stirred for 1 hour, and then collected by suction filtration. It dried with the vacuum dryer (40 degreeC) overnight, and obtained the product of 3.1 parts. Yield 67%. The compound was identified by the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII). It confirmed that it was a target object in m / z = 366 (molecular weight 365.4).

[Formula 66]

2.7 parts of 7-trifluoromethyl- 2-methylquinolines, 2.5 parts of naphthalenedicarboxylic acid anhydrides, and 30 parts of benzoic acid were mixed, and it stirred at 200 degreeC for 7 hours. After standing to cool, 100 parts of methanol was added, followed by stirring for 1 hour. And the solid precipitated was collected by suction filtration. Further, the solid was poured into 200 parts of methanol, stirred for 1 hour, and then collected by suction filtration. It dried with the vacuum dryer (40 degreeC) overnight, and obtained the product of 2.9 parts. Yield 58%. The compound was identified by the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII). It confirmed that it was a target object in m / z = 392 (molecular weight 391.3).

(67)

2.7 parts of 8-n-butyloxy-2-methylquinolines, 2.5 parts of naphthalenedicarboxylic acid anhydrides, and 30 parts of benzoic acid were mixed, and it stirred at 200 degreeC for 7 hours. After standing to cool, 100 parts of methanol was added, followed by stirring for 1 hour. And the solid precipitated was collected by suction filtration. Further, the solid was poured into 200 parts of methanol, stirred for 1 hour, and then collected by suction filtration. It dried with the vacuum dryer (40 degreeC) overnight, and obtained the product of 3.1 parts. The yield was 62%. The compound was identified by the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII). It confirmed that it was a target object in m / z = 396 (molecular weight 395.5).

(68)

3.4 parts of 8- (2-ethylhexyloxy) -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. After standing to cool, 100 parts of methanol was added, followed by stirring for 1 hour. And the solid precipitated was collected by suction filtration. Further, the solid was poured into 200 parts of methanol, stirred for 1 hour, and then collected by suction filtration. It dried with the vacuum dryer (40 degreeC) overnight, and obtained the product of 5.0 parts. Yield 88%. The compound was identified by the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII). It confirmed that it was a target object in m / z = 452 (molecular weight 451.5).

(69)

4.4 parts of 8- (2-ethylhexyloxy) -5-phenyl- 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. After standing to cool, 100 parts of methanol was added, followed by stirring for 1 hour. And the solid precipitated was collected by suction filtration. Further, the solid was poured into 200 parts of methanol, stirred for 1 hour, and then collected by suction filtration. It dried with the vacuum dryer (40 degreeC) overnight, and obtained the product of 5.7 parts. Yield 85%. The compound was identified by the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII). It confirmed that it was a target object in m / z = 528 (molecular weight 527.7).

(70)

4.1 parts of 8-dodecaoxy-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. After standing to cool, 100 parts of methanol was added, followed by stirring for 1 hour. And the solid precipitated was collected by suction filtration. Further, the solid was poured into 200 parts of methanol, stirred for 1 hour, and then collected by suction filtration. It dried with the vacuum dryer (40 degreeC) overnight, and obtained the product of 3.6 parts. Yield 57%. The compound was identified by the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII). It confirmed that it was a target object in m / z = 508 (molecular weight 507.6).

(71)

4.4 parts of 8- (2-ethylhexyloxy) -5-bromo-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. After standing to cool, 100 parts of methanol was added, followed by stirring for 1 hour. And the solid precipitated was collected by suction filtration. Further, the solid was poured into 200 parts of methanol, stirred for 1 hour, and then collected by suction filtration. It dried with the vacuum dryer (40 degreeC) overnight, and obtained the product of 4.1 parts. Yield 61%. The compound was identified by the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII). It confirmed that it was a target object in m / z = 531 (molecular weight 530.5).

(72)

2.9 parts of 6-trifluoromethyloxy-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. After cooling, 100 parts of methanol was added, followed by stirring for 1 hour. And the solid precipitated was collected by suction filtration. Further, the solid was poured into 200 parts of methanol, stirred for 1 hour, and then collected by suction filtration. It dried with the vacuum dryer (40 degreeC) overnight, and obtained the product of 4.3 parts. Yield 83%. The compound was identified by the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII). It confirmed that it was a target object in m / z = 408 (molecular weight 407.3).

(73)

3.4 parts of 6- (2-ethylhexyloxy) -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. After standing to cool, 100 parts of methanol was added, followed by stirring for 1 hour. And the solid precipitated was collected by suction filtration. In addition, the solid was poured into 200 parts of methanol, stirred for 1 hour, and the solid was collected by suction filtration. It dried with the vacuum dryer (40 degreeC) overnight, and obtained the product of 3.9 parts. Yield 68%. The compound was identified by the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII). It confirmed that it was a target object in m / z = 452 (molecular weight 451.5).

&Lt; EMI ID =

2.9 parts of 6- (2-ethoxyethoxy) -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. After standing to cool, 100 parts of methanol was added, followed by stirring for 1 hour. And the solid precipitated was collected by suction filtration. In addition, the solid was poured into 200 parts of methanol, stirred for 1 hour, and the solid was collected by suction filtration. It dried with the vacuum dryer (40 degreeC) overnight, and obtained the product of 3.3 parts. Yield 64%. The compound was identified by the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII). It confirmed that it was a target object in m / z = 412 (molecular weight 411.5).

(75)

3.4 parts of 6- (2- (1,3- dioxane-2-yl) ethoxy) -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. After standing to cool, 100 parts of methanol was added, followed by stirring for 1 hour. And the solid precipitated was collected by suction filtration. In addition, the solid was poured into 200 parts of methanol, stirred for 1 hour, and the solid was collected by suction filtration. It dried with the vacuum dryer (40 degreeC) overnight, and obtained the product of 3.0 parts. Yield 53%. The compound was identified by the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII). It confirmed that it was a target object in m / z = 454 (molecular weight 453.5).

[Formula 76]

3.4 parts of 4- (2-ethylhexyloxy) -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. After standing to cool, 100 parts of methanol was added, followed by stirring for 1 hour. And the solid precipitated was collected by suction filtration. In addition, the solid was poured into 200 parts of methanol, stirred for 1 hour, and the solid was collected by suction filtration. It dried with the vacuum dryer (40 degreeC) overnight, and obtained the product of 4.2 parts. Yield 74%. The compound was identified by the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII). It confirmed that it was a target object in m / z = 452 (molecular weight 451.5).

[Formula 77]

3.8 parts of ethyl 5- (2-methylquinolin-8-yloxy) pentanoate, 2.5 parts of naphthalenedicarboxylic anhydrides, and 30 parts of benzoic acid were mixed, and it stirred at 200 degreeC for 7 hours. After cooling, 100 parts of methanol was added, followed by stirring for 1 hour. And the solid precipitated was collected by suction filtration. In addition, the solid was poured into 200 parts of methanol, stirred for 1 hour, and the solid was collected by suction filtration. It dried with the vacuum dryer (40 degreeC) overnight, and obtained the product of 4.5 parts. Yield 74%. The compound was identified by the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII). It confirmed that it was a target object in m / z = 482 (molecular weight 481.5).

(78)

2.0 parts of 8-hydroxy-2-methylquinolines, 2.5 parts of naphthalenedicarboxylic acid anhydrides, and 30 parts of benzoic acid were mixed, and it stirred at 200 degreeC for 7 hours. After standing to cool, 100 parts of methanol was added, followed by stirring for 1 hour. And the solid precipitated was collected by suction filtration. In addition, the solid was poured into 200 parts of methanol, stirred for 1 hour, and the solid was collected by suction filtration. It dried with the vacuum dryer (40 degreeC) overnight, and obtained the product of 3.7 parts. The yield was 86%. The compound was identified by the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII). It confirmed that it was a target object in m / z = 339 (molecular weight 339.3).

(79)

2.0 parts of quinophthalone pigment | dye 15 were mixed with 20 parts of N, N- dimethylacetamides, 0.3 part of sodium hydroxide and 1.8 parts of 2-ethylhexyl 4- bromo butyrate were further mixed, and it stirred at 90 degreeC for 1 hour. After cooling, 100 parts of methanol and 100 parts of water were added, followed by stirring for 1 hour. And the solid precipitated was collected by suction filtration. Further, the solid was poured into 100 parts of methanol, stirred for 1 hour, and the solid was collected by suction filtration. It dried with the vacuum dryer (40 degreeC) overnight, and obtained the product of 1.6 parts. Yield 51%. The compound was identified by the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII). It confirmed that it was a target object in m / z = 538 (molecular weight 537.7).

(80)

2.0 parts of quinophthalone pigment | dye 15 were mixed with 20 parts of N, N- dimethylacetamides, 0.3 part of sodium hydroxide and 1.9 parts of 2-ethylhexyl 5-bromo- gillacetic acid were further mixed, and it stirred at 90 degreeC for 1 hour. After cooling, 100 parts of methanol and 100 parts of water were added, followed by stirring for 1 hour. And the solid precipitated was collected by suction filtration. Furthermore, the solid was put into 100 parts of methanol, stirred for 1 hour, and the solid was collected by suction filtration. It dried with the vacuum dryer (40 degreeC) overnight, and obtained the product of 2.0 parts. The yield was 62%. The compound was identified by the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII). It confirmed that it was a target object in m / z = 552 (molecular weight 551.7).

[Formula 81]

2.0 parts of quinophthalone pigment | dyes 15 are mixed with 20 parts of N, N- dimethylacetamides, and 0.3 parts of sodium hydroxide and 2- (2- (2-ethylhexyloxy) ethoxy) ethyl-2-bromobutanoate 2.4 parts was further mixed, and it stirred at 100 degreeC for 2 hours. After cooling, the reaction solution was added to 50 parts of water, and 100 parts of chloroform was further added to extract an organic layer. Magnesium sulfate was added to the organic layer, dried, filtered and concentrated under reduced pressure. The resulting concentrate was purified by silica gel column chromatography (chloroform / ethyl acetate = 10/1 (volume ratio)) to give 2.8 parts of product. The yield was 76%. The compound was identified by the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII). It confirmed that it was a target object in m / z = 626 (molecular weight 625.8).

(82)

2.0 parts of quinophthalone pigment | dyes 15 are mixed with 20 parts of N, N- dimethylacetamides, and 0.3 parts of sodium hydroxide, 2- (2- (2-ethylhexyloxy) ethoxy) ethyl-5-bromopentanoate 2.5 parts of the mixture was further mixed and stirred at 100 ° C for 2 hours. After cooling, the reaction solution was added to 50 parts of water, and 100 parts of chloroform was further added to extract an organic layer. Magnesium sulfate was added to the organic layer, dried, filtered and concentrated under reduced pressure. The obtained concentrate was purified by silica gel column chromatography (chloroform / ethyl acetate = 10/1 (volume ratio)) to obtain a product of 2.7 parts. The yield was 72%. The compound was identified by the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII). It confirmed that it was a target object in m / z = 640 (molecular weight 639.8).

(83)

2.0 parts of quinophthalone pigment | dye 15 are mixed with 20 parts of N, N- dimethylacetamides, 0.3 part of sodium hydroxide, bis (2-ethylhexyl) 7-oxabicyclo [4, 1, 0] heptane -3,4- 9.7 parts of dicarboxylate were further mixed, and it stirred at 150 degreeC for 10 hours. After cooling, the reaction solution was added to 50 parts of water, and 100 parts of chloroform was further added to extract an organic layer. Magnesium sulfate was added to the organic layer, dried, filtered and concentrated under reduced pressure. The obtained concentrate was purified by silica gel column chromatography (chloroform / ethyl acetate = 10/1 (volume ratio)) to obtain 1.3 parts of the product. Yield 30%. The compound was identified by the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII). It confirmed that it was a target object in m / z = 750 (molecular weight 749.9).

(84)

2.0 parts of Disperse Yellow 160 was mixed with 20 parts of N, N- dimethylacetamide, 0.3 part of sodium hydroxide and 1.8 part of 2-ethylhexyl 4-bromo butyrate were further mixed, and it stirred at 90 degreeC for 1 hour. After cooling, 100 parts of methanol and 100 parts of water were added, followed by stirring for 1 hour. And the solid precipitated was collected by suction filtration. Furthermore, the solid was put into 100 parts of methanol, stirred for 1 hour, and the solid was collected by suction filtration. It dried with the vacuum dryer (40 degreeC) overnight, and obtained the product of 2.0 parts. Yield 60%. The compound was identified by the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII). It confirmed that it was a target object in m / z = 538 (molecular weight 537.7).

(85)

It synthesize | combined based on the pigment | dye (IV) synthesis method of Unexamined-Japanese-Patent No. 6-009891.

&Lt; EMI ID =

Disperse Yellow 54 was used.

[Chemical Formula 87]

Disperse Yellow 64 was used.

<Preparation of acrylic resin solution>

70.0 parts of cyclohexanone was put into the reaction vessel provided with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirring device in a separable four-necked flask, the temperature was raised to 80 ° C, and the nitrogen was replaced in the reaction vessel. N-butyl methacrylate 13.3 parts, 2-hydroxyethyl methacrylate 4.6 parts, methacrylic acid 4.3 parts, paracumyl phenol ethylene oxide modified acrylate ("Aronix M110" by Toagosei Co., Ltd.) 7.4 parts A mixture of 0.4 part of 2,2'-azobis isobutylonitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight of 26000. After cooling to room temperature, approximately 2 g of the resin solution was sampled, dried by heating at 180 ° C. for 20 minutes, and the non-volatile content was measured. Then, methoxypropyl acetate was added to the synthesized resin solution so that the non-volatile content was 20% by weight. The solution was prepared.

Herein, the polymerization average molecular weight (Mw) of the acrylic resin is measured using a TSKgel column (manufactured by Tosoh Corporation) and GPC (manufactured by Tosoh Corporation, HLC-8210 GPC) equipped with a RI detector, using THF as a developing solvent. It is the weight average molecular weight (Mw) of polystyrene conversion.

<Manufacturing method of pigment>

(Production of Blue Pigment 1)

200 parts of phthalocyanine-based blue pigment CI pigment blue 15 ("LIONOL BLUE ES" made by Toyo Ink Corporation), 1400 parts of sodium chloride, and 360 parts of diethylene glycol are put in stainless steel 1 gallon kneader (product made by Inoue Sesakujo) And kneaded at 80 ° C. for 6 hours. Subsequently, the kneaded product was poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to a suspension state, filtered, washed with water repeatedly to remove sodium chloride and diethylene glycol, and dried overnight at 85 ° C. to 190 Negative blue pigment 1 was obtained. The average primary particle diameter of the obtained pigment was 79 nm.

(Production of Purple Pigment 1)

200 parts of dioxazine system purple pigment CI pigment violet 23 ("LIONOGEN VIOLET RL" made by Toyo Ink Corporation), 1400 parts of sodium chloride, and 360 parts of diethylene glycol are put in stainless steel 1 gallon kneader (product made by Inoue Sesakujo), 80 It knead | mixed for 6 hours at ° C. Subsequently, the kneaded product was poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to a suspension state, filtered, washed with water repeatedly to remove sodium chloride and diethylene glycol, and dried overnight at 85 ° C. to 190 Negative purple pigment 1 was obtained. The average primary particle diameter of the obtained pigment was 28 nm.

(Production of Blue Pigment 2)

60.0 parts of phthalonitrile, 300 parts of 1-cronaphthalenes, and 15.6 parts of aluminum chlorides were put into the glass separable four neck flask, and it stirred under reflux for 6 hours. Thereafter, the heating was stopped, and after cooling to about 200 ° C, the mixture was filtered while heated and sprayed and washed with 600 parts of hot toluene and 300 parts of acetone. The obtained wet cake was dispersed in 250 parts of toluene and stirred under reflux for 3 hours. Again, the filtrate was filtered while heating, and sprayed and washed with 600 parts of hot toluene and 300 parts of acetone, and then dispersed in 1500 parts of ion-exchanged water, and the mixture was heated and stirred at 60 to 70 ° C. for 60 minutes. It vacuum-dried at 50 degreeC after filtration and water washing, and obtained the blue solid aluminum phthalocyanine pigment (AlPc-Cl) which has a target structure. 30 parts of obtained pigments were melt | dissolved gradually, maintaining the temperature at about 5 degreeC in 1200 parts of concentrated sulfuric acid, and it stirred at this temperature for 1 hour. This was added to 6000 parts of ice water, stirring so that temperature might not exceed 5 degreeC, and it stirred for 1 hour after completion | finish of the addition process. After filtration and washing with water, 6500 parts of ion-exchanged water was redispersed and filtered again. After washing with water, the wet cake was redispersed in 2500 parts of 4% ammonia water and stirred under reflux for 6 hours. After filtration, the cake was washed with ion-exchanged water and then vacuum dried at 50 ° C. to obtain a blue solid aluminum phthalocyanine pigment (AlPc-OH) having a target structure.

50 parts of this (AlPc-OH) pigment, 150 parts of sodium chloride, and 25 parts of diethylene glycol were put in a stainless 1 gallon kneader (manufactured by Inoue Sesakujo Co., Ltd.), and kneaded at 120 ° C for 6 hours. Subsequently, the kneaded product was poured into 5 liters of warm water, stirred for 1 hour while heating to 80 占 폚, and then in suspension, filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying overnight at 85 占 폚. Blue pigment 2 was obtained. The average primary particle diameter of the obtained pigment was 28 nm.

(Production of green pigment 1)

A phthalocyanine green pigment CI pigment green 58 ("FASTGEN GREEN A110" by DIC Corporation) was used in the state which is a commercial item. The average primary particle diameter of green pigment 1 was 22 nm.

(Production of Yellow Pigment 1)

270 parts of kinophthalone type yellow pigment CI pigment yellow 138 (BASF company brand name pariotol yellow -K0961HD), 1350 parts of sodium chloride, and 500 parts of diethylene glycol are put in stainless steel 1 gallon kneader (made by Inoue Sesakujo), and it is 120 degreeC 6 hours kneading. Subsequently, the kneaded product was poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to a suspension state, filtered, washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight to dry. Negative yellow pigment 3 was obtained. The average primary particle diameter of the obtained pigment was 36 nm.

(Production of Yellow Pigment 2)

200 parts of nickel complex system yellow pigment CI pigment yellow 150 ("E-4GN" made by Lanxess Corporation), 1400 parts of sodium chloride, and 360 parts of diethylene glycol are put in a stainless gallon kneader (made by Inoue Sesakujo), and it is 120 degreeC 6 hours kneading. Subsequently, the kneaded product was poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to a suspension state, filtered, washed with water repeatedly to remove sodium chloride and diethylene glycol, and dried overnight at 85 ° C. to 190 Negative yellow pigment 2 was obtained. The volume average primary particle diameter of the obtained pigment was 67 nm.

(Production of Yellow Pigment 3)

To 500 parts of isoindolin series yellow pigment CI pigment yellow 139 ("Irgafoa yellow 2R-CF" made by Chiba Japan company), 500 parts of sodium chloride and 250 parts of diethylene glycol to stainless 1 gallon kneader (product made in Inoue Sesakujo) It put and knead | mixed at 120 degreeC for 8 hours. Next, the kneaded product was poured into 5 liters of warm water, stirred for 1 hour while heating to 80 ° C. to a suspension state, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 490 parts of yellow pigment 1 were obtained. The average primary particle diameter of the obtained pigment was 92 nm.

(Production of Red Pigment 1)

200 parts of anthraquinone series red pigment CI pigment red 177 ("chromo tarred A2B" made by Chiba Japan company), 1400 parts of sodium chloride, and 360 parts of diethylene glycol are put in stainless steel 1 gallon kneader (product made by Inoue Sesakujo), 80 It knead | mixed for 6 hours at ° C. Subsequently, this kneaded product was poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to a suspension state, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of red pigments 1 were obtained. The average primary particle diameter of the obtained pigment was 54 nm.

(Production of colored composition Q-1)

After stirring and mixing the following mixture to make it uniform, it was made to disperse | distribute with Eiger-Mill ("Mini Model M-250 'MKII" by Eiger Japan Co., Ltd.) for 5 hours using the zirconium oxide beads of diameter 0.5mm, and it was a filter of 5.0 micrometers It filtered through and produced the coloring composition Q-1.

Kinophthalone dye 1 ': 11.0 parts

Acrylic resin solution which we adjusted first: 40.0 parts

Cyclohexanone ： 48.0 parts

(Production of coloring composition Q-2-24)

Hereinafter, except having changed the quinophthalone pigment | dye 1 into the quinophthalone pigment | dye shown in Table 2, it carried out similarly to coloring composition Q-1, and produced coloring composition Q-2-24.

(Production of colored composition DP-1)

After stirring and mixing the following mixture to make it uniform, it was made to disperse | distribute with Eiger-Mill ("Mini Model M-250 'MKII" made from Eiger Japan Co., Ltd.) for 5 hours using the zirconium oxide beads of diameter 0.5mm, and it was a filter of 5.0 micrometers. It filtered with and produced the coloring composition (DP-1).

Blue pigment 1 '(C.I. pigment blue 15: 6)': 11.0 parts

Acrylic resin solution which we adjusted first ： 40.0 parts

Propylene glycol monomethyl ether acetate (PGMAC): 48.0 parts

Resin type dispersant ("EFKA4300" made by Chiba Japan Corporation): 1.0 part

(Production of colored composition DP-2-8)

Hereinafter, except having changed the blue pigment 1 into the pigment shown in Table 3, it carried out similarly to the coloring composition DP-1, and produced the coloring composition DP-2-8.

[Examples 1-20, Reference Examples 1-7]

<Coloring composition Q-1-24, coating film foreign material test of DP-5-7>

Evaluation was performed by producing a test substrate and counting the number of particles. The coloring composition was apply | coated so that a dry coating might be set to about 2.0 micrometers on a transparent substrate, and it heated at 230 degreeC for 20 minutes in oven, and obtained the test board | substrate. Evaluation evaluated the surface using the metallographic microscope by the Olympus system company "BX60." The magnification is 500 times and the transmission counts the number of observable particles in any 5 field of view. In the following evaluation result, (circle) and (circle) are favorable, (triangle | delta) is a level which has many foreign substances but there is no problem in use, and x shows the coating unevenness by a foreign substance.

◎: Less than five

○: Five or more, less than 20

△: 20 or more, less than 100

× ： More than 100

The results are shown in Table 4 below.

<Spectral evaluation of coloring composition Q-1-24, DP-5-7>

The coating film was created so that the transmittance | permeability of 450 nm wavelength may be set to 5% on the transparent substrate, and the value of the transmittance | permeability of 500 nm and 550 nm at that time was measured. The higher the transmittance of 500 nm and 550 nm, the better the brightness. In the following evaluation result, the transmittance | permeability of 500 nm and 550 nm at the time of normalizing a quinophthalone pigment | dye and a yellow pigment is 99% or more in (circle), (triangle | delta) is 97 or more and less than 99%, and x is less than 97%. It is high and preferable that it is 99% or more. The results are shown in Table 4 below. Moreover, the spectrum of the coating film of Example 5 and the reference examples 1 and 3 is shown to FIGS.

As for Examples 1-20, there was little coating film foreign material and the favorable result was shown. In addition, Examples 1-20 were the result which was excellent in the spectral characteristic, and showed the spectral shape which brightness increases. Although the transmittance | permeability in 550 nm was comparatively favorable, the reference examples 2-6 showed the spectral shape which the transmittance | permeability in 500 nm is low and the brightness improvement cannot be anticipated.

Reference Examples 1 to 4 using a dye having a hydroxyl group in the chinoline ring were compared with the spectral shapes of Examples 1 to 20 using a dye without a hydroxyl group (for example, in Example 5 of FIG. 1 and Reference Examples 1 and 3). Spectrophotometer of coating film) The pigment | dye which has low transmittance | permeability in 500 nm and has a hydroxyl group in a chinoline ring is a pigment | dye which cannot anticipate the improvement of lightness.

<Manufacturing method of a blue resist material>

The following mixture was stirred and mixed to make it uniform, and then filtered through a 1.0 μm filter to obtain a blue resist material B-1.

Coloring composition (DP-1) '： 48.0 parts

Coloring composition (DP-2) '： 12.0 parts

Acrylic resin solution adjusted earlier ： 11.0 parts

Trimethylolpropane triacrylate: 4.2 parts

(`` NK ester ATMPT '' made by Shin-Nakamura Kagaku Corporation)

Photopolymerization initiator ("irgacua 907" made by Chiba Japan Corporation) 1.2 parts

Sensitizer ("EAB-F" made by Hodogaya Kagakusha) 0.4 0.4 part

Propylene Glycol Monomethyl Ether Acetate (PGMAC) ： 23.2 parts

Example 21

<Adjustment of Resist Material G-1>

The following mixture was stirred and mixed to make it uniform, and then filtered through a 1.0 μm filter to obtain a green resist material (G-1).

Coloring composition (DP-3) '： 18.0 parts

Coloring composition (Q-1) 4: 42.0 parts

Acrylic resin solution adjusted earlier ： 11.0 parts

Trimethylolpropane triacrylate ： 4.2 parts

(`` NK ester ATMPT '' made by Shin-Nakamura Kagaku Corporation)

Photopolymerization initiator ("Iruga cua 907" made by Chiba Japan Corporation: 1.2 parts)

Sensitizer ("EAB-F" made by Hodogaya Kagakusha) 0.4 0.4 part

Propylene glycol monomethyl ether acetate (PGMAC): 23.2 parts

[Examples 22-66, Reference Examples 8-15]

<Adjustment of Resist Materials G-2 to 46, R-1 to 4, and Y-1 to 4>

Hereinafter, except having changed the kind and compounding quantity of a coloring composition as shown to Tables 5 and 6, it carried out similarly to the resist material G-1, and obtained resist materials G-2-4, R-1-4, Y-1-4.

<Evaluation of resist material>

Each test of the color characteristics (Y: brightness), coating film foreign material, heat resistance, and light resistance of the obtained resist material G-1-46, R-1-4, Y-1-4 was performed by the following method. The test results are shown in Table 7.

<Color characteristic (Y: brightness)>

On the glass substrate, in the C light source, the resist materials G-1 to 46 were coated with a resist material at the thickness of the film as if x = 0.264 and y = 0.600, and the substrate was heated at 230 ° C. for 20 minutes. The resist materials R-1-4 apply | coated the resist material to the film thickness which seems to be x = 0.340 and y = 0.640, and heated this board | substrate at 230 degreeC for 20 minutes. The resist materials Y-1-4 apply | coated the resist material to the film thickness which seems to be x = 0.440 and y = 0.506, and heated this board | substrate at 230 degreeC for 20 minutes. Then, the brightness Y of the obtained board | substrate was measured with the microscopic spectrophotometer (Olymps Kogaku Corporation "OSP-SP200").

The results are shown in Table 7 below.

<Coating foreign material test>

The resist material was apply | coated so that a dry-coating film might be set to about 2.5 micrometers on a transparent substrate, and after full-surface ultraviolet exposure, it heated in 230 degreeC for 20 minutes and left to cool, and obtained the evaluation board | substrate. Evaluation evaluated the surface using the metallographic microscope by the Olympus system company "BX60." The magnification is set to 500 times, and the number of particles that can be seen at any five fields by transmission is counted. In the following evaluation result, (circle) and (circle) are favorable, (triangle | delta) is a level which has many foreign substances but there is no problem in use, and x shows the coating unevenness by a foreign substance.

◎: Less than five

○: Five or more, less than 20

△: 20 or more, less than 100

× ： More than 100

The results are shown in Table 7 below.

<Coating film heat resistance test>

A resist material was applied on the transparent substrate so as to have a dry coating of about 2.5 μm, subjected to ultraviolet exposure through a mask having a predetermined pattern, and then sprayed with an alkaline developer with a spray to remove the uncured portion to form a desired pattern. Then, after chromaticity 1 (L * (1), a * (1), b * (1)) in C light source of the coating film obtained after heating and cooling in 230 degreeC for 20 minutes, and cooling, it is a microspectral photometer (Olympus nose) It measured using Gaku Corporation "OSP-SP200". Furthermore, after that, it heated at 230 degreeC for 1 hour as an heat test, and chromaticity 2 (L * (2), a * (2), b * (2)) in C light source was measured. Using the measured color difference value, color difference (DELTA) Eab * was computed according to the following formula, and the heat resistance of the coating film was evaluated in the following four steps. Moreover, if evaluation is more than (triangle | delta), it is a level which is satisfactory practically.

ΔEab * = √ ((L * (2)-L * (1)) 2+ (a * (2)-a * (1)) 2+ (b * (2)-b * (1)) 2)

◎ ： ΔEab * is less than 1.5

○: ΔEab * is 1.5 or more but less than 3.0

Δ: ΔEab * is 3.0 or more but less than 5.0

X: ΔEab * is 5.0 or more

The results are shown in Table 7 below.

<Film coating light resistance test>

A test substrate was produced in the same procedure as the coating film heat resistance test, and chromaticity 1 (L * (1), a * (1), and b * (1)) at the C light source was determined by a microscopic spectrophotometer (Olympus Kogaku Co., Ltd., "OSP-"). SP200 "). Then, the board | substrate was put into the light resistance tester ("SUNTESTCPS +" by TOYOSEIKI Corporation), and it was left to stand for 500 hours. After removing the substrate, the chromaticity 2 (L * (2), a * (2), b * (2)) in the C light source was measured, and the color difference ΔEab * was calculated in the same manner as the coating film heat resistance test, and the coating film heat resistance test The solvent resistance of the coating film was evaluated based on the same criteria. Moreover, if evaluation is more than (triangle | delta), it is a level which is satisfactory practically.

The results are shown in Table 7 below.

<Coating Solvent Resistance Test>

A test substrate was produced in the same procedure as the coating film heat resistance test, and chromaticity 1 (L * (1), a * (1), and b * (1)) at the C light source was determined by a microscopic spectrophotometer (Olympus Kogaku Co., Ltd., "OSP-"). SP200 "). Thereafter, the substrate was immersed in N-methylpyrrolidone for 30 minutes. After removing the substrate, chromaticity 2 (L * (2), a * (2), b * (2)) in the C light source was measured, and the color difference ΔEab * was calculated in the same manner as the coating film heat resistance test, and the coating film heat resistance test The solvent resistance of the coating film was evaluated based on the same criteria. Moreover, if evaluation is more than (triangle | delta), it is a level which is satisfactory practically.

The results are shown in Table 7 below.

The resist materials (G-1 to 20, G-22 to 41, R-1 to 3, and Y-1 to 3) of Examples 21 to 66 exhibited lightness (Y), coating foreign matter, heat resistance, light resistance, and solvent resistance. Good results were shown.

On the other hand, since the resist materials G-44 and G-45 of Reference Examples 11 and 12 have poor heat resistance and light resistance, actual use thereof is difficult. The resist materials (G-21, G-43-46, R-4, and Y-4) of the reference examples 8-15 were the results with low brightness (Y) compared with the Example.

[Example 58]

<Color filter (CF-1)>

A black matrix is patterned on the glass substrate, and a red coat material (R-1) is applied on the substrate to a thickness of a film such as a C light source, x = 0.640, y = 0.340 to form a colored film. It was. A photomask was passed through the film, and ultraviolet rays of 300mJ / cm ² were irradiated with an ultrahigh pressure mercury lamp. After spray development with an alkaline developer consisting of 0.2% by weight aqueous sodium carbonate solution to remove unexposed portions, the substrate was washed with ion-exchanged water and heated at 230 ° C. for 20 minutes to form a red filter segment. By the same method, the green resist material (G-36) becomes x = 0.264 and y = 0.600, and becomes x = 0.150 and y = 0.060 using a blue resist material (B-1). It applied to the thickness of the same film | membrane, respectively, and formed the green filter segment and the blue filter segment, and obtained the color filter (CF-1).

<Production of Liquid Crystal Display Device>

The transparent ITO electrode layer was formed on the obtained RGB color filter, and the polyimide orientation layer was formed on it. On the other surface of this glass substrate, the color display device was produced in combination with the 3-wavelength CCFL light source of a polarizing plate. On the other hand, the TFT array and the pixel electrode were formed on one surface of another (second) glass substrate, and the polarizing plate was formed on the other surface. The two glass substrates thus prepared were disposed to face the electrode layers so as to face each other, and the spacers were aligned while keeping the distance between the two substrates constant, and the surroundings were sealed with a sealant to leave the openings for injecting the liquid crystal composition. . After inject | pouring a liquid crystal composition from an opening part, the opening part was sealed. The color display device was manufactured by combining the liquid crystal display device thus produced with the three-wavelength CCFL light source of the backlight unit.

[Examples 68-71, Reference Examples 16, 17]

(Color filter (CF-2-7))

Hereinafter, by the same method as the preparation of the color filter CF-1, the color filters (CF-2 to ~) of Examples 68 to 71, and Reference Examples 16 and 17 by the combination of the resist material shown in Table 8 and the three-wavelength CCFL light source 7) and color display device.

Then, in the obtained color display apparatus, the light source was light-emitted, the color image was displayed, and the brightness Y of the filter segment part of each color was measured with the microscopic spectrophotometer (Olymps Kogaku Corporation "OSP-SP200"). The results are shown in Table 8.

Comparing Examples 68, 69 and Reference Example 16, the color filter formed by using the quinophthalone dye of the present embodiment has at least one filter segment (green or red) compared to the filter segment using a conventional pigment. In the color filters (CF-2, 3) using the quinophthalone pigment | dye of this embodiment, the brightness improved. As a result, the brightness of white display became high and the improvement of the performance as a color filter was confirmed.

In addition, it was confirmed that the color filter (CF-1) formed by using the quinophthalone pigment | dye of this embodiment for both green and red of Example 67 further improved brightness, and as a result, the brightness of white display became high.

In addition, when Example 71 is compared with Reference Example 17, the color filter formed by using the quinophthalone dye of the present embodiment has at least one filter segment (yellow) compared to a filter segment containing a pigment that has been used conventionally. Also in the color filter (CF-6) containing the quinophthalone pigment | dye of this embodiment, the brightness improved, As a result, the brightness of a white display became high and the improvement of the performance as a color filter was confirmed.

In addition, when the green, red, and yellow of Example 70 all contained the color filter dye of the present embodiment (CF-5), the brightness was further improved, and as a result, the brightness of the white display was confirmed to increase. .

From the above results, by using the quinophthalone pigment | dye of this embodiment and the coloring composition which mix | blended it, high brightness of a color filter is possible and other physical properties can be used suitably without a problem.

<< embodiment VI >>

In addition, the weight average molecular weight (Mw) of resin is as follows.

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

Polymerization average molecular weight (Mw) of resin was polystyrene conversion measured using THF as a developing solvent in GPC (Tosoh Corporation, HLC-8120 GPC) equipped with RI detector using TSKgel column (made by Tosoh Corporation). It is the weight average molecular weight (Mw) of.

Next, the manufacturing method of the binder resin solution, the coloring agent, the micro pigment, and the acrylic resin solution used by the Example and the reference example is demonstrated.

<Method for producing binder resin solution>

(Preparation of acrylic resin solution 1)

196 parts of cyclohexanone were put into a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube, and a stirring device in a separable four-necked flask, the temperature was raised to 80 ° C., and the inside of the reaction vessel was replaced with nitrogen. From the dropping tube, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylates, 12.0 parts of methacrylic acid, paracumyl phenol ethylene oxide modified acrylate ("Aronix M110 made by Toagosei Co., Ltd.") A mixture of 20.7 parts and 1.1 parts of 2,2'-azobisisobutylonitrile was dripped over 2 hours. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain a solution of acrylic resin. After cooling to room temperature, about 2 parts of a resin solution was sampled, and it heat-dried at 180 degreeC for 20 minutes, and measured a non volatile matter, The methoxy propyl acetate was added to the synthesized resin solution so that a non volatile matter might be 20 mass%, and an acrylic resin Solution 1 was prepared. The weight average molecular weight (Mw) was 26000.

(Preparation of acrylic resin solution 2)

207 parts of cyclohexanone were placed in a separable four-necked flask with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube, and a stirring device, and the temperature was raised to 80 ° C., and the nitrogen was replaced in the reaction vessel. 20 parts of methacrylic acid, 20 parts of paracumyl phenol ethylene oxide modified acrylates (Aronix M110 made by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2, from a dripping pipe The mixture of 1.33 parts of 2'- azobisisobutylonitrile was dripped over 2 hours. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain a copolymer resin solution. Subsequently, with respect to the entire amount of the obtained copolymer solution, the nitrogen gas was stopped and stirred while injecting dry air for 1 hour, and then cooled to room temperature, followed by 2-methacryloyloxyethyl isocyanate (Carenz MOI manufactured by Showa Denko). The mixture of 6.5 parts, dibutyltin laurate 0.08 parts, and 26 parts of cyclohexanone was dripped at 70 degreeC over 3 hours. After completion of the dropwise addition, the reaction was continued for 1 hour to obtain a solution of an acrylic resin. After cooling to room temperature, about 2 parts of a resin solution was sampled, it heat-dried at 180 degreeC for 20 minutes, and a non-volatile content was measured, and cyclohexanone was added to the synthesized resin solution so that a non-volatile content may be 20 mass%, and the acrylic resin solution 2 was prepared. The weight average molecular weight (Mw) was 18000.

<Manufacturing method of a coloring agent>

(Preparation of hydroxyaluminum phthalocyanine 1)

In the reaction vessel, 225 parts of phthalodinitrile and 78 parts of aluminum chloride anhydride were added and stirred in 1250 parts of n-amyl alcohol. To this, 266 parts of DBU (1,8-Diazabicyclo [4.0]] undec-7-ene) were added, the temperature was raised, and the mixture was refluxed at 136 ° C for 5 hours. The reaction solution cooled to 30 degreeC with stirring was poured into the mixed solvent of 5000 parts of methanol and 10000 parts of water under stirring, and the blue suspension was obtained. The suspension was filtered, washed with 2000 parts of methanol and 4000 parts of water mixed solvent, and dried to obtain 135 parts of chloro aluminum phthalocyanine. Further, 100 parts of chloro aluminum phthalocyanine was slowly added to 1200 parts of concentrated sulfuric acid at room temperature in the reaction vessel. It stirred at 40 degreeC for 3 hours, and poured sulfuric acid solution into 24000 parts of 3 degreeC cold waters. The blue precipitate was filtrated, washed with water and dried to obtain 102 parts of hydroxyaluminum phthalocyanine 1 represented by the following formula (3).

[Formula 88]

(Preparation of hydroxyaluminum phthalocyanine 2)

In the production of hydroxyaluminum phthalocyanine 1, hydroxyaluminum phthalocyanine 2 represented by the following formula (4) was obtained by the same manufacturing method except that 250 parts of 4-methylphthalodinitriles were changed instead of phthalodinitrile.

(89)

(Preparation of hydroxyaluminum phthalocyanine 3)

In the production of hydroxyaluminum phthalocyanine 1, hydroxyaluminum phthalocyanine 3 represented by the following formula (5) was obtained by the same manufacturing method, except that 285 parts of 4-chlorophthalodidinini was changed instead of phthalodinitrile.

(90)

(Production of Blue Colorant (BC-1))

100 parts of hydroxyaluminum phthalocyanine 1, 1200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a stainless 1 gallon kneader (manufactured by Inoue Sesakujo), and kneaded at 70 ° C for 6 hours. The kneaded product was poured into 3000 parts of warm water, stirred for 1 hour while heating to 70 ° C, and the mixture was stirred. Repeated filtration and washing to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 ° C to give a blue colorant ( BC-1) was obtained. The average primary particle diameter was 30.4 nm.

(Production of Blue Coloring Agent (B-1))

In a reaction vessel, 100 parts of hydroxyaluminum phthalocyanine 1 and 49.5 parts of diphenyl phosphate were added to 1000 parts of methanol, and heated to 40 ° C to react for 8 hours. After cooling this to room temperature, the product was filtered, washed with methanol, and dried, and 114 parts of specific phthalocyanine pigment | dyes represented by Formula (1-1) were obtained. Then, the salt milling process was performed. 100 parts of specific phthalocyanine pigment | dye represented by Formula (1-1), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were put into the stainless 1 gallon kneader (made by Inoue Sesakujo), and it knead | mixed at 70 degreeC for 6 hours. The kneaded product was poured into 3000 parts of warm water, stirred for 1 hour while heating to 70 ° C, and the mixture was stirred. Repeated filtration and washing to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 ° C to give a blue colorant ( B-1) 98 parts were obtained. The average primary particle diameter was 31.2 nm.

[Formula 91]

(Production of Blue Coloring Agent (B-2))

100 parts of hydroxyaluminum phthalocyanine 1 and 43.2 parts of diphenylphosphinic acid were added to 1000 parts of methanol in a reaction vessel, and it heated at 40 degreeC and made it react for 8 hours. After cooling this to room temperature, the product was filtered, washed with methanol, and dried, and 112 parts of specific phthalocyanine pigment | dyes represented by Formula (1-2) were obtained. The blue coloring agent (B-2) was obtained for the specific phthalocyanine pigment | dye represented by obtained Formula (1-2) by the salt milling method similar to a blue coloring agent (B-1). The average primary particle diameter was 29.5 nm.

&Lt; EMI ID =

(Production of Blue Coloring Agent (B-3))

100 parts of hydroxyaluminum phthalocyanine 2 and 28.0 parts of phenylphosphinic acid were added to 1000 parts of methanol in a reaction vessel, and it heated at 40 degreeC and made it react for 8 hours. After cooling this to room temperature, the product was filtered, washed with methanol, and dried, and 102 parts of specific phthalocyanine pigment | dyes represented by Formula (1-3) were obtained. The blue coloring agent (B-3) was manufactured for the specific phthalocyanine pigment | dye represented by obtained Formula (1-3) by the salt milling method similar to a blue coloring agent (B-1). The average primary particle diameter was 33.1 nm.

&Lt; EMI ID =

(Production of Blue Coloring Agent (B-4))

In a reaction vessel, 100 parts of hydroxyaluminum phthalocyanine 3 and 41.5 parts of dibutyl phosphate were added to 1000 parts of methanol, and the mixture was heated to 40 ° C and reacted for 8 hours. After cooling this to room temperature, the product was filtered, washed with methanol, and dried, and 109 parts of specific phthalocyanine pigment | dyes represented by Formula (1-4) were obtained. The blue coloring agent (B-4) was manufactured for the specific phthalocyanine pigment | dye represented by obtained Formula (1-4) by the salt milling method similar to a blue coloring agent (B-1). The average primary particle diameter was 28.9 nm.

(94)

(Production of Green Colorant (G-1))

100 parts of CI pigment green 58 ("FASTGEN GREEN A110" by DIC Corporation), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were put into the stainless 1 gallon kneader (made by Inoue Sesakujo), and it knead | mixed at 70 degreeC for 6 hours. The kneaded product was poured into 3000 parts of warm water, stirred for 1 hour while heating to 70 ° C, and the mixture was stirred. Repeated filtration and washing to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 ° C. 97 parts of G-1 were obtained. The average primary particle diameter was 28.2 nm.

(Manufacture of Kinophthalone 1)

20 parts of 8-hydroxy-2-methylquinoline, 25 parts of naphthalenedicarboxylic acid anhydrides, and 300 parts of benzoic acid were mixed, and it stirred at 200 degreeC for 7 hours. After cooling, 1000 parts of methanol was added, followed by stirring for 1 hour. And the solid precipitated was collected by suction filtration. In addition, the solid was poured into 2000 parts of methanol, stirred for 1 hour, and the solid was collected by suction filtration. 37 parts of quinophthalones 1 which dry with a vacuum dryer (40 degreeC) overnight, and are represented by following formula (6) were obtained. The compound was identified by the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII). It confirmed that it was a target object in m / z = 339 (molecular weight 339.3).

&Lt; EMI ID =

(Production of Yellow Colorant (Y-1))

29 parts of 6-hexyl-2-methylquinoline, 25 parts of naphthalenedicarboxylic acid anhydrides, and 300 parts of benzoic acid were mixed, and it stirred at 200 degreeC for 7 hours. After cooling, 1000 parts of methanol was added, followed by stirring for 1 hour. And the solid precipitated was collected by suction filtration. In addition, the solid was poured into 2000 parts of methanol, stirred for 1 hour, and the solid was collected by suction filtration. 42 parts of specific quinophthalone pigment | dyes (yellow coloring agent (Y-1)) which dry with a vacuum dryer (40 degreeC) overnight, and are represented by Formula (2-1) were obtained. The compound was identified by the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII). It confirmed that it was a target object in m / z = 408 (molecular weight 407.5).

&Lt; EMI ID =

(Production of Yellow Colorant (Y-2))

34 parts of 8- (2-ethylhexyloxy) -2-methylquinoline, 25 parts of naphthalenedicarboxylic acid anhydrides, and 300 parts of benzoic acid were mixed, and it stirred at 200 degreeC for 7 hours. After cooling, 1000 parts of methanol was added, followed by stirring for 1 hour. And the solid precipitated was collected by suction filtration. Furthermore, the solid was put into 2000 parts of methanol, stirred for 1 hour, and the solid was collected by suction filtration. 50 parts of specific quinophthalone pigment | dyes (yellow coloring agent (Y-2)) which dry with a vacuum dryer (40 degreeC) overnight, and are represented by Formula (2-5) were obtained. The compound was identified by the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII). It confirmed that it was a target object in m / z = 452 (molecular weight 451.5).

[Formula 97]

(Production of Yellow Colorant (Y-3))

44 parts of 8- (2-ethylhexyloxy) -5-phenyl- 2-methylquinoline, 25 parts of naphthalenedicarboxylic anhydrides, and 300 parts of benzoic acid were mixed, and it stirred at 200 degreeC for 7 hours. After cooling, 1000 parts of methanol was added, followed by stirring for 1 hour. And the solid precipitated was collected by suction filtration. Furthermore, the solid was put into 2000 parts of methanol, stirred for 1 hour, and the solid was collected by suction filtration. 57 parts of specific quinophthalone pigment | dyes (yellow coloring agent (Y-3)) which dry with a vacuum dryer (40 degreeC) overnight, and are represented by Formula (2-6) were obtained. The compound was identified by the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII). It confirmed that it was a target object in m / z = 528 (molecular weight 527.7).

(98)

(Production of Yellow Colorant (Y-4))

46 parts of 8-dodecaoxy-5-bromo-2-methylquinoline, 25 parts of naphthalenedicarboxylic acid anhydrides, and 300 parts of benzoic acid were mixed, and it stirred at 200 degreeC for 7 hours. After cooling, 1000 parts of methanol was added, followed by stirring for 1 hour. And the solid precipitated was collected by suction filtration. Furthermore, the solid was put into 2000 parts of methanol, stirred for 1 hour, and the solid was collected by suction filtration. 46 parts of specific quinophthalone pigment | dyes (yellow coloring agent (Y-4)) which dry with a vacuum dryer (40 degreeC) overnight, and are represented by Formula (2-8) were obtained. The compound was identified by the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII). It confirmed that it was a target object in m / z = 531 (molecular weight 530.5).

[Formula 99]

(Production of Yellow Colorant (Y-5))

34 parts of 6- (2-ethylhexyloxy) -2-methylquinoline, 25 parts of naphthalenedicarboxylic acid anhydrides, and 300 parts of benzoic acid were mixed, and it stirred at 200 degreeC for 7 hours. After cooling, 1000 parts of methanol was added, followed by stirring for 1 hour. And the solid precipitated was collected by suction filtration. Furthermore, the solid was put into 2000 parts of methanol, stirred for 1 hour, and the solid was collected by suction filtration. 43 parts of specific quinophthalone pigment | dyes (yellow coloring agent (Y-5)) which dry with a vacuum dryer (40 degreeC) overnight, and are represented by Formula (2-10) were obtained. The compound was identified by the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII). It confirmed that it was a target object in m / z = 452 (molecular weight 451.5).

(100)

(Production of Yellow Colorant (Y-6))

29 parts of 6- (2-ethoxyethoxy) -2-methylquinoline, 25 parts of naphthalenedicarboxylic anhydrides, and 300 parts of benzoic acid were mixed, and it stirred at 200 degreeC for 7 hours. After cooling, 1000 parts of methanol was added, followed by stirring for 1 hour. And the solid precipitated was collected by suction filtration. Furthermore, the solid was put into 2000 parts of methanol, stirred for 1 hour, and the solid was collected by suction filtration. 39 parts of specific quinophthalone pigment | dyes (yellow coloring agent (Y-6)) which dry with a vacuum dryer (40 degreeC) overnight, and are represented by Formula (2-11) were obtained. The compound was identified by the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII). It confirmed that it was a target object in m / z = 412 (molecular weight 411.5).

(101)

(Production of Yellow Colorant (Y-7))

34 parts of 6- (2- (1,3- dioxane-2-yl) ethoxy) -2-methylquinoline, 25 parts of naphthalenedicarboxylic anhydrides, and 300 parts of benzoic acid were mixed, and it stirred at 200 degreeC for 7 hours. After cooling, 1000 parts of methanol was added, followed by stirring for 1 hour. And the solid precipitated was collected by suction filtration. Furthermore, the solid was put into 2000 parts of methanol, stirred for 1 hour, and the solid was collected by suction filtration. 33 parts of specific quinophthalone pigment | dyes (yellow coloring agent (Y-7)) which dry with a vacuum dryer (40 degreeC) overnight, and are represented by Formula (2-12) were obtained. The compound was identified by the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII). It confirmed that it was a target object in m / z = 454 (molecular weight 453.5).

&Lt; EMI ID =

(Production of Yellow Colorant (Y-8))

34 parts of 4- (2-ethylhexyloxy) -2-methylquinoline, 25 parts of naphthalenedicarboxylic acid anhydrides, and 300 parts of benzoic acid were mixed, and it stirred at 200 degreeC for 7 hours. After cooling, 1000 parts of methanol was added, followed by stirring for 1 hour. And the solid precipitated was collected by suction filtration. Furthermore, the solid was put into 2000 parts of methanol, stirred for 1 hour, and the solid was collected by suction filtration. 42 parts of specific quinophthalone pigment | dyes (yellow coloring agent (Y-8)) which dry with a vacuum dryer (40 degreeC) overnight, and are represented by Formula (2-13) were obtained. The compound was identified by the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII). It confirmed that it was a target object in m / z = 452 (molecular weight 451.5).

&Lt; EMI ID =

(Production of Yellow Colorant (Y-9))

20 parts of quinophthalone 1 shown by Formula (6) are mixed with 200 parts of N, N- dimethylacetamides, 3 parts of sodium hydroxide and 18 parts of 2-ethylhexyl 4- bromo butyric acid are further mixed, and it is 90 degreeC Stirred for 1 hour. After cooling, 1000 parts of methanol and 1000 parts of water were added, followed by stirring for 1 hour. And the solid precipitated was collected by suction filtration. Furthermore, the solid was put into 1000 parts of methanol, stirred for 1 hour, and the solid was collected by suction filtration. 16 parts of specific quinophthalone pigment | dyes (yellow coloring agent (Y-9)) which dry with a vacuum dryer (40 degreeC) overnight, and are represented by Formula (2-27) were obtained. The compound was identified by the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII). It confirmed that it was a target object in m / z = 538 (molecular weight 537.7).

&Lt; EMI ID =

(Production of Yellow Colorant (Y-10))

20 parts of quinophthalone 1 shown by Formula (6) are mixed with 200 parts of N, N- dimethylacetamides, 3 parts of sodium hydroxide and 19 parts of 2-ethylhexyl-5-bromo-gilic acid are further mixed, and it is 90 degreeC Stirred for 1 hour. After cooling, 1000 parts of methanol and 1000 parts of water were added, followed by stirring for 1 hour. And the solid precipitated was collected by suction filtration. Furthermore, the solid was put into 1000 parts of methanol, stirred for 1 hour, and the solid was collected by suction filtration. 20 parts of specific quinophthalone pigment | dyes (yellow coloring agent (Y-10)) which dry with a vacuum dryer (40 degreeC) overnight, and are represented by Formula (2-28) were obtained. The compound was identified by the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII). It confirmed that it was a target object in m / z = 552 (molecular weight 551.7).

&Lt; EMI ID =

(Production of Yellow Colorant (Y-11))

20 parts of commercially available CI disperse yellow 160 are mixed with 200 parts of N, N-dimethylacetamide, and 3 parts of sodium hydroxide and 18 parts of 2-ethylhexyl-4-bromo butyrate are further mixed at 90 ° C for 1 hour. Stirred. After cooling, 1000 parts of methanol and 1000 parts of water were added, followed by stirring for 1 hour. And the solid precipitated was collected by suction filtration. Furthermore, the solid was put into 1000 parts of methanol, stirred for 1 hour, and the solid was collected by suction filtration. 20 parts of specific quinophthalone pigment | dyes (yellow coloring agent (Y-11)) which dry with a vacuum dryer (40 degreeC) overnight, and are represented by Formula (2-30) were obtained. The compound was identified by the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII). It confirmed that it was a target object in m / z = 538 (molecular weight 537.7).

&Lt; EMI ID =

(Production of Yellow Colorant (YC-3))

100 parts of CI Pigment Yellow 138 (trade name Pariotol Yellow-K0961HD manufactured by BASF Corporation), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a stainless 1 gallon kneader (manufactured by Inoue Sesakujo), and kneaded at 70 ° C for 6 hours. The kneaded product was poured into 3000 parts of warm water, stirred for 1 hour while heating to 70 ° C, and the mixture was stirred. Repeated filtration and washing to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 ° C. YC-3) 98 parts were obtained. The average primary particle diameter was 35.5 nm.

Example 1

(Green Coloring Composition (DG-1))

After stirring and mixing the mixture of the following composition uniformly, it disperse | distributed with Eiger-Mill ("Mini Model M-250 'MKII" made from Eiger Japan Co., Ltd.) for 5 hours using the zirconium oxide beads of diameter 0.5mm, and then 5.0 micrometers It filtered with the filter of and produced the green coloring composition (GP-1). At this time, when producing an application board | substrate, the ratio of the blue coloring agent (B-1) and the yellow coloring agent (Y-1) was selected so that it might match chromaticity of x = 0.290 and y = 0.600 in C light source.

Blue colorant (B-1) 5.2 parts

Yellow colorant (Y-1) 5.8 parts

Resin-type dispersant (BYK-LPN6919 made by BIG Chemie Co., Ltd.) 부 5.5 parts

Acrylic resin solution 1 28.5parts

Propylene glycol monomethyl ether acetate 39.0 parts

16.0 parts cyclohexanone

[Examples 2 to 24 and Reference Examples 1 to 10]

(Green coloring composition (DG-2-34))

Green coloring composition (DG-1) of Example 1 except changing the blue coloring agent (B-1) and the yellow coloring agent (Y-1) into the combination of the coloring agent shown in Table 1, and also changing the compounding ratio of a coloring agent. In the same manner as described above, a green coloring composition (DG-2 to 34) was obtained. In addition, as for the compounding ratio of a blue coloring agent and a yellow coloring agent, when the coating substrate was produced, the ratio was selected so that it might match x = 0.290 and y = 0.600 chromaticity in C light source. In addition, the total content of a coloring agent is all 11.0 parts.

<Film production and evaluation>

Evaluation of the lightness (color characteristic), heat resistance, and light resistance of the green coating film produced using the obtained green coloring composition (DG-1-34) was performed by the following method. Table 1 shows the results of the evaluation.

(Evaluation of brightness of coating)

Apply green coloring composition (DG-1-34) using a spin coater on a glass substrate 100 mm x 100 mm, 1.1 mm thick, then dry at 70 degreeC for 20 minutes, then heat at 220 degreeC for 30 minutes, By allowing to cool, a coating film substrate was produced. The brightness Y (C) of the obtained coating film was measured using the microspectrophotometer (Olymps Kogaku Co., Ltd. "OSP-SP100"). The produced coating film board | substrate was made to match chromaticity of x = 0.290 and y = 0.600 by C light source after the heat processing at 220 degreeC. Regarding the brightness Y (C), if it is 0.2 point or more, it can be said that there is a distinct difference.

(Evaluation of Heat Resistance of Coating Film)

Apply green coloring composition (DG-1-34) using a spin coater on a glass substrate 100 mm x 100 mm, 1.1 mm thick, then dry at 70 degreeC for 20 minutes, then heat at 220 degreeC for 30 minutes, By allowing to cool, a coating film substrate was produced. The produced coating film board | substrate was made to match chromaticity of x = 0.290 and y = 0.600 by C light source after the heat processing at 220 degreeC. The chromaticity ([L * (1), a * (1), b * (1)]) in the C light source of the obtained coating film was measured using the microspectrophotometer (Olymps Kogaku Co., Ltd. "OSP-SP100"). Furthermore, after that, it heated at 230 degreeC for 1 hour as a heat resistance test, measured chromaticity ([L * (2), a * (2), b * (2)]) in C light source, and measured the color difference (DELTA) Eab according to the following formula. * Was obtained and evaluated in the following three steps.

ΔEab * = √ ((L * (2)-L * (1)) ² + (a * (2)-a * (1)) ² + (b * (2)-b * (1)) ² )

○: ΔEab * is less than 5.0

Δ: ΔEab * is 5.0 or more but less than 10.0

X: ΔEab * is 10.0 or more

(Light resistance evaluation of coating film)

A coating film substrate was produced in the same manner as in the evaluation of heat resistance, and the chromaticity ([L * (1), a * (1), b * (1)]) at the C light source was measured by a microscopic spectrophotometer (Olympus Kogaku Co., Ltd. "OSP"). -SP100 "). Subsequently, a UV blocking filter (“COLORED OPTICAL GLASS L38” manufactured by Hoya Corporation) was attached to the substrate and irradiated with ultraviolet rays for 100 hours using a 470 W / m ² xenon lamp, and then the chromaticity of the C light source ([L * ( 2), a * (2), b * (2)]) were measured, and the color difference ΔEab * was calculated according to the above formula, and evaluated on the same basis as for heat resistance.

Yellow coloring agent (YC-1); C.I. which is a commercial item. Dispause Yellow 54

Yellow colorant (YC-2); CI dispose yellow 64 which is a commercial item

As shown in Table 1, the green coloring composition containing the phthalocyanine pigment | dye which the coloring agent which is a characteristic of embodiment shown by General formula (8A), and the quinophthalone type pigment | dye represented by General formula (6) is excellent in brightness, and the heat resistance of a coating film and Lightfastness was also a good result.

On the other hand, the green coloring composition (DG-25-30, 33, 34) of Reference Examples 1-6, 9, and 10 was low in brightness, and was a result which has a problem in heat resistance and light resistance. In addition, although the green coloring composition (DG-31, 32) of Reference Example 7, 8 had no problem in heat resistance and light resistance, it was a result with low brightness compared with an Example.

<The manufacturing method of a green photosensitive coloring composition>

[Example 25]

(Green Photosensitive Coloring Composition (RG-1))

After stirring and mixing the mixture of the following composition uniformly, it filtered with 1.0 micrometer filter and obtained the green photosensitive coloring composition (RG-1).

Green coloring composition (DG-1) 55.0 parts

Acrylic resin solution 29.8 parts

Photopolymerizable monomer ("Aronix M402" made by Toagosei Co., Ltd.) 4.6 parts

Photopolymerization initiator ("Irugacure OXE02" made by Chiba Japan Corporation) 0.8 parts

Propylene glycol monomethyl ether acetate # 19.8

10.0 parts cyclohexanone

[Examples 26-48, Reference Examples 11-20]

(Green photosensitive coloring composition (RG-2-34))

Except having changed the green coloring composition (DG-1) into the green coloring composition shown in Table 2, it carried out similarly to Example 25, and obtained the green photosensitive coloring composition (RG-2-34).

<Film production and evaluation>

Evaluation of the brightness (color characteristic), heat resistance, light resistance, and voltage retention of the green coating film produced using the obtained green photosensitive coloring composition (RG-1-34) was performed by the following method. Table 2 shows the results of the evaluation.

(Evaluation of brightness of coating)

A green photosensitive coloring composition (RG-1 to 34) was applied onto a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater, dried at 70 ° C. for 20 minutes, and accumulated in light using an ultrahigh pressure mercury lamp. Ultraviolet exposure was performed at 150 mJ / cm ² , and development was carried out with an alkali developer at 23 ° C. to obtain a coating film substrate. Subsequently, after heating and cooling at 220 degreeC for 30 minutes, the brightness Y (C) of the obtained coating film board | substrate was measured using the microspectrophotometer (Olymps Kogaku Corporation "OSP-SP100"). The produced coating film board | substrate was made to match chromaticity of x = 0.290 and y = 0.600 by C light source after the heat processing at 220 degreeC. As an alkaline developer, what consists of 8.0 mass% of sodium carbonate 1.5 mass% sodium hydrogencarbonate 0.5 mass% anionic surfactant ("Perryex NBL" by Kao Corporation), and 90 mass% of water was used. Regarding the brightness Y (C), if it is 0.2 point or more, it can be said that there is a distinct difference.

(Evaluation of Heat Resistance of Coating Film)

The green photosensitive coloring composition (RG-1 to 34) was applied onto a glass substrate 100 mm × 100 mm, 1.1 mm thick using a spin coater, then dried at 70 ° C. for 20 minutes, and accumulated light quantity was 150 mJ using an ultrahigh pressure mercury lamp. Ultraviolet light exposure was performed at / cm ² , and development was carried out with an alkali developer at 23 ° C. Then, after heating and cooling at 220 degreeC for 30 minutes, the coating film board | substrate was obtained. The produced coating film board | substrate was made to match chromaticity of x = 0.290 and y = 0.600 by C light source after the heat processing at 220 degreeC. The chromaticity ([L * (1), a * (1), b * (1)]) in the C light source of the obtained coating film was measured using the microspectrophotometer (Olymps Kogaku Co., Ltd. "OSP-SP100"). Then, it heats at 230 degreeC for 1 hour as a heat resistance test, the chromaticity ([L * (2), a * (2), b * (2)]) in C light source is measured, and color difference (DELTA) Eab according to the following formula. * Was obtained and evaluated in the following three steps.

ΔEab * = √ ((L * (2)-L * (1)) ² + (a * (2)-a * (1)) ² + (b * (2)-b * (1)) ² )

○: ΔEab * is less than 5.0

Δ: ΔEab * is 5.0 or more but less than 10.0

X: ΔEab * is 10.0 or more

(Light resistance evaluation of coating film)

A coating film substrate was produced in the same manner as in the evaluation of heat resistance, and the chromaticity ([L * (1), a * (1), b * (1)]) at the C light source was measured by a microscopic spectrophotometer (Olympus Kogaku Co., Ltd. "OSP"). -SP100 "). Subsequently, a UV blocking filter (“COLORED OPTICAL GLASS L38” manufactured by Hoya Corporation) was attached to the substrate and irradiated with ultraviolet rays for 100 hours using a 470 W / m ² xenon lamp, and then the chromaticity of the C light source ([L * ( 2), a * (2), b * (2)]) were measured, and the color difference ΔEab * was calculated according to the above formula, and evaluated on the same basis as the heat resistance.

(Voltage retention evaluation)

A green photosensitive coloring composition (RG-1 to 34) was applied onto a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater so that the thickness of the dry film was 2.0 μm, and the UV light was accumulated at a total amount of 50 mJ / cm ² . Exposure was performed and image development was performed with the alkali developing solution of 23 degreeC, and the coating-film board | substrate was obtained. Subsequently, after heating and cooling at 220 degreeC for 30 minutes, 0.05 part of coating films were cut out from the obtained coating board | substrate, and it immersed in 1.5 parts of liquid crystals (MLC-2041 by Merck Co., Ltd.), and aged at 120 degreeC for 1 hour. After centrifugation at 4000 rpm for 15 minutes, the clear liquid of the upper portion was taken to prepare a coating film-extracted liquid crystal sample liquid.

On the other hand, two glass substrates having an ITO transparent electrode having an effective electrode size of 10 mm x 10 mm were disposed to face each other so that the ITO transparent electrode faces faced each other, and a small cell was produced using a sealant such that the cell gap was 9 µm. A resist-extracted liquid crystal sample solution was injected into the small cell between the cell gaps, a voltage was supplied at 60 ° C. at a voltage of 5 V for 60 μs, and the cell voltage [V1] after 16.67 m seconds after voltage release was measured by VHR manufactured by Toyo Technica. It measured by -1S. The measurement was repeated five times, and the measured cell voltages were averaged. And using the obtained cell voltage, voltage retention (%) was calculated | required from the following formula and evaluated in the following three steps.

Voltage retention (%) = ([V1] / 5) x 100

○: 95% or more

△: 90% or more less than 95%

× ： Less than 90%

As shown in Table 2, the green photosensitive coloring composition containing the phthalocyanine pigment | dye which the coloring agent which is the characteristic of this embodiment represented by General formula (8A), and the quinophthalone type pigment | dye represented by General formula (6) is excellent in brightness, At the same time, good results were obtained in heat resistance, light resistance and voltage retention.

On the other hand, the green photosensitive coloring composition (RG-25-30, 33, 34) of Reference Examples 11-16, 19, and 20 was low in brightness, and had a bad heat resistance and light resistance. In addition, the reference examples 15-18 which used CI pigment green 58 had the result with a bad voltage retention compared with an Example.

<Production of color filter>

First, the red photosensitive coloring composition and blue photosensitive coloring composition used for preparation of a color filter were produced.

(Production of Red Photosensitive Coloring Composition (RR-1))

After stirring and mixing the mixture of the following composition uniformly, it disperse | distributed with Eiger-Mill ("Mini Model M-250 'MKII" made from Eiger Japan Co., Ltd.) for 5 hours using the zirconium oxide beads of diameter 0.5mm, and then 5.0 micrometers It filtered with the filter of and produced the red coloring composition (DR-1).

Red Pigment (C.I. Pigment Red 254)

Red Pigment (C.I. Pigment Red 177) # 2.4

Resin type dispersant ("EFKA4300" made by Chiba Japan Corporation) 1.0 parts

Acrylic resin solution 1 35.0 parts

Propylene glycol monomethyl ether acetate 52.0 parts

Subsequently, the mixture of the following composition was stirred and mixed so that it might become uniform, and it filtered with 1.0 micrometer filter and produced the red photosensitive coloring composition (RR-1).

Red coloring composition (DR-1) 42.0 parts

Acrylic resin solution 2 13.2parts

Photopolymerizable monomer ("Aronix M400" made by Toagosei Co., Ltd.) 2.8 parts

Photopolymerization initiator ("irgacua 907" made by Chiba Japan Corporation) 부 2.0 parts

Sensitizer ("EAB-F" made by Hodogaya Kagaku Kogyo Kogyo) 0.4 part

Ethylene glycol monomethyl ether acetate 39.6 parts

(Production of Blue Photosensitive Coloring Composition (RB-1))

After stirring and mixing the mixture of the following composition uniformly, it disperse | distributed with Eiger-Mill ("Mini Model M-250 'MKII" made from Eiger Japan Co., Ltd.) for 5 hours using the zirconium oxide beads of diameter 0.5mm, and then 5.0 micrometers It filtered with the filter of and produced the blue coloring composition (DB-1).

Blue pigment (C.I. pigment blue 15: 6) 7.2 parts

Purple Pigment (C.I. Pigment Violet 23) 4.8parts

Resin-type dispersant ("EFKA4300" made by Chiba Japan Corporation) 1.0 part

Acrylic resin solution 1 35.0 parts

Propylene glycol monomethyl ether acetate 52.0 parts

Then, the mixture of the following composition was stirred and mixed so that it might become uniform, and it filtered with 1.0 micrometer filter and produced the blue photosensitive coloring composition (RB-1).

Blue coloring composition (DB-1) # 34.0 parts

Acrylic resin solution 2 15.2 parts

Photopolymerizable monomer ("Aronix M400" made by Toagosei Co., Ltd.) 3.3 parts

Photopolymerization initiator ("Iruga cua 907" made by Chiba Japan Corporation) 2.0 parts

Sensitizer ("EAB-F" made by Hodogaya Kagaku Kogyo Kogyo) 0.4 part

Ethylene glycol monomethyl ether acetate 45.1 parts

(Production of color filter)

The black matrix was pattern-processed on the glass substrate, and the red photosensitive coloring composition (RR-1) was apply | coated with the spin coater on the said board | substrate, and the coloring film was formed. A photomask was passed through the film, and ultraviolet rays of 150 mJ / cm ² were irradiated with an ultrahigh pressure mercury lamp. After spray development with an alkaline developer consisting of 0.2% by weight aqueous sodium carbonate solution to remove unexposed portions, the substrate was washed with ion-exchanged water and heated at 220 ° C. for 20 minutes to form a red filter segment. Here, the red filter segment was made to match chromaticity of x = 0.640 and y = 0.330 in C light source (hereinafter also used for green and blue) after heat processing at 220 degreeC. In the same manner, the green filter segment is adapted to the chromaticity of x = 0.290 and y = 0.600 using the green photosensitive coloring composition (RG-6), and the blue filter segment uses 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 the color filter was obtained.

By using green photosensitive coloring composition (RG-6), the high brightness of a color filter was possible and it could use suitably also without a physical property.

<< embodiment VII >>

Hereinafter, "PGMAC" means propylene glycol monomethyl ether acetate. In addition, the measuring method of the weight average molecular weight (Mw) and contrast ratio of resin are 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 as two columns in succession, and using THF as a solvent. It is one polystyrene equivalent molecular weight.

<Contrast ratio>

The light from the backlight unit for liquid crystal display is polarized through the polarizing plate, passes through the coating film of the coloring composition applied on the glass substrate, and reaches the other polarizing plate. At this time, when the polarizing plate and the polarizing plane of the polarizing plate are parallel, light passes through the polarizing plate, but when the polarizing plane is orthogonal, the light is blocked by the polarizing plate. However, when the light polarized by the polarizing plate passes through the coating film of the coloring composition, scattering or the like occurs due to the colorant particles, and when a deviation occurs in a part of the polarizing plane, when the polarizing plates are parallel, the amount of light transmitted is reduced, and the polarizing plate When it is orthogonal, some light transmits. This transmitted light was measured as the brightness | luminance on a polarizing plate, and ratio of the brightness | luminance at the time of orthogonal to the brightness | luminance when a polarizing plate is parallel was computed as contrast ratio.

(Contrast ratio) = (Brightness in parallel) / (Brightness in orthogonal)

Therefore, when scattering is caused by the colorant in the coating film, the brightness ratio at orthogonality is increased, 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. On the occasion of measurement, it measured through the black mask which made the hole of 1 cm square through the measurement part.

First, the preparation method of the quinophthalone pigment [A1] and the quinophthalone pigment [A2], the binder resin solution, the resin-type dispersant solution, the quinophthalone pigment [B], and the aluminum phthalocyanine pigment which were used by the Example and the reference example, and a pigment The refinement | miniaturization method of this, the manufacturing method of a green coloring composition and a red coloring composition, the green photosensitive coloring composition, and the manufacturing method of a red photosensitive coloring composition are demonstrated.

<Manufacturing method of a quinophthalone pigment | dye [A1]>

[Kinophthalone pigment | dye (A1-1)]

&Lt; EMI ID =

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. After cooling, 100 parts of methanol was added, followed by stirring for 1 hour. And the solid precipitated was collected by suction filtration. In addition, the solid was poured into 200 parts of methanol, stirred for 1 hour, and 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: burka Dartonikus company autoflexII). It confirmed that it was a target object in m / z = 366 (molecular weight 365.4).

[Kinophthalone pigment | dye (A1-2)]

(108)

In the same manner as the quinophthalone dye (A1-1), N-bromosuccine is used to prepare a dye obtained by reacting 8- (1,3-dioxane-2-yl) methyl-2-methylquinoline with naphthalenedicarboxylic acid. Brominated with mid and synthesize | combined, the quinophthalone pigment | dye (A1-2) was obtained. The product identified the compound with the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII), and confirmed that it was a target object.

[Kinophthalone pigment | dye (A1-3-14)]

In the same manner as the quinophthalone dye (A1-1), the corresponding 2-methylquinoline and naphthalene carboxylic anhydride were reacted to obtain a quinophthalone dye (A1-3 to 14). The product identified the compound with the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII), and confirmed that it was a target object.

<Manufacturing method of a quinophthalone pigment | dye [A2]>

[Kinophthalone pigment | dye (A2-1)]

(109)

10.8 parts of 6-iso-propyl-2-methylquinoline, 12.1 parts of trimellitic anhydride, and 60 parts of benzoic acid were mixed, and it reacted at 200 degreeC for 7 hours. The purified yellow solid was washed with dimethylformamide to obtain 14 g of a yellow substance. 0.2 g of pyridine and o-dichlorobenzene were added to 5 g of yellow water, followed by 3.8 parts of thionyl chloride, followed by distillation under reduced pressure, and then 1.76 g of 3-amino-2-propanol was added and reacted at 180 ° C for 7 hours, followed by cooling. After washing with hexane and drying, column purification with silica gel was carried out to obtain a yellow powder. The structure identified the compound with the mass spectrometer (TOF-MS: Bruker-Dartonicus company autoflexII), and confirmed that it was a target object.

[Kinophthalone pigment | dye (A2-2)]

(110)

In the same manner as the quinophthalone dye (A2-1), 5-bromo-8- (1,3-dioxane-2-yl) methyl-2-methylquinoline and phthalic anhydride were reacted to obtain a yellow powder. The compound was identified by the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII), and it confirmed that it was a target object.

[Kinophthalone pigment | dye (A2-3-16)]

In the same manner as the quinophthalone dye (A2-1), the corresponding 2-methylquinoline and phthalic anhydride were reacted to obtain a quinophthalone dye (A2-3 to 16). The compound was identified by the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII), and it confirmed that it was a target object.

Table 1 shows the structures of the produced quinophthalone dye [A1] and the quinophthalone dye [A2].

<Method for producing binder resin solution>

(Acrylic Resin Solution 1)

196 parts of cyclohexanone were added to a reaction vessel provided with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube, and a stirring device in a separable four-necked flask, the temperature was raised to 80 ° C., and the inside of the reaction vessel was replaced with nitrogen. 20.7 parts of benzyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylates, 12.0 parts of methacrylic acid, paracumyl phenol ethylene oxide modified acrylate ("Aronix M110" made by Toagosei Co., Ltd.) from a dripping pipe A mixture of 1.1 parts of 2,2'-azobisisobutylonitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain a solution of acrylic resin. After cooling to room temperature, approximately 2 parts of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes, and the nonvolatile content was measured. PGMAC was added to the synthesized resin solution so that the nonvolatile content was 20% by mass, and the acrylic resin solution 1 ( Resin solution 1) was obtained. The weight average molecular weight (Mw) was 26000.

(Acrylic Resin Solution 2)

370 parts of cyclohexanone were put into a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube, and a stirring device, and the temperature was raised to 80 ° C. A mixture of 18.2 parts of cydyl methacrylate, 53 parts of methyl methacrylate and 2.0 parts of 2,2'-azobisisobutylonitrile was added dropwise over 2 hours. After dripping was further made to react at 100 degreeC for 3 hours, the thing which melt | dissolved 1.0 part of azobisisobutylonitrile with 50 parts of cyclohexanone was added, and reaction was continued at 100 degreeC for 1 hour. Next, the inside of the container was replaced with air substitution, 0.5 parts of trisdimethylaminophenol and 0.1 part of hydroquinone were added to 9.3 parts of acrylic acid (equivalent to glycidyl group) in the container, and the solid dispersion was continued at 120 ° C. for 6 hours. The reaction was complete | finished when it reached 0.5, and the solution of acrylic resin was obtained. Furthermore, 19.5 parts of tetrahydrophthalic anhydride (equivalent of the produced hydroxyl group) and 0.5 part of triethylamine were added, and it was made to react at 120 degreeC for 3.5 hours, and the acrylic resin solution was obtained.

After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. First, PGMAC was added to the synthesized resin solution so that the nonvolatile content was 20% by weight. Resin solution 2) was obtained. The weight average molecular weight (Mw) was 19000.

<Production of Resin Dispersant Solution>

(Resin Dispersant Solution 1)

In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 80 parts of n-butyl methacrylate and 120 parts of benzyl methacrylate were placed and replaced with nitrogen gas. The inside of a reaction vessel was heated to 80 degreeC, the solution which melt | dissolved 0.1 part of 2,2'- azobisisobutylonitrile was added to 12 mercapto 1 and 2 propanediol 12 parts, and it was made to react for 10 hours. It was confirmed by the solid content measurement that 95% reacted. 30 parts of pyromellitic dianhydrides, 242 parts of cyclohexanone, and a 1, 8- diazabicyclo [5. 4. 0.40 part of 0] -7-undecene was added, and it was made to react at 120 degreeC for 7 hours. It confirmed that 98% or more of acid anhydrides were semiesterified by the measurement of acid value, reaction was complete | finished, and the resin type dispersing agent 1 was obtained. After cooling to room temperature, about 2 parts of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. First, cyclohexanone was added to the synthesized resin solution so that the nonvolatile content was 20% by mass, and the resinous dispersant was added. Solution 1 (dispersant 1) was prepared. The weight average molecular weight (Mw) was 9500.

(Resin Dispersant Solution 2)

The resin type dispersant ("BYK-LPN6919" by Big Chemical Co., Ltd.) was diluted with PGMAC, and the non-volatile content 20% by weight of resin type dispersant solution 2 (dispersant 2) was adjusted.

<Manufacturing method of a quinophthalone pigment [B]>

(Production of a quinophthalone pigment (B-1))

First, compound (1) was obtained according to the synthesis method as described in Unexamined-Japanese-Patent No. 2008-81566.

[Formula 111]

Subsequently, 100 parts of compounds (1), 70 parts of 2,3-naphthalenedicarboxylic anhydride and 143 parts of benzoic acid were added to 300 parts of methyl benzoate, and it heated at 180 degreeC and made it react for 4 hours. By TOF-MS, the production | generation of the quinophthalone pigment (B-1) shown by following formula (50) and the loss | disappearance of the compound (1) which are raw materials were confirmed. Furthermore, after cooling to room temperature, the reaction mixture was poured into 3130 parts of acetone and stirred at room temperature for 1 hour. The product was filtered off, and the mixture was washed with methanol and dried to obtain 120 parts of quinophthalone pigment (B-1). It confirmed that it was a quinophthalone pigment (B-1) as a result of the mass spectrometry by TOF-MS.

(112)

(Production of a quinophthalone pigment (B-2))

First, the compound (2) was obtained by the method similar to the synthesis | combination of a compound (1) according to the synthesis | combining method of Unexamined-Japanese-Patent No. 2008-81566, using a quinophthalone pigment (B-1) as a raw material.

(113)

Subsequently, 100 parts of compounds (2), 108 parts of tetrachlorophthalic anhydride, and 143 parts of benzoic acid were added to 300 parts of methyl benzoate, and it heated at 180 degreeC and made it react for 4 hours. By TOF-MS, the production | generation of a quinophthalone pigment (B-2) and the loss | disappearance of the compound (2) which are raw materials were confirmed. Furthermore, after cooling to room temperature, the reaction mixture was poured into 3510 parts of acetone and stirred at room temperature for 1 hour. The product was filtered off, and the mixture was washed with methanol and dried to obtain 120 parts of quinophthalone pigment (B-2) represented by the following formula (51). It confirmed that it was a quinophthalone pigment (B-2) as a result of the mass spectrometry by TOF-MS.

(114)

<Method for producing aluminum phthalocyanine pigment>

(Aluminum Phthalocyanine Pigment (C-1))

225 parts of phthalodinitrile and 78 parts of aluminum chloride anhydrides were added and stirred in 1250 parts of n-amyl alcohols in the reaction container. To this, 266 parts of DBU (1,8-Diazabicyclo [4.0.] Undec-7-ene) were added, the temperature was raised, and the mixture was refluxed at 136 ° C for 5 hours. The reaction solution cooled to 30 degreeC with stirring was poured in 5000 parts of methanol, and the mixed solvent of 10000 parts of water under stirring, and the blue suspension was obtained. The suspension was filtered, washed with 2000 parts of methanol and 4000 parts of water mixed solvent and dried to obtain 135 parts of chloro aluminum phthalocyanine. Furthermore, 100 parts of chloro aluminum phthalocyanine was slowly added to 1200 parts of concentrated sulfuric acid at room temperature in reaction container. It stirred at 40 degreeC for 3 hours, and poured sulfuric acid solution into 24000 parts of 3 degreeC cold waters. The blue precipitate was filtered, washed with water and dried to obtain 102 parts of an aluminum phthalocyanine pigment (C-1) represented by the following formula (53).

(115)

(Aluminum Phthalocyanine Pigment (C-2))

In a reaction vessel, 100 parts of aluminum phthalocyanine pigment (C-1) represented by Formula (53) and 49.5 parts of diphenyl phosphate were added to 1000 parts of methanol, and the mixture was heated to 40 ° C and allowed to react for 8 hours. After cooling this to room temperature, the product was filtered, and after wash | cleaning with methanol, it dried and obtained 114 parts of aluminum phthalocyanine pigments (C-2) shown by following formula (54).

&Lt; EMI ID =

(Aluminum Phthalocyanine Pigment (C-3))

In a reaction vessel, 100 parts of aluminum phthalocyanine pigment (C-1) represented by Formula (53) and 43.2 parts of diphenylphosphinic acid were added to 1000 parts of methanol, and heated to 40 ° C to react for 8 hours. After cooling this to room temperature, the product was filtered, washed with methanol, and dried, and 112 parts of aluminum phthalocyanine pigments (C-3) shown by following formula (55) were obtained.

(117)

<Miniaturization method of pigment>

(Yellow colorant (PY-1))

100 parts of a quinophthalone pigment (B-1), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were put into the stainless 1 gallon kneader (made by Inoue Sesakujo Co., Ltd.), and it knead | mixed at 60 degreeC for 6 hours, and was salt milling. The resultant kneaded product was poured into 3 liters of warm water, stirred for 1 hour while heating to 70 ° C to obtain a suspension, filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 ° C for 98 parts. A yellow coloring agent (PY-1) was obtained. The average primary particle diameter was 31.3 nm.

(Yellow colorant (PY-2))

40 parts of quinophthalone pigments (B-2), 60 parts of CI pigment yellow 138 ("Pariotol yellow -K0960-HD" made by BASF Corporation), 1200 parts of sodium chloride, and 120 parts of diethylene glycol are made of stainless steel 1 gallons (Inoue Se Sakujo Co., Ltd.), and kneaded at 60 ° C for 8 hours. Subsequently, this kneaded product was poured into warm water, stirred for 1 hour while heating to about 70 ° C. to a suspension state, filtered, washed with water repeatedly to remove sodium chloride and diethylene glycol, and dried overnight at 80 ° C. to give a yellow colorant. (PY-2) 97 parts were obtained. The average primary particle diameter was 36.8 nm.

(Yellow colorant (PY-3))

100 parts of CI pigment yellow 138 (trade name Pariotol Yellow-K0961HD manufactured by BASF Corporation), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a stainless 1 gallon kneader (manufactured by Inoue Sesakujo), and kneaded at 70 ° C for 6 hours. The kneaded product was poured into 3000 parts of warm water, stirred for 1 hour while heating to 70 ° C, and the mixture was stirred. Repeated filtration and washing to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 ° C. PY-3) 98 parts was obtained. The average primary particle diameter was 35.5 nm.

(Yellow colorant (PY-4))

500 parts of metal complex type yellow pigment CI pigment yellow 150 (Lanxses company "E4GN"), 2500 parts of sodium chloride, and 250 parts of diethylene glycol are put into a stainless 1 gallon kneader (made by Inoue Sesakujo), and kneaded at 100 degreeC for 6 hours. It was. Subsequently, this kneaded product was poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to a suspension state, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. A yellow coloring agent (PY-4) was obtained. The volume average primary particle diameter of the obtained pigment was 28.3 nm.

(Yellow colorant (PY-5))

500 parts of isoindolin series yellow pigment CI pigment yellow 139 ("Pariotol yellow -D1819" made by BASF Corporation), 2500 parts of sodium chloride, and 250 parts of diethylene glycol are put in a stainless steel gallon kneader (product made by Inoue Sesakujo Co., Ltd.), and it is 100 It knead | mixed for 6 hours at ° C. Subsequently, this kneaded product was poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to a suspension state, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. A yellow coloring agent (PY-5) was obtained. The volume average primary particle diameter of the obtained pigment was 29.3 nm.

(Green colorant (PG-1))

500 parts of green pigment CI pigment green 58 (zinc phthalocyanine, `` pastgeingin A110 '' made by DIC Corporation), 1500 parts of sodium chloride, and 250 parts of diethylene glycol are placed in a stainless 1 gallon kneader (manufactured by Inoue Sesakujo Co., Ltd.), and 120 ° C. Kneaded for 8 hours. Subsequently, this kneaded product was poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to a suspension state, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. A green colorant (PG-1) was obtained. The volume average primary particle diameter of the obtained pigment was 25.2 nm.

(Green colorant (PG-2))

500 parts of green pigment CI pigment green 36 ("Ryonor green 6YK" made by Toyo Ink Corporation), 2500 parts of sodium chloride, and diethylene glycol: 250 parts are put in stainless steel 1 gallon kneader (made by Inoue Sesakujo), and it is 2 at 100 degreeC Time kneaded. Subsequently, this kneaded product was poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to a suspension state, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 490 parts of green colorants (PG-2) were obtained. The volume average primary particle diameter of the obtained pigment was 26.6 nm.

(Green colorant (PG-3))

500 parts of green pigments (CI Pigment Green 7, Toyo Ink Sezosha Co., Ltd. "Riono Green Y-101"), 1500 parts of sodium chloride, and 250 parts of diethylene glycol are put in a stainless 1 gallon kneader (manufactured by Inoue Sesakujo Co., Ltd.), 120 It knead | mixed for 8 hours at ° C. Subsequently, this kneaded product was poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to a suspension state, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. A green colorant (PG-3) was obtained. The volume average primary particle diameter of the obtained pigment was 33.1 nm.

(Red colorant (PR-1))

500 parts of red pigments (CI Pigment Red 177, `` Chromofutard red A2B '' made by Chiba Specialty Chemicals), 1500 parts of sodium chloride and 250 parts of diethylene glycol are put in stainless steel 1 gallon kneader (product made by Inoue Sesakujo Corporation) And kneaded at 120 ° C for 8 hours. Subsequently, this kneaded product was poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to a suspension state, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. A red coloring agent (PR-1) was obtained. The volume average primary particle diameter of the obtained pigment was 28.3 nm.

(Blue colorant (PB-1))

100 parts of aluminum phthalocyanine pigment (C-1), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were put into the stainless 1 gallon kneader (made by Inoue Sesakujo), and it knead | mixed at 70 degreeC for 6 hours. The kneaded product was poured into 3000 parts of warm water, stirred for 1 hour while heating to 70 ° C, and the mixture was stirred. Repeated filtration and washing to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 ° C to give a blue colorant ( PB-1) was obtained. The average primary particle diameter was 30.4 nm.

(Blue colorant (PB-2))

The blue coloring agent (PB-2) was obtained by the salt milling method similar to a blue coloring agent (PB-1) except having changed the aluminum phthalocyanine pigment (C-1) into the aluminum phthalocyanine pigment (C-2). The average primary particle diameter was 31.2 nm.

(Blue colorant (PB-3))

A blue coloring agent (PB-3) was obtained by the salt milling method similar to a blue coloring agent (PB-1) except having changed the aluminum phthalocyanine pigment (C-1) into the aluminum phthalocyanine pigment (C-3). The average primary particle diameter was 29.5 nm.

(Blue colorant (PB-4))

500 parts of blue pigments (CI pigment blue 15: 6, "Heriogen blue L-6900F" made by BASF Corporation), 2500 parts of sodium chloride, and 250 parts of diethylene glycol are put in a 1 gallon kneader (made by Inoue Sesakujo) made of stainless, 100 degreeC 2 hours kneading at. Subsequently, this kneaded product was poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to a suspension state, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 490 parts of blue coloring agents (PB-4) were obtained. The volume average primary particle diameter of the obtained pigment was 26.6 nm.

(Blue colorant (PB-5))

500 parts of α type copper phthalocyanine-based cyan pigments (CI pigment blue 15: 1, Toyo Ink Sezosha "Rion nor blue 7120-V"), sodium chloride: 2500 parts and diethylene glycol: 250 parts of stainless steel 1 gallons (Inoue) Sesakujo Co., Ltd.) and kneaded at 100 ° C for 2 hours. Subsequently, this kneaded product was poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to a suspension state, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 490 parts of blue coloring agents (PB-5) were obtained. The volume average primary particle diameter of the obtained pigment was 35.2 nm.

The obtained coloring agent is shown in Table 2.

<Manufacturing method of a green coloring composition (DG-1)>

After stirring and mixing the mixture of the following composition uniformly, it disperse | distributed with Eiger-Mill ("Mini Model M-250 'MKII" made from Eiger Japan Co., Ltd.) for 5 hours using the zirconium oxide beads of diameter 0.5mm, and then 5.0 micrometers It filtered with the filter of and obtained the green coloring composition (DG-1).

Green colorant (PG-1) 10.0 parts

Resin-type dispersant solution 2 0.010.0part

Acrylic resin solution 1 40.0part

PGMAC Part 40.0

<The manufacturing method of red coloring composition (DR-1)>

After stirring and mixing the mixture of the following composition uniformly, it disperse | distributed with Eiger-Mill ("Mini Model M-250 'MKII" made from Eiger Japan Co., Ltd.) for 5 hours using the zirconium oxide beads of diameter 0.5mm, and then 5.0 micrometers It filtered with the filter of and obtained the red coloring composition (DR-1).

Red colorant (PR-1) 3.3 parts

Red colorant (Pigment Red 254) 6.7 parts

`` IRGAPHOR RED B-CF '' made in Chiba specialty chemicals company

Resin-type dispersant solution 2-10.0 parts

Acrylic resin solution 1 40.0part

PGMAC Part 40.0

<The manufacturing method of green photosensitive coloring composition (RG-1)>

After stirring and mixing the mixture of the following composition uniformly, it filtered with the 1 micrometer filter and produced the photosensitive coloring composition (RG-1).

Coloring composition (DG-1) 60.0 parts

Acrylic resin solution 1 15.0parts

(Resin solution # 1)

Photopolymerizable monomer A 3.0part

(`` Aronix M402 '' made by Toagosei Corporation)

Photopolymerization initiator 1.6 parts

(`` Irgacua 379 '' made in Chiba Japan Corporation)

Cyclohexanone 20.4 parts

<The manufacturing method of red photosensitive coloring composition (RR-1)>

After stirring and mixing the mixture of the following composition uniformly, it filtered with the 1 micrometer filter and produced the photosensitive coloring composition (RR-1).

Coloring composition (DR-1) 60.0 parts

Acrylic resin solution 1-15.0 parts

(Resin solution # 1)

Photopolymerizable monomer A 3.0part

(`` Aronix M402 '' made by Toagosei Corporation)

Photopolymerization initiator 1.6 parts

(`` Irgacua 379 '' made in Chiba Japan Corporation)

Cyclohexanone 20.4 parts

Example 1

(Coloring composition (P-1))

The mixture which consists of the following components was stirred for 0.5 hours so that it might become uniform, heating at 50 degreeC. Thereafter, using a 0.5 mm diameter zirconium oxide beads, the mixture was dispersed for 0.5 hour in an Eiger-mill (“Mini Model M-250 MKII” manufactured by Eiger Japan), followed by filtration with a 5 μm filter to obtain a coloring composition (P-1). ) Was produced.

Quinophthalone pigment | dye (A1-1) # 5.0 part

Quinophthalone pigment | dye (A2-1) # 5.0 part

Acrylic resin solution 1-50.0 parts

(Resin solution # 1)

Cyclohexanone 40.0 parts

[Examples 2 to 24, Reference Examples 1 and 2]

(Coloring composition (P-2-24 and P-46, 47))

Except having changed the quinophthalone pigment | dye, resin type dispersing agent solution, the acrylic resin solution, the kind of solvent, and compounding quantity (weight part) as shown in Table 3, it carried out similarly to coloring composition (P-1), and colored composition (P-2-24) ) And coloring composition (P-46, 47) were produced. In addition, when using a coloring agent together, the total amount of a coloring agent is 10 parts in all coloring compositions.

The abbreviation of Table 3 is shown below.

Organic solvent

Anon: Cyclohexanone

[Example 25]

(Coloring composition (P-25))

After stirring and mixing the mixture which consists of the following components, heating at 50 degreeC so that it may become uniform, it is made into 5 by Eiger-Mill ("Mini Model M-250 MKII" by Eiger Japan company) using 0.5 mm diameter zirconium oxide beads. After disperse | distributing time, it filtered with the filter of 5 micrometers and produced the coloring composition 22 (P-22).

Quinophthalone pigment | dye (A1-1) 부 2.5 parts

Quinophthalone pigment | dye (A2-1) '2.5 parts

Yellow colorant (PY-1) 5.0 parts

Resin type dispersant solution 1 10.0part

(Dispersant 1)

Acrylic resin solution 1 40.0part

(Resin solution # 1)

Cyclohexanone 40.0 parts

[Examples 26-45, Reference Examples 3-8]

(Coloring composition (P-26-45 and P-48-53))

Kinophthalone pigments, pigments, resinous dispersant solution, acrylic resin solution, the type of solvent, and the amount of compounding (parts by weight) were changed as shown in Table 4, the same as the coloring composition (P-25), and the coloring composition (P-26) 45) and the coloring composition (P-48-53) were produced. In addition, when using a coloring agent together, the total amount of a coloring agent is 10.0 parts in all coloring compositions.

The abbreviation of Table 4 is shown below.

Organic solvent

Anon: Cyclohexanone

[Evaluation of Coloring Composition]

Evaluation of contrast ratio and coloring power was performed about the coloring composition (P-1-53) by the following method. The results are shown in Tables 5 and 6.

(Contrast Ratio Evaluation)

The obtained coloring composition (P-1-53) was apply | coated using the spin coater on the glass substrate of 100 mm x 100 mm, 1.1 mm thickness, and then it dried at 70 degreeC for 20 minutes, and cooled and produced the coating film substrate. The initial contrast ratio (initial CR) of the obtained coated substrate was measured. At this time, the coating film was produced by adjusting the coating | coating conditions of a spin coater so that the thickness of the film | membrane measured using the surface shape measuring apparatus "Dektak8 (made by Veeco)" might be 1 micrometer.

(Color evaluation)

The obtained coloring composition (P-1-32 and P34-53) and green coloring composition (DG-1) were mixed, and the green coloring composition was produced. In addition, as for the mixture ratio of coloring composition (P-1-32 and P-34-53) and green coloring composition (DG-1), when the coating substrate was all produced, chromaticity of x = 0.290 and y = 0.600 in C light source. The ratio was chosen to fit. Next, the obtained mixed coloring composition was apply | coated so that it might become y = 0.600 in a C light source using a spin coater, and then the coating board | substrate was obtained by drying at 70 degreeC for 20 minutes. The coloring power was evaluated by the measurement result of the film thickness of the obtained coating substrate. The thickness measurement of the obtained coating film was performed using the surface shape measuring apparatus "Dektak8 (made by Veeco)." The results were judged according to the following criteria. The smaller the thickness of the film | membrane which gives the target chromaticity, the larger the coloring power is, and it can be said to be excellent.

◎: Less than 2.40 [μm]

○: 2.40 or more and less than 2.56 [μm]

×: 2.56 or more [μm]

Furthermore, the obtained coloring composition (P-33) and the red coloring composition (DR-1) were mixed, and the red coloring composition was created. In addition, the mixing | blending ratio of the coloring composition (P-33) and the red coloring composition (DR-1) selected the ratio so that it might match with chromaticity of x = 0.640 and y = 0.334 in C light source, when both produced the coating board | substrate. Next, the obtained mixed coloring composition was apply | coated so that it might become x = 0.640 in a C light source using a spin coater, and then the coating board | substrate was obtained by drying at 70 degreeC for 20 minutes. The coloring power was evaluated according to the measurement result of the film thickness of the obtained coating substrate. The measurement of the obtained coating film thickness was performed using the surface shape measuring apparatus "Dektak8 (made by Veeco)". The results were judged according to the following criteria. The smaller the thickness of the film | membrane which gives the target chromaticity, the larger the coloring power is, and it can be said that it is excellent.

◎: Less than 1.52 [μm]

○: 1.52 or more less than 1.60 [μm]

X: 1.60 or more [μm]

As shown in Table 5 and Table 6, the coloring composition in which the coloring agent which is the characteristic of this embodiment contains the quinophthalone pigment | dye [A1] of a specific structure and the quinophthalone pigment | dye [A2] of a specific structure is very contrast ratio. It is high and has excellent coloring power.

Especially, when the coloring agent contains a pigment like Example 25-45 (coloring composition (P-25-45)), contrast ratio was more favorable.

Moreover, when Example 3 (coloring composition (P-3)) and Examples 6 and 7 (coloring composition (P-6, 7)) are compared, the coloring composition (P-6, 7) containing a resinous dispersing agent is included. The side was better in terms of contrast ratio.

On the other hand, when it did not contain a quinophthalone pigment | dye [A2] like the coloring composition of a reference example, it was a result with low contrast ratio under the influence of fluorescence. In addition, when the quinophthalone pigment | dye [A1] was not included, since the fluorescence did not come out, contrast ratio was favorable, but the coloring power was very bad result.

[Example 46]

(Photosensitive coloring composition (R-1))

After stirring and mixing the mixture of the following composition uniformly, it filtered with the 1 micrometer filter and produced the photosensitive coloring composition (R-1).

Coloring composition (P-1) 60.0 parts

Acrylic resin solution 1 15.0 parts

(Resin solution # 1)

Photopolymerizable monomer A 3.0part

(`` Aronics M402 '' made by Toagosei Corporation)

Photopolymerization initiator 1.6 parts

(`` Irgacua 379 '' made in Chiba Japan Corporation)

Cyclohexanone 20.4 parts

[Examples 47-90, Reference Examples 9-16]

(Photosensitive coloring composition (R-2-53))

The photosensitive coloring composition (R-1), except that the coloring composition, acrylic resin solution, photopolymerizable monomer, photopolymerization initiator, sensitizer, organic solvent, type of antioxidant, and blending amount (parts by weight) were changed as shown in Tables 7-9. In the same manner, a photosensitive coloring composition (R-2 to 53) was produced.

It shows below about the abbreviation in Tables 7-9. Photopolymerizable monomer and photopolymerizable monomer A: Dipentaerythritol hexaacrylate / pentaacrylate mixture ("Aronix M402" by Toagosei Co., Ltd.) Photoinitiator, initiator A: 2- (dimethylamino) -2- [ (4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone ("irgacua 379" by Chiba Japan Co., Ltd.), initiator B: ethanone, 1- [9 -Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyl oxime) ("Irgacua OXE02" made by Chiba Japan) A sensitizer, a sensitizer A: 4,4'-diethylaminobenzophenone ("EAB-F" made by Hodogaya Kagakusha) antioxidant, antioxidant A: hintphenol-based antioxidant pentaerythritol tetrakis [3- (3,5-di-) tert-butyl-4-hydroxyphenyl) propionate antioxidant B: sulfur-based antioxidant 3,3'- thiodipropane dioctadecyl antioxidant C: phosphorus oxidation Paper tris [2,4-di- (tert) -butylphenyl] phosphine antioxidant D: Hindamine type antioxidant bis (2,2,6,6- tetramethyl-4- piperidyl) sebacate Antioxidant E: Salicylic acid ester type | system | group Antioxidant Salicylic acid p-octylphenyl Organic solvent Anion: Cyclohexanone

[Evaluation of the photosensitive coloring composition]

About the photosensitive coloring composition (R-1-53), evaluation of contrast ratio, coloring power, and lightness was performed by the following method. The results are shown in Tables 10-12.

(Contrast Ratio Evaluation)

The obtained photosensitive coloring composition (R-1-53) was apply | coated using the spin coater on the glass substrate of 100 mm x 100 mm, 1.1 mm thickness, and it dried at 70 degreeC for 20 minutes, and then cooled and produced the coating film substrate. The initial contrast ratio (initial CR) of the obtained coated substrate was measured. At this time, the coating conditions of the spin coater were adjusted and the coating film was produced so that the thickness of the film measured using the surface shape measuring apparatus "Dektak8 (made by Veeco)" might be 1 micrometer.

(Color evaluation)

The obtained photosensitive coloring composition (R-1-32 and R-34-53) and green photosensitive coloring composition (RG-1) were mixed, and the green photosensitive coloring composition was produced. In addition, the compounding ratio of green photosensitive coloring composition (R-1-53) and green photosensitive coloring composition (RG-1) is made so that it may match chromaticity of x = 0.290 and y = 0.600 in C light source, when all the coating substrates were produced. The ratio was chosen. Next, the obtained mixed coloring composition was apply | coated so that it might become y = 0.600 in a C light source using a spin coater, and then the coating board | substrate was obtained by drying at 70 degreeC for 20 minutes. The coloring power was evaluated according to the measurement result of the film thickness of the obtained coating substrate. The measurement of the thickness of the obtained coating film was performed using the surface shape measuring apparatus "Dektak8 (made by Veeco)". The result was judged according to the following criteria. The thinner the thickness of the film imparting the desired chromaticity, the greater the coloring power.

◎: Less than 3.91 [μm]

○: 3.11 or more and less than 4.17 [μm]

X: 4.17 or more [μm]

The obtained photosensitive coloring composition (R-33) and the red photosensitive coloring composition (RR-1) were mixed, and the red coloring composition was created. In addition, as for the compounding ratio of the photosensitive coloring composition (R-33) and the red photosensitive coloring composition (RR-1), when the coating substrate was all produced, it selects ratio so that it might match x = 0.640 and y = 0.334 chromaticity in C light source. It was. Next, the obtained mixed coloring composition was apply | coated so that it might become x = 0.640 in a C light source using a spin coater, and then the coating board | substrate was obtained by drying at 70 degreeC for 20 minutes. The coloring power was evaluated according to the measurement result of the film thickness of the obtained coating substrate. The measurement of the thickness of the obtained coating film was performed using the surface shape measuring apparatus "Dektak8 (made by Veeco)". The results were judged according to the following criteria. It can be said that it is excellent in coloring power, so that the thickness of the film | membrane which gives a target chromaticity is thinner.

◎: Less than 2.47 [μm]

○: 2.47 or more and less than 2.61 [μm]

X: 2.61 or more [μm]

(Evaluation of brightness of coating)

The photosensitive coloring composition (R-1-32, R-34-53) was apply | coated using the spin coater on the glass substrate of 100 mm x 100 mm, 1.1 mm thickness, and then it dried at 70 degreeC for 20 minutes, and then 220 degreeC The coating film board | substrate was produced by heating and cooling for 30 minutes at. The brightness Y (C) of the obtained coating film was measured using the microspectrophotometer (Olymps Kogaku Co., Ltd. "OSP-SP100"). The produced coating film board | substrate was made to match chromaticity of x = 0.290 and y = 0.600 by C light source after the heat processing at 220 degreeC.

In addition, about the photosensitive coloring composition (R-33), the brightness was evaluated by the method mentioned above except having made chromaticity match the chromaticity of x = 0.640 and y = 0.334.

As shown in Tables 10-12, the photosensitive coloring composition in which the coloring agent which is the characteristic of this embodiment contains the quinophthalone pigment | dye [A1] of a specific structure and the quinophthalone pigment | dye [A2] of a specific structure has a very high contrast ratio. The coloring power was also excellent.

Especially, when Example 70-90 (photosensitive coloring composition (R-25-45)) further contains a pigment, contrast ratio was more favorable. Moreover, when comparing Example 48 (photosensitive coloring composition (R-3)) and Examples 51 and 52 (photosensitive coloring composition (R-6, 7)), the photosensitive coloring composition (R-6) containing a resin type dispersing agent , 7) were better in terms of contrast ratio.

On the other hand, when the quinophthalone pigment | dye [A2] was not included like the photosensitive coloring composition of a reference example, it was a result with low contrast ratio under the influence of fluorescence. In addition, when the quinophthalone pigment | dye [A1] was not included, since the fluorescence did not come out, contrast ratio was favorable, but the coloring power was very bad result.

In addition, about the lightness, all the photosensitive coloring compositions of this embodiment were higher in brightness than the photosensitive coloring composition of a reference example, and were favorable results. Moreover, the brightness of the photosensitive coloring composition (R-30, 31-33, 36-45) containing a zinc phthalocyanine pigment or an aluminum phthalocyanine pigment as a pigment was very high brightness, and was excellent.

[Production of color filter]

First, the blue photosensitive coloring composition used for preparation of a color filter was produced. In addition, the photosensitive coloring composition (R-33) was used about red, and the photosensitive coloring composition (R-41) was used about green.

(Production of Blue Photosensitive Coloring Composition (RB-1))

After stirring and mixing the mixture of the following composition uniformly, it disperse | distributed with Eiger-Mill ("Mini Model M-250 'MKII" made from Eiger Japan Co., Ltd.) for 5 hours using the zirconium oxide beads of diameter 0.5mm, and then 5.0 micrometers It filtered with the filter of and produced the blue coloring composition (DB-6).

Blue pigment (C.I. pigment blue 15: 6) 7.2 part

Purple Pigment (C.I. Pigment Violet 23) 4.8

Resin type dispersant ("EFKA4300" made by Chiba Japan Corporation) 1.0 parts

Acrylic resin solution 1 35.0 parts

PGMAC Part 52.0

Then, the mixture of the following composition was stirred and mixed so that it might become uniform, and it filtered with 1.0 micrometer filter and produced the blue photosensitive coloring composition (RB-1).

Blue coloring composition (DB-6) # 34.0 parts

Acrylic resin solution 2 15.2 parts

Photopolymerizable monomer ("Aronix M400" made by Toagosei Co., Ltd.) 3.3 parts

Photopolymerization initiator ("Iruga cua 907" made by Chiba Japan Corporation) 2.0 parts

Sensitizer ("EAB-F" made by Hodogaya Kagaku Kogyo Kogyo) 0.4 part

Ethylene glycol monomethyl ether acetate 45.1 parts

(Production of color filter)

A black matrix was patterned on the glass substrate, and a red photosensitive coloring composition (R-33) was used as a spin coater on the substrate so as to be x = 0.640 and y = 0.334 in the C light source (hereinafter also used in green and blue). It applied to the thickness of the film | membrane to form, and the coloring film was formed. A photomask was passed through the film, and ultraviolet rays of 300mJ / cm ² were irradiated with an ultrahigh pressure mercury lamp. After spray development with an alkaline developer consisting of 0.2% by weight aqueous sodium carbonate solution to remove unexposed portions, the substrate was washed with ion-exchanged water and heated at 230 ° C. for 20 minutes to form a red filter segment. In the same manner, the green photosensitive coloring composition (R-41) was applied so that x = 0.150 and y = 0.060 using the blue photosensitive coloring composition (RB-1) so as to be y = 0.600, and the green filter segment and blue A filter segment was formed to obtain a color filter.

By using the red photosensitive coloring composition (R-33) and the green photosensitive coloring composition (R-41), it was possible to produce a color filter having high contrast ratio and high brightness.

<< embodiment VIII >>

<Manufacturing method of a quinophthalone pigment | dye>

Kenophthalone pigment 1

(118)

6.8 parts of 8-hydroxyquinaldine, 9 parts of 4-ethoxy phthalic anhydride, and 30 parts of benzoic acid were mixed, and it stirred at 200 degreeC for 5 hours. After cooling, 50 parts of methanol was added and the mixture was stirred for 1 hour. And the solid precipitated was collected by suction filtration. Further, the solid was poured into 400 parts of methanol, stirred for 1 hour, and the solid was collected by suction filtration. It dried with the vacuum dryer (40 degreeC) overnight, and obtained the product of 6.1 parts. Yield 42%. The compound was identified by the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII). It confirmed that it was a target object in m / z = 333.23 (molecular weight 333.10).

Quinophthalone Dye 2

(119)

9.7 parts of 8-hydroxyquinaldine, 10 parts of 4-hydroxyphthalic anhydride, 30 parts of benzoic acid, and 40 parts of methyl benzoate were mixed, and it stirred at 200 degreeC for 5 hours. After cooling, 50 parts of methanol was added and the mixture was stirred for 1 hour. And the solid precipitated was collected by suction filtration. Further, the solid was poured into 400 parts of methanol, stirred for 1 hour, and the solid was collected by suction filtration. It dried with the vacuum dryer (40 degreeC) overnight, and obtained the product of 3.4 parts. Yield 18%. The compound was identified by the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII). It confirmed that it was a target object in m / z = 305.15 (molecular weight 305.07).

Example 1

Quinophthalone Dye 3

(120)

3.0 parts of quinophthalone pigment | dyes 1 were mixed with 30 parts of N, N- dimethylacetamide, 0.4 part of sodium hydroxide and 2.1 parts of 1-bromo- 2-ethylhexanes were further mixed, and it stirred at 105 degreeC for 1 hour. After cooling, 20 parts of chloroform and 100 parts of water were added, and the organic layer was extracted. Five parts of magnesium sulfate was added to the organic layer, which was then dried, filtered and concentrated under reduced pressure. The obtained concentrate was purified by silica gel column chromatography (chloroform / ethyl acetate = 5/1 (volume ratio)) to give 3.2 parts of the product. Yield 81%. The compound was identified by the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII). It confirmed that it was a target object in m / z = 445.33 (molecular weight 445.23).

[Example 2]

Quinophthalone Dye 4

(121)

3.0 parts of 8- (2-ethylhexyloxy) -5-phenyl- 2-methylquinoline, 1.7 parts of 4-ethoxy phthalic anhydride, and 30 parts of benzoic acid were mixed, and it stirred at 200 degreeC for 5 hours. After cooling, 100 parts of methanol was added, followed by stirring for 1 hour. And the solid precipitated was collected by suction filtration. In addition, the solid was poured into 200 parts of methanol, stirred for 1 hour, and the solid was collected by suction filtration. It dried with the vacuum dryer (40 degreeC) overnight, and obtained the product of 3.4 parts. Yield 75%. The compound was identified by the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII). It confirmed that it was a target object in m / z = 521.35 (molecular weight 521.26).

[Example 3]

Quinophthalone Dye 5

[Formula 122]

3.0 parts of quinophthalone pigment | dye 1 were mixed with 30 parts of N, N- dimethylacetamide, 0.4 part of sodium hydroxide and 1.7 part of 1-bromodiethyl ether were further mixed, and it stirred at 105 degreeC for 1 hour. After cooling, 20 parts of chloroform and 100 parts of water were added, and the organic layer was extracted. After adding 5 parts of magnesium sulfate to the organic layer, it was dried, filtered and distinguished, and it concentrated under reduced pressure. The obtained concentrate was purified by silica gel column chromatography (chloroform / ethyl acetate = 5/1 (volume ratio)) to give 3.0 parts of the product. Yield 83%. The compound was identified by the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII). It confirmed that it was a target object in m / z = 405.32 (molecular weight 405.16).

Example 4

Quinophthalone Dye 6

(123)

3.0 parts of quinophthalone pigment | dyes 2 were mixed with 30 parts of N, N- dimethylacetamide, 0.9 parts of sodium hydroxide and 4.2 parts of 1-bromo- 2-ethylhexanes were further mixed, and it stirred at 105 degreeC for 1 hour. After cooling, 20 parts of chloroform and 100 parts of water were added, and the organic layer was extracted. After adding 5 parts of magnesium sulfate to an organic layer, it dried, filtered, and distinguished, and it concentrated under reduced pressure. The obtained concentrate was purified by silica gel column chromatography (chloroform / ethyl acetate = 7/1 (volume ratio)) to give 4.1 parts of the product. Yield 78%. The compound was identified by the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII). It confirmed that it was a target object in m / z = 529.45 (molecular weight 529.32).

[Example 5]

Quinophthalone Pigment 7

(124)

3.0 parts of 8- (2-ethylhexyloxy) -2-methylquinoline, 2.7 parts of 4-cyclohexyloxy phthalic anhydride, and 30 parts of benzoic acid were mixed, and it stirred at 200 degreeC for 5 hours. After standing to cool, 100 parts of methanol was added, followed by stirring for 1 hour. And the solid precipitated was collected by suction filtration. In addition, the solid was poured into 200 parts of methanol, stirred for 1 hour, and the solid was collected by suction filtration. It dried with the vacuum dryer (40 degreeC) overnight, and obtained the product of 4.6 parts. Yield 83%. The compound was identified by the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII). It confirmed that it was a target object in m / z = 499.29 (molecular weight 499.27).

[Example 6]

Quinophthalone Dye 8

(125)

3.0 parts of 8- (2-ethylhexyloxy) -2-methylquinoline, 2.7 parts of 4-phenoxy phthalic anhydride, and 30 parts of benzoic acid were mixed, and it stirred at 200 degreeC for 5 hours. After cooling, 100 parts of methanol was added, followed by stirring for 1 hour. And the solid precipitated was collected by suction filtration. In addition, the solid was poured into 200 parts of methanol, stirred for 1 hour, and the solid was collected by suction filtration. It dried with the vacuum dryer (40 degreeC) overnight, and obtained the product of 4.4 parts. Yield 81%. The compound was identified by the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII). It confirmed that it was a target object in m / z = 493.41 (molecular weight 493.23).

[Example 7]

Quinophthalone Pigment 9

(126)

3.0 parts of quinophthalone pigment | dyes 2 were mixed with 30 parts of N, N- dimethylacetamide, 0.9 part of sodium hydroxide and 5.3 parts of 1-bromo-4- trifluoromethylbenzene were further mixed, and it stirred at 105 degreeC for 1 hour. . After cooling, 20 parts of chloroform and 100 parts of water were added, and the organic layer was extracted. To the organic layer was added 5 parts of magnesium sulfate, dried, filtered and separated, and concentrated under reduced pressure. The resulting concentrate was purified by silica gel column chromatography (chloroform / ethyl acetate = 5/1 (volume ratio)) to give 4.5 parts of products. Yield 78%. The compound was identified by the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII). It confirmed that it was a target object in m / z = 593.58 (molecular weight 593.11).

[Example 8]

Quinophthalone Dye 10

(127)

3.0 parts of 8- (2-ethylhexyloxy) -2-methylquinoline, 2.6 parts of 4- (2-ethoxyethoxy) phthalic anhydride, and 30 parts of benzoic acid were mixed, and it stirred at 200 degreeC for 5 hours. After cooling, 100 parts of methanol was added, followed by stirring for 1 hour. And the solid precipitated was collected by suction filtration. In addition, the solid was poured into 200 parts of methanol, stirred for 1 hour, and the solid was collected by suction filtration. It dried with the vacuum dryer (40 degreeC) overnight, and obtained the product of 4.3 parts. The yield was 79%. The compound was identified by the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII). It confirmed that it was a target object in m / z = 489.46 (molecular weight 489.25).

[Example 9]

Quinophthalone Pigment 11

(128)

3.0 parts of 8- (2-ethylhexyloxy) -2-methylquinoline, 3.1 parts of 4- (2- (1,3-dioxane-2-yl) ethoxy) phthalic anhydride, 30 parts of benzoic acid are mixed, and 200 Stir at 5 ° C. for 5 hours. After standing to cool, 100 parts of methanol was added, followed by stirring for 1 hour. And the solid precipitated was collected by suction filtration. In addition, the solid was poured into 200 parts of methanol, stirred for 1 hour, and the solid was collected by suction filtration. It dried with the vacuum dryer (40 degreeC) overnight, and obtained the product of 4.3 parts. Yield 74%. The compound was identified by the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII). It confirmed that it was a target object in m / z = 531.56 (molecular weight 531.26).

[Example 10]

Quinophthalone Pigment 12

&Lt; EMI ID =

3.0 parts of 2-ethylhexyl 5- (2-methylquinolin-8-yloxy) butanoate and methyl 4- (1,3-dioxo-1,3-dihydroisobenzofuran 5-yloxy) buta 2.2 parts of noate and 30 parts of benzoic acid were mixed, and it stirred at 200 degreeC for 5 hours. After cooling, 100 parts of methanol was added, followed by stirring for 1 hour. And the solid precipitated was collected by suction filtration. Further, the solid was poured into 200 parts of methanol, stirred for 1 hour, and the solid was collected by suction filtration. It dried with the vacuum dryer (40 degreeC) overnight, and obtained the product of 3.6 parts. The yield was 72%. The compound was identified by the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII). It confirmed that it was a target object in m / z = 603.62 (molecular weight 603.28).

[Example 11]

Quinophthalone Pigment 13

(130)

3.0 parts of quinophthalone pigment | dyes 2 were mixed with 30 parts of N, N- dimethylacetamides, 0.9 part of sodium hydroxide and 6.6 parts of 2-ethylhexyl 4- bromo butyrate were further mixed, and it stirred at 105 degreeC for 1 hour. After cooling, 20 parts of chloroform and 100 parts of water were added, and the organic layer was extracted. After adding 5 parts of magnesium sulfate to an organic layer, it dried, filtered, and distinguished and concentrated under reduced pressure. The obtained concentrate was purified by silica gel column chromatography (chloroform / ethyl acetate = 10/1 (volume ratio)) to obtain a product of 4.9 parts. The yield was 71%. The compound was identified by the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII). It confirmed that it was a target object in m / z = 701.67 (molecular weight 701.39).

[Example 12]

Quinophthalone Pigment 14

[Formula 131]

3.0 parts of quinophthalone pigment | dyes 2 were mixed with 30 parts of N, N- dimethylacetamides, 0.9 part of sodium hydroxide, and 6.9 parts of 2-ethylhexyl 5-bromo-gilic acid were further mixed, and it stirred at 105 degreeC for 1 hour. After cooling, 20 parts of chloroform and 100 parts of water were added, and the organic layer was extracted. After adding 5 parts of magnesium sulfate to an organic layer, it dried, filtered, and distinguished and concentrated under reduced pressure. The obtained concentrate was purified by silica gel column chromatography (chloroform / ethyl acetate = 10/1 (volume ratio)) to give 5.0 parts of products. Yield 70%. The compound was identified by the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII). It confirmed that it was a target object in m / z = 729.83 (molecular weight 729.42).

[Example 13]

Quinophthalone Pigment 15

(132)

3.0 parts of 2-ethylhexyl 5- (2-methylquinolin-8-yloxy) pentanoate and 2-ethylhexyl 4- (1,3-dioxo-1,3-dihydroisobenzofuran-5-one jade C) butanoate 3.0 parts and benzoic acid 30 parts were mixed and stirred at 200 ° C for 5 hours. After standing to cool, 100 parts of methanol was added, followed by stirring for 1 hour. And the solid precipitated was collected by suction filtration. In addition, the solid was poured into 200 parts of methanol, stirred for 1 hour, and the solid was collected by suction filtration. It dried with the vacuum dryer (40 degreeC) overnight, and obtained the product of 3.5 parts. Yield 65%. The compound was identified by the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII). It confirmed that it was a target object in m / z = 715.90 (molecular weight 715.41).

[Example 14]

Quinophthalone Pigment 16

(133)

3.0 parts of quinophthalone pigment | dyes 2 are mixed with 30 parts of N, N- dimethylacetamides, 0.9 part of sodium hydroxide, and 8.0 parts of 2- (2-ethylhexyloxy) ethyl 5-bromo-gi-acetic acid are further mixed, and it is 105 degreeC. Stirred for 1 hour. After cooling, 20 parts of chloroform and 100 parts of water were added, and the organic layer was extracted. After adding 5 parts of magnesium sulfate to an organic layer, it dried, filtered, and distinguished and concentrated under reduced pressure. The resulting concentrate was purified by silica gel column chromatography (chloroform / ethyl acetate = 10/1 (volume ratio)) to give 5.9 parts of product. Yield 73%. The compound was identified by the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII). It confirmed that it was a target object in m / z = 817.88 (molecular weight 817.48).

[Example 15]

Quinophthalone Pigment 17

(134)

3.0 parts of quinophthalone pigment | dyes 2 are mixed with 30 parts of N, N- dimethylacetamides, 0.9 parts of sodium hydroxide, and 9.3 parts of 2- (3- (2-ethylhexyloxy) propoxy) ethyl 5-bromo-gi acetates are further added. It mixed and stirred at 105 degreeC for 1 hour. After cooling, 20 parts of chloroform and 100 parts of water were added, and the organic layer was extracted. After adding 5 parts of magnesium sulfate to an organic layer, it dried, filtered, and distinguished and concentrated under reduced pressure. The resulting concentrate was purified by silica gel column chromatography (chloroform / ethyl acetate = 10/1 (volume ratio)) to give 6.4 parts of product. The yield was 71%. The compound was identified by the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII). It confirmed that it was a target object in m / z = 919.91 (molecular weight 919.54).

[Example 16]

Quinophthalone Pigment 18

(135)

3.0 parts of quinophthalone pigment | dyes 1 are mixed with 30 parts of N, N- dimethylacetamide, and 0.5 parts of sodium hydroxide and 7-oxabicyclo [4. 1.4.5 parts of [0] heptane 3-carboxylic acid 2-ethylhexyl were further mixed, and it stirred at 105 degreeC for 1 hour. After cooling, 20 parts of chloroform and 100 parts of water were added, and the organic layer was extracted. After adding 5 parts of magnesium sulfate to an organic layer, it dried, filtered, and distinguished and concentrated under reduced pressure. The obtained concentrate was purified by silica gel column chromatography (chloroform / ethyl acetate = 10/1 (volume ratio)) to obtain a product of 3.9 parts. Yield 75%. The compound was identified by the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII). It confirmed that it was a target object in m / z = 587.51 (molecular weight 587.29).

Example 17

Quinophthalone Pigment 19

&Lt; EMI ID =

3.0 parts of 4-hydroxy-3- (2-methylquinolin-8-yloxy) cyclohexanecarboxylic acid-2-ethylhexyl, 2.1 parts of 5- (2-phenoxyethoxy) phthalic anhydride, and 30 parts of benzoic acid It stirred at 200 degreeC for 5 hours. After cooling, 100 parts of methanol was added, followed by stirring for 1 hour. And the solid precipitated was collected by suction filtration. In addition, the solid was poured into 200 parts of methanol, stirred for 1 hour, and the solid was collected by suction filtration. It dried with the vacuum dryer (40 degreeC) overnight, and obtained the product of 3.6 parts. Yield 73%. The compound was identified by the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII). It confirmed that it was a target object in m / z = 679.76 (molecular weight 679.31).

[Example 18]

Quinophthalone Pigment 20

(137)

Bis (2-ethylhexyl) 4-hydroxy-5- (2-methylquinolin-8-yloxy) cyclohexane- 1,2-dicarboxylic acid 3.0 parts and 5- (2-phenoxy ethoxy) phthalic anhydride 1.5 parts and 30 parts of benzoic acid were mixed, and it stirred at 200 degreeC for 5 hours. After cooling, 100 parts of methanol was added, followed by stirring for 1 hour. And the solid precipitated was collected by suction filtration. In addition, the solid was poured into 200 parts of methanol, stirred for 1 hour, and the solid was collected by suction filtration. It dried with the vacuum dryer (40 degreeC) overnight, and obtained the product of 3.4 parts. Yield 78%. The compound was identified by the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII). It confirmed that it was a target object in m / z = 835.88 (molecular weight 834.43).

[Example 19]

Quinophthalone Pigment 21

&Lt; EMI ID =

3.0 parts of bis (2-ethylhexyl) 4-hydroxy-5- (2-methylquinolin-8-yloxy) cyclohexane- 1,2-dicarboxylic acid and 1.4 parts of 5-phenoethoxy phthalic anhydride, benzoic acid 30 The parts were mixed and stirred at 200 ° C. for 5 hours. After cooling, 100 parts of methanol was added, followed by stirring for 1 hour. And the solid precipitated was collected by suction filtration. In addition, the solid was poured into 200 parts of methanol, stirred for 1 hour, and the solid was collected by suction filtration. It dried with the vacuum dryer (40 degreeC) overnight, and obtained the product of 3.2 parts. Yield 75%. The compound was identified by the mass spectrometer (TOF-MS: burka Dartonikus company autoflexII). It confirmed that it was a target object in m / z = 819.72 (molecular weight 819.43).

[Referential Example 1]

Quinophthalone Pigment 22

[Chemical Formula 139]

It synthesize | combined based on the pigment | dye (IV) synthesis method of Unexamined-Japanese-Patent No. 6-009891.

[Reference Example 2]

Quinophthalone Pigment 23

&Lt; EMI ID =

Disperse Yellow 54 was used.

<Preparation of acrylic resin solution>

Into a separable four-necked flask, 70.0 parts of cyclohexanone was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and an agitator. The temperature was raised to 80 ° C, and the inside of the reaction vessel was replaced with nitrogen, followed by a dropping tube. N-butyl methacrylate 13.3 parts, 2-hydroxyethyl methacrylate 4.6 parts, methacrylic acid 4.3 parts, paracumyl phenol ethylene oxide modified acrylate ("Aronix M110" by Toagosei Co., Ltd.) 7.4 parts A mixture of 0.4 part of 2,2'-azobisisobutylonitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight of 26000. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. First, methoxypropyl acetate was added to the synthesized resin solution so that the nonvolatile content was 20% by weight. The solution was prepared.

Here, the polymerization average molecular weight (Mw) of the acrylic resin is a GPC (manufactured by Tosoh, HLC-8120 GPC) equipped with a RI detector using a TSKgel column (manufactured by Tosoh Corporation), and using THF as a developing solvent. It is the weight average molecular weight (Mw) of the polystyrene conversion measured.

<Manufacturing method of pigment>

(Production of Blue Pigment 1)

200 parts of phthalocyanine-based blue pigment CI pigment blue 15 ("LIONOL BLUE ES" made by Toyo Ink Corporation), 1400 parts of sodium chloride, and 360 parts of diethylene glycol are put in stainless steel 1 gallon kneader (product made by Inoue Sesakujo) And kneaded at 80 ° C. for 6 hours. Subsequently, this kneaded product was poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to a suspension state, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of blue pigments 1 were obtained. The average primary particle diameter of the obtained pigment was 79 nm.

(Production of Purple Pigment 1)

200 parts of dioxazine system purple pigment CI pigment violet 23 ("LIONOGEN VIOLET RL" made by Toyo Ink Corporation), 1400 parts of sodium chloride, and 360 parts of diethylene glycol are put in stainless steel 1 gallon kneader (product made by Inoue Sesakujo), 80 It knead | mixed for 6 hours at ° C. Subsequently, this kneaded product was poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to a suspension state, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of purple pigment 1 were obtained. The average primary particle diameter of the obtained pigment was 28 nm.

(Production of green pigment 1)

Phthalocyanine green pigment CI pigment green 58 ("FASTGEN GREEN A110" by DIC Corporation) was used as it is a commercial item. The average primary particle diameter of green pigment 1 was 22 nm.

(Production of Blue Pigment 2)

In the reaction vessel, 225 parts of phthalodinitrile and 78 parts of aluminum chloride anhydride were mixed and stirred in 1250 parts of n-amyl alcohol. To this, 266 parts of DBU (1,8-Diazabicyclo [4.0] undec-7-ene) were added, the temperature was raised, and the mixture was refluxed at 136 ° C for 5 hours. The reaction solution cooled to 30 degreeC with stirring was injected into the mixed solvent which consists of 5000 parts of methanol and 10000 parts of water, stirring, and obtained the blue suspension. This suspension was filtered, washed with a mixed solvent consisting of 2000 parts of methanol and 4000 parts of water, and dried to obtain 135 parts of chloro aluminum phthalocyanine (AlPc-Cl). Subsequently, 100 parts of chloro aluminum phthalocyanine was added at 1200 parts of concentrated sulfuric acid in a reaction container at room temperature. After stirring for 3 hours at 40 degreeC, this sulfuric acid solution was poured into 24000 parts of 3 degreeC cold waters. The produced blue precipitate was filtered, washed with water and dried to obtain 92 parts of hydroxyaluminum phthalocyanine (AlPc-OH).

2000 parts of N, N-dimethylformamide, 100 parts of AlPc-OH, and 53.9 parts of diphenyl phosphate were added to the reaction container. After reacting for 3 hours at 85 ° C, this solution was poured into 12000 parts of water. The reaction product was filtered, washed with 24000 parts of water, and dried overnight at 60 ° C. under reduced pressure to obtain 123 parts of aluminum phthalocyanine (AlPc-DPP). 50 parts of this AlPc-DPP pigment, 150 parts of sodium chloride, and 25 parts of diethylene glycol were put in a stainless 1 gallon kneader (manufactured by Inoue Sesakujo Co., Ltd.), and kneaded at 120 ° C for 6 hours. Subsequently, the kneaded product was poured into 5 liters of warm water, stirred for 1 hour while heating to 80 占 폚, and then in suspension, filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying overnight at 85 占 폚. Blue pigment 2 was obtained. The average primary particle diameter of the obtained pigment was 29 nm.

(Production of Yellow Pigment 1)

270 parts of kinophthalone type yellow pigment CI pigment yellow 138 (BASF company brand name pariotol yellow -K0961HD), 1350 parts of sodium chloride, and 500 parts of diethylene glycol are put in stainless steel 1 gallon kneader (made by Inoue Sesakujo), and it is 120 degreeC 6 hours kneading. Subsequently, this kneaded product was poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to a suspension state, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 250 parts of yellow pigments 3 were obtained. The average primary particle diameter of the obtained pigment was 36 nm.

(Production of Yellow Pigment 2)

200 parts of nickel complex system yellow pigment CI pigment yellow 150 ("E-4GN" made by Lanxess Corporation), 1400 parts of sodium chloride, and 360 parts of diethylene glycol are put in a stainless gallon kneader (made by Inoue Sesakujo), and it is 120 degreeC 6 hours kneading. Subsequently, this kneaded product was poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to a suspension state, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of yellow pigments 2 were obtained. The average primary particle diameter of the obtained pigment was 67 nm.

(Production of Yellow Pigment 3)

To 500 parts of isoindolin series yellow pigment CI pigment yellow 139 ("Irgafoa yellow 2R-CF" made by Chiba Japan company), 500 parts of sodium chloride and 250 parts of diethylene glycol to stainless 1 gallon kneader (product made in Inoue Sesakujo) It put and knead | mixed at 120 degreeC for 8 hours. Subsequently, the kneaded product was poured into 5 liters of warm water, stirred for 1 hour while heating to 80 占 폚, and then in suspension, filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying overnight at 85 占 폚. 490 parts of yellow pigment 1 were obtained. The average primary particle diameter of the obtained pigment was 92 nm.

(Production of Red Pigment 1)

200 parts of anthraquinone series red pigment CI pigment red 177 ("chromo tarred A2B" made by Chiba Japan company), 1400 parts of sodium chloride, and 360 parts of diethylene glycol are put in stainless steel 1 gallon kneader (product made by Inoue Sesakujo), 80 It knead | mixed for 6 hours at ° C. Then, the kneaded product was poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to a suspension state, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of red pigments 1 were obtained. The average primary particle diameter of the obtained pigment was 54 nm.

(Production of colored composition Q-1)

After stirring and mixing the following mixture to make it uniform, it was made to disperse | distribute with Eiger-Mill ("Mini Model M-250 'MKII" by Eiger Japan Co., Ltd.) for 5 hours using the zirconium oxide beads of diameter 0.5mm, and it was a filter of 5.0 micrometers It filtered through and produced the coloring composition Q-1.

Kinophthalone pigment | dye # 1: 1 11.0 parts

Acrylic resin solution adjusted first ： 40.0 parts

Cyclohexanone ： 48.0 parts

(Production of coloring composition Q-2-23)

Hereinafter, except having changed the quinophthalone pigment | dye 1 into the quinophthalone pigment | dye shown in Table 1, it carried out similarly to coloring composition Q-1, and produced coloring compositions Q-2 -23.

(Production of colored composition DP-1)

After stirring and mixing the following mixture to make it uniform, it was made to disperse | distribute with Eiger-Mill ("Mini Model M-250 'MKII" made from Eiger Japan Co., Ltd.) for 5 hours using the zirconium oxide beads of diameter 0.5mm, and it was a filter of 5.0 micrometers. It filtered with and produced the coloring composition (DP-1).

Blue pigment 1 '(C.I. pigment blue 15: 6)': 11.0 parts

Acrylic resin solution which we adjusted first ： 40.0 parts

Propylene glycol monomethyl ether acetate (PGMAC): 48.0 parts

Resin type dispersant ("EFKA4300" made by Chiba Japan Corporation): 1.0 part

(Production of colored composition DP-2-8)

Hereinafter, except having changed the blue pigment 1 into the pigment shown in Table 2, it carried out similarly to the coloring composition DP-1, and produced the coloring compositions DP-2-8.

[Examples 20-38, Reference Examples 3-9]

<Coloring composition Q-1-23, coating film foreign material test of DP-5-7>

Evaluation was performed by producing a test substrate and counting the number of particles. The coloring composition was apply | coated so that a dry coating film might be set to about 2.0 micrometers on a transparent substrate, and it heated in 230 degreeC for 20 minutes, and obtained the test board | substrate. Evaluation performed surface observation using the metallographic microscope by the Olympus system company "BX60." The magnification is set to 500 times, and the transmission counts the number of particles that can be observed in any 5 fields. In the following evaluation result, (circle) and (circle) are favorable, (triangle | delta) is a level which has many foreign substances but there is no problem in use, and x is a coating unevenness by a foreign substance.

◎: Less than five

○: Five or more, less than 20

△: 20 or more, less than 100

× ： More than 100

The results are shown in Table 3 below.

<Spectral evaluation of coloring composition Q-1-23, DP-5-7>

The coating film was created so that the transmittance | permeability of 450 nm wavelength may be set to 5% on the transparent substrate, and the value of the transmittance | permeability of 500 nm and 550 nm at that time was measured. The higher the transmittance of 500 nm and 550 nm, the better the brightness. In the following evaluation result, the transmittance | permeability of 500 nm and 550 nm at the time of normalizing a quinophthalone pigment | dye and a yellow pigment is 99% or more in (circle), (triangle | delta) is 97 or more and less than 99%, and x is less than 97%. It is more preferable that it is 99% or more. The results are shown in Table 3 below. Moreover, the spectrum of the coating film of Example 1 and the reference examples 1 and 4 is shown to FIGS.

In Examples 20-38, there were few coating film foreign substances and was a favorable result. In addition, Examples 20-38 were the result which was excellent in the spectral characteristic, and showed the spectral shape which brightness increases. Reference Examples 5 to 8 exhibited a relatively good transmittance at 550 nm, but a low transmittance at 500 nm and exhibited a spectral shape in which brightness enhancement could not be expected.

Reference Examples 3 to 7 using a dye having a hydroxyl group in the chinoline ring were compared with the spectral shapes of Examples 20 to 38 using a dye without a hydroxyl group (for example, Example 20 and Reference Example of FIGS. 1 to 3). Spectroscopy of 3, 6 coating film) The pigment | dye which has low transmittance | permeability in 500 nm and which has a hydroxyl group in a quinoline ring is a pigment which cannot anticipate the improvement of lightness.

<Manufacturing method of a blue resist material>

The following mixture was stirred and mixed to make it uniform, and then filtered through a 1.0 μm filter to obtain a blue resist material B-1.

Coloring composition (DP-1) '： 48.0 parts

Coloring composition (DP-2) '： 12.0 parts

Acrylic resin solution adjusted earlier ： 11.0 parts

Trimethylolpropane triacrylate ： 4.2 parts

(`` NK ester ATMPT '' made by Shin-Nakamura Kagaku Corporation)

Photopolymerization initiator ("irgacua 907" made by Chiba Japan Corporation) 1.2 parts

Sensitizer ("EAB-F" made by Hodogaya Chemical Corporation) 0.4 0.4 part

Propylene Glycol Monomethyl Ether Acetate (PGMAC) ： 23.2 parts

[Example 39]

<Adjustment of Resist Material G-1>

The following mixture was stirred and mixed to make it uniform, and then filtered through a 1.0 μm filter to obtain a green resist material (G-1).

Coloring composition (DP-3) '： 18.0 parts

Coloring composition (Q-1) '： 42.0 parts

Acrylic resin solution adjusted first: 11.0 parts

Trimethylolpropane triacrylate ： 4.2 parts

(`` NK ester ATMPT '' made by Shin-Nakamura Kagaku Corporation)

Photopolymerization initiator ("irgacua 907" made by Chiba Japan Corporation) 1.2 parts

Sensitizer ("EAB-F" made by Hodogaya Chemical Corporation) 0.4: 0.4 copy

Propylene glycol monomethyl ether acetate (PGMAC): 23.2 parts

[Examples 40-82, Reference Examples 10-18]

<Adjustment of resist materials G-2 to 45, R-1 to 4, Y-1 to 4>

Hereinafter, except having changed the kind and compounding quantity of a coloring composition as it shows in Tables 5 and 6, it carried out similarly to the resist material G-1, and obtained resist materials G-2 ~ 45, R-1-4, Y-1-4.

<Evaluation of resist material>

Each test of the obtained resist materials G-1 to 45, R-1 to 4, and Y-1 to 4 of the color characteristics (Y: brightness), coating foreign substances, heat resistance, and light resistance was performed by the following method. The results of the test are shown in Table 6.

<Color characteristic (Y: brightness)>

On the glass substrate, in the C light source, the resist materials G-1 to 45 were coated with a resist material at a thickness of a film such that x = 0.264 and y = 0.600, and the substrate was heated at 230 ° C. for 20 minutes. The resist material R-1-4 apply | coated the resist material to the thickness of the film which becomes x = 0.340 and y = 0.640, and heated this board | substrate at 230 degreeC for 20 minutes. The resist materials Y-1-4 apply | coated the resist material to the thickness of the film which becomes x = 0.440 and y = 0.506, and heated this board | substrate at 230 degreeC for 20 minutes. Then, the brightness Y of the obtained board | substrate was measured with the microscopic spectrophotometer (Olymps Kogaku Corporation "OSP-SP200").

The results are shown in Table 6 below.

<Coating foreign material test>

The resist material was apply | coated so that a dry coating film might be set to about 2.5 micrometers on a transparent board | substrate, and after performing full ultraviolet-ray exposure, it heated at 230 degreeC for 20 minutes in an oven, and left to cool to obtain an evaluation substrate. Evaluation performed surface observation using the metallographic microscope by the Olympus system company "BX60." The magnification is set to 500 times, and the number of particles that can be seen at any five fields by transmission is counted. In the following evaluation result, (double-circle) and (circle) are favorable, (triangle | delta) is a level which has many foreign substances but there is no problem in use, and x is coating unevenness by a foreign substance.

◎: Less than five

○: Five or more, less than 20

△: 20 or more, less than 100

× ： More than 100

The results are shown in Table 6 below.

<Coating film heat resistance test>

The resist material was applied on the transparent substrate so as to have a dry coating of about 2.5 μm, subjected to ultraviolet exposure through a mask having a predetermined pattern, and then sprayed with an alkaline developer with a spray to remove the uncured portion to form a desired pattern. Subsequently, heating at 230 ° C. for 20 minutes in an oven, and using chromatic spectrophotometer (Olympus Co. It measured using Cossa "OSP-SP200". Then, it heated at 230 degreeC for 1 hour in oven as a heat test, and measured chromaticity 2 (L * (2), a * (2), b * (2)) in C light source. Using the measured color difference value, color difference (DELTA) Eab * was computed according to the following formula, and the heat resistance of the coating film was evaluated in the following four steps. Moreover, if evaluation is more than (triangle | delta), it is a level which is satisfactory practically. ΔEab * = √ ((L * (2)-L * (1)) 2+ (a * (2)-a * (1)) 2+ (b * (2)-b * (1)) 2)

◎ ： ΔEab * is less than 1.5

○: ΔEab * is 1.5 or more but less than 3.0

Δ: ΔEab * is 3.0 or more and less than 5.0

X: ΔEab * is 5.0 or more

The results are shown in Table 6 below.

<Film coating light resistance test>

A test substrate was produced in the same procedure as the coating film heat resistance test, and chromaticity 1 (L * (1), a * (1), and b * (1)) at the C light source was determined by a microscopic spectrophotometer (Olympus Kogaku Co., Ltd., "OSP-"). SP200 "). Then, the board | substrate was put into the light resistance tester ("SUNTESTCPS +" by TOYOSEIKI Corporation), and it was left to stand for 500 hours. After removing the substrate, chromaticity 2 (L * (2), a * (2), b * (2)) in the C light source was measured, and the color difference ΔEab * was calculated in the same manner as the coating film heat resistance test, and the coating film heat resistance test The solvent resistance of the coating film was evaluated by the same criteria. Moreover, if evaluation is more than (triangle | delta), it is a level which is satisfactory practically.

The results are shown in Table 6 below.

<Coating Solvent Resistance Test>

A test substrate was produced in the same procedure as the coating film heat resistance test, and chromaticity 1 (L * (1), a * (1), and b * (1)) at the C light source was determined by a microscopic spectrophotometer (Olympus Kogaku Co., Ltd., "OSP-"). SP200 "). Thereafter, the substrate was immersed in N-methylpyrrolidone for 30 minutes. After removing the substrate, chromaticity 2 (L * (2), a * (2), b * (2)) in the C light source was measured, and the color difference ΔEab * was calculated in the same manner as the coating film heat resistance test, and the coating film heat resistance test The solvent resistance of the coating film was evaluated according to the same criteria. Moreover, if evaluation is more than (triangle | delta), it is a level which is satisfactory practically.

The results are shown in Table 6 below.

In the resist materials (G-1 to 19, G-25 to 43, R-1 to 3, and Y to 3) of Examples 39 to 82, the brightness (Y), coating foreign matter, heat resistance, light resistance, and solvent resistance Good results were shown.

In contrast, the resist materials (G-20 to G-24, G-44, 45, R-4, and Y-4) of Reference Examples 10 to 16 are Examples 39 to 82 (G-1 to 19 and G-25). The brightness (Y) was low compared with -43, R-1-3, Y-1-3).

[Example 83]

<Color filter (CF-1)>

A black matrix was patterned on the glass substrate, and a red resist material (R-1) was applied on the substrate to a thickness of a film such as a C light source x = 0.640 and y = 0.340 to form a colored film. . A photomask was passed through the film, and ultraviolet rays of 300mJ / cm ² were irradiated with an ultrahigh pressure mercury lamp. Then, spray development was carried out with an alkaline developer consisting of 0.2% by weight aqueous sodium carbonate solution to remove unexposed portions, and then washed with ion-exchanged water, and the substrate was heated at 230 ° C. for 20 minutes to form a red filter segment. By the same method, the green resist material (G-15) becomes x = 0.264 and y = 0.060 using the blue resist material (B-1) in the thickness of the film which becomes x = 0.264 and y = 0.600. It applied to the thickness of the same film | membrane, respectively, and formed the green filter segment and the blue filter segment, and obtained the color filter (CF-1).

<Production of Liquid Crystal Display Device>

On the obtained RGB color filter, the transparent ITO electrode layer was formed, and the polyimide orientation layer was formed thereon. On the other surface of this glass substrate, the color display device was produced combining with the 3 wavelength CCFL light source of a polarizing plate. On the other hand, the TFT array and the pixel electrode were formed on one surface of another (second) glass substrate, and the polarizing plate was formed on the other surface. The two glass substrates prepared in this way were arranged so that the electrode layers faced each other, were aligned while keeping the distance between the two substrates constant using spacer beads, and the circumference was sealed with a sealant to leave the openings for injecting the liquid crystal composition. . After inject | pouring a liquid crystal composition from an opening part, the opening part was sealed. The color display device was manufactured by combining the liquid crystal display device thus produced with the three-wavelength CCFL light source of the backlight unit.

[Examples 83 to 87, Reference Examples 19 and 20]

(Color filter (CF-2-7))

Hereinafter, by the same method as the preparation of the color filter CF-1, the color filter (CF-2 ~) of Examples 83 to 87, Reference Examples 19 and 20 by the combination of the resist material shown in Table 8 and the three wavelength CCFL light source 7) and color display device.

Then, in the obtained color display apparatus, the light source was light-emitted and the color image was displayed, and the brightness Y of the filter segment part of each color was measured with the microspectral spectrophotometer (OLYMPOS KOGAKU "OSP-SP200"). The results are shown in Table 8.

Comparing Examples 84 and 85 with Reference Example 19, the color filter formed by using the quinophthalone dye of the present embodiment was seen in at least one filter segment (green or red) compared to the filter segment using a conventional pigment. Brightness improved in the color filter (CF-2,3) using the quinophthalone pigment | dye of embodiment. As a result, the brightness of white display became high and the improvement of the performance as a color filter was confirmed.

In addition, it was confirmed that the color filter (CF-1) formed by using the quinophthalone pigment | dye of this embodiment for both green and red of Example 83 further improves brightness, and as a result, the brightness of white display became high. .

In addition, when comparing Example 87 with Reference Example 20, the color filter formed using the quinophthalone dye of the present embodiment has at least one filter segment (yellow) as compared with the filter segment containing the pigment used in the prior art. Also in the color filter (CF-6) containing the quinophthalone pigment | dye of this embodiment, the brightness improved, As a result, the brightness of a white display became high and the improvement of the performance as a color filter was confirmed.

In addition, when the green, red, and yellow of Example 86 both contained the color filter dye of the present embodiment (CF-5), the brightness was further improved, and as a result, the brightness of the white display was confirmed to increase.

From the above results, by using the quinophthalone pigment | dye of this embodiment and the coloring composition which mix | blended it, high brightness of a color filter is possible and other physical properties can be used suitably without a problem.

Claims (16)

It contains a coloring agent, binder resin, and a solvent,
The said coloring agent contains the coloring agent represented by General formula (1), The coloring composition for color filters characterized by the above-mentioned.
[Chemical Formula 1]

In this formula,
In the general formula ^{(1), R 1 ~ R} 13 each independently represent a hydrogen atom, a halogen atom, a substituent which may have an alkyl group, the substituent may have a good good alkoxyl group, an optionally substituted aryl group, -SO ₃ H ; -COOH; And monovalent to trivalent metal salts of these acid groups; alkylammonium salts, phthalimidomethyl groups which may have a substituent, or sulfamoyl groups which may have a substituent;
Adjacent groups of R ¹ to R ⁴ and / or R ¹⁰ to R ¹³ are integrated to form an aromatic ring which may have a substituent.
The method of claim 1,
The coloring agent represented by General formula (1) is a coloring agent chosen from general formula (1A)-(1C), The coloring composition for color filters characterized by the above-mentioned.
(2)

In this formula,
In General Formulas (1A) to (1C), R ¹⁴ to R ²⁸ , R ²⁹ to R ⁴³ , and R ⁴⁴ to R ⁶⁰ are each independently: a hydrogen atom; A halogen atom; Alkyl group which may have a substituent; An alkoxyl group which may have a substituent; The import FIG aryl group substituents; -SO ₃ H, -COOH, and monovalent-trivalent metal salts of these acidic groups; alkyl ammonium salts; Phthalimidomethyl group which may have a substituent; Or the sulfamoyl group which may have a substituent is shown.
3. The method of claim 2,
The said coloring agent further contains the coloring agent chosen from general formula (8A) and (8B), The coloring composition for color filters characterized by the above-mentioned.
(3)

In this formula,
In General Formula (8A), X ₁ to X ₄ each independently represent an alkyl group which may have a substituent, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, a heterocyclic group which may have a substituent, and a substituent An alkoxyl group which may have, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, or an arylthio group which may have a substituent,
Y ₁ to Y ₄ each independently represent a halogen atom, a nitro group, a phthalimidomethyl group which may have a substituent, or a sulfamoyl group which may have a substituent. Z represents a hydroxyl group, a chlorine atom, -OP (= O) R ₁ R ₂ , or -O-SiR ₃ R ₄ R ₅ . R ₁ to R ₅ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxyl group which may have a substituent, or an aryloxy group which may have a substituent, and R May be combined with each other to form a ring,
m ₁ to m ₄ and n ₁ to n ₄ each independently represent an integer of 0 to 4, and m ₁ + n ₁ , m ₂ + n ₂ , m ₃ + n ₃ , and m ₄ + n ₄ are each 0 to 4; May be the same or different.
[Chemical Formula 4]

In this formula,
In General Formula (8B), X ₅ to X ₁₂ are each independently an alkyl group which may have a substituent, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, a heterocyclic group which may have a substituent, or a substituent An alkoxyl group which may have, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, or an arylthio group which may have a substituent,
Y ₅ to Y ₁₂ each independently represent a halogen atom, a nitro group, a phthalimidomethyl group which may have a substituent, or a sulfamoyl group which may have a substituent;
L represents -O-SiR ₆ R ₇ -O-, -O-SiR ₆ R ₇ -O-SiR ₈ R ₉ -O-, or -O-P (= O) R ₁₀ -O-, and R represents ₆ to R ₁₀ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxyl group which may have a substituent, or an aryloxy group which may have a substituent,
m ₅ to m ₁₂ and n ₅ to n ₁₂ each independently represent an integer of 0 to 4, and m ₅ + n ₅ , m ₆ + n ₆ , m ₇ + n ₇ , m ₈ + n ₈ , and m ₉ + n ₉ , m _{10 + n 10, m 11 +} n 11, m 12 + n 12 are each from 0 to 4, or different may be the same.
3. The method of claim 2,
The said coloring agent contains a dispersing agent further, The coloring composition for color filters characterized by the above-mentioned.
5. The method of claim 4,
The dispersant isocyanate of the urethane prepolymer (E) having an isocyanate group at both ends formed by reacting a hydroxyl group of a vinyl polymer (A) having two hydroxyl groups in one end region with an isocyanate group of a diisocyanate (B). A pigment dispersant obtained by reacting a group with at least a primary and / or secondary amino group of an amine compound containing at least a polyamine (C), and the vinyl polymer (A) having ethylenic unsaturated having at least one of an ethylene oxide chain or a propylene oxide chain. The coloring composition for color filters containing monomer (a1) in a copolymerization composition.
3. The method of claim 2,
The said coloring agent further contains the coloring agent represented by General formula (6), The coloring composition for color filters characterized by the above-mentioned.
[Chemical Formula 5]

In this formula,
In general formula (6), R <_1> -R <_6> is respectively independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, or -O- R ₇ is represented, wherein R ₇ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group, provided that R ₁ to R ₆ are not all hydrogen atoms.
It contains a coloring agent, binder resin, and a solvent,
The said coloring agent contains the coloring agent represented by General formula (6), The coloring composition for color filters characterized by the above-mentioned.
[Chemical Formula 6]

In this formula,
In general formula (6), R <_1> -R <_6> is respectively independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, or -O- R ₇ is represented, wherein R ₇ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group, provided that R ₁ to R ₆ are not all hydrogen atoms.
The method of claim 7, wherein
The said coloring agent further contains the coloring agent chosen from general formula (8A) and (8B), The coloring composition for color filters characterized by the above-mentioned.
(7)

In this formula,
In General Formula (8A), X ₁ to X ₄ each independently represent an alkyl group which may have a substituent, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, a heterocyclic group which may have a substituent, and a substituent An alkoxyl group which may have, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, or an arylthio group which may have a substituent,
Y ₁ to Y ₄ each independently represent a halogen atom, a nitro group, a phthalimidomethyl group which may have a substituent, or a sulfamoyl group which may have a substituent;
Z represents a hydroxyl group, a chlorine atom, -OP (= O) R ₁ R ₂ , or -O-SiR ₃ R ₄ R ₅ , wherein R ₁ to R ₅ each independently represent a hydrogen atom, a hydroxyl group, and a substituent An alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxyl group which may have a substituent, or an aryloxy group which may have a substituent may be represented, and R may combine with each other to form a ring,
m ₁ to m ₄ and n ₁ to n ₄ each independently represent an integer of 0 to 4, and m ₁ + n ₁ , m ₂ + n ₂ , m ₃ + n ₃ , and m ₄ + n ₄ are each 0 to 4; May be the same or different.
[Chemical Formula 8]

In this formula,
In General Formula (8B), X ₅ to X ₁₂ are each independently an alkyl group which may have a substituent, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, a heterocyclic group which may have a substituent, or a substituent An alkoxyl group which may have, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, or an arylthio group which may have a substituent,
Y ₅ to Y ₁₂ each independently represent a halogen atom, a nitro group, a phthalimidomethyl group which may have a substituent, or a sulfamoyl group which may have a substituent;
L represents -O-SiR ₆ R ₇ -O-, -O-SiR ₆ R ₇ -O-SiR ₈ R ₉ -O-, or -O-P (= O) R ₁₀ -O-, and R represents ₆ to R ₁₀ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxyl group which may have a substituent, or an aryloxy group which may have a substituent,
m ₅ to m ₁₂ and n ₅ to n ₁₂ each independently represent an integer of 0 to 4, and m ₅ + n ₅ , m ₆ + n ₆ , m ₇ + n ₇ , m ₈ + n ₈ , and m ₉ + n ₉ , m _{10 + n 10, m 11 +} n 11, m 12 + n 12 , respectively, may be different to 0-4, may be the same.
9. The method according to claim 7 or 8,
The said coloring agent further contains the coloring agent represented by General formula (7), The coloring composition for color filters characterized by the above-mentioned.
[Chemical Formula 9]

In this formula,
In general formula (7), R <_1> -R <_6> is respectively independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, or -O —R ₁₁ , wherein R ₁₁ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group,
R ₇ to R ₁₀ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a carboxyl group, a substituted or unsubstituted sulfoamide group, A substituted or unsubstituted heterocyclic moiety, -S-R ₁₂ , -O-R ₁₂ , or -COO-R ₁₂ , wherein R ₁₂ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or It is a substituted or unsubstituted aryl group.
It contains a coloring agent, binder resin, and a solvent,
The said coloring agent contains the coloring agent represented by General formula (7A), The coloring composition for color filters characterized by the above-mentioned.
[Formula 10]

In this formula,
In General Formula (7A), R ₁ to R ₆ each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, or -O-. R ₁₁ represents where R ₁₁ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group,
R ₇ to R ₁₀ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a carboxyl group, a substituted or unsubstituted sulfoamide group , substituted or represents a cyclic heterocyclic _{residue, -S-R 12, -O-} R 12, -COO-R ₁₂ or unsubstituted, wherein R ₁₂ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, Or a substituted or unsubstituted aryl group, provided that at least one of R ₇ to R ₁₀ is —O—R ₁₂ .
The method of claim 10,
The coloring agent represented by the said General formula (7A) is a coloring agent represented by General formula (7B), The coloring composition for color filters characterized by the above-mentioned.
(11)

In this formula,
In General Formula (7B), R ₁₃ is a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. R ₁₄ to R ₁₇ each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or —O-R ₁₈ , wherein R ₁₈ is substituted or unsubstituted An alkyl group or a substituted or unsubstituted aryl group, provided that at least one of R ₁₄ to R ₁₇ is —O—R ₁₈ .
The method according to any one of claims 1, 7, 10 and 11,
The said coloring agent contains a yellow coloring agent further, The coloring agent for color filters characterized by the above-mentioned.
The method of claim 12,
The yellow colorant is selected from the group consisting of CI pigment yellow 138, CI pigment yellow 139, CI pigment yellow 150 and CI pigment yellow 185.
The method according to any one of claims 1 to 11,
The coloring composition for color filters containing the coloring agent chosen from the group which consists of a green coloring agent, a blue coloring agent, and a red coloring agent.
The method according to any one of claims 1 to 11,
It contains a photopolymerizable monomer and / or a photoinitiator, The coloring composition for color filters characterized by the above-mentioned.
16. The method according to any one of claims 1 to 15,
The color filter provided with the filter segment formed using the coloring composition for color filters.

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