TWI466954B - Coloring composition and color filter for color filter - Google Patents

Description

Coloring composition and color filter for color filter

The present invention relates to a coloring agent for a color filter, a coloring composition, and a color filter formed therefor, which are used in the manufacture of a color filter used in a color liquid crystal display device, a color image sensor device, or the like.

The liquid crystal display device is a display device in which a liquid crystal layer sandwiched between two polarizing plates is controlled by a light amount that controls the amount of light passing through the first polarizing plate to control the amount of light passing through the second polarizing plate. The type of liquid crystal (TN: Twisted Nematic) type is the mainstream. The liquid crystal display device can be used as a display color by providing a color filter between two polarizing plates. In recent years, it has been used for televisions and personal computer displays, and has high contrast value for color filters. The demand for high brightness and high color reproducibility is improved.

The color filter is arranged in parallel or crosswise with a fine strip (striped) color filter segment having two or more different hues on the surface of a transparent substrate such as glass, or is arranged by vertical and horizontal fixing of fine color filter segments. Configured to form. In general, color filter segments of three colors of red, green, and blue are formed in a large amount, and each segment has a fineness of micrometers to several hundreds of micrometers, and each color tone is arranged neatly in a fixed arrangement.

In general, in a color liquid crystal display device, a transparent electrode that drives a liquid crystal on a color filter is formed by vapor deposition or sputtering, and an alignment film is formed thereon so that liquid crystals are aligned in a fixed direction. The transparent electrode and the alignment film may have sufficient performance, and the formation thereof generally needs to be above 200 ° C, more preferably 230. It is carried out at a high temperature above °C. Therefore, in terms of manufacturing, the color filter is required to use a coloring agent excellent in heat resistance and light resistance.

The color filter segment is manufactured using a yellow pigment on the coloring agent for coloring, and in the point of having high light transmittance, C.I. Pigment Yellow No. 138 is often used. However, the C.I. Pigment Yellow No. 138, although having a better brightness, is preferably more preferred. In addition, in recent years, the demand for high contrast of color filters has become stronger, but C.I. Pigment Yellow No. 138 has a problem of low contrast.

A quinoline yellow compound is known as a pigment dispersant which stabilizes the dispersion of C.I. Pigment Yellow No. 138. For example, in Patent Document 1, a quinophthalone compound containing a sulfonic acid has been disclosed, and in Patent Document 2, a quinoline yellow compound to which a quinone imine methyl group is added has also been disclosed. The dispersibility of C.I. Pigment Yellow No. 138 can be improved by using these pigment dispersants, but the comparative values have not yet achieved the desired characteristics.

In Patent Document 3, a quinophthalone compound having the following compound (1) as a starting material is disclosed, and a pigment composition having improved dispersion stability over time is disclosed.

In Patent Document 4, it is described that a compound which is dimerized by using a quinophthalone structure can provide an excellent coloring property and sharpness. Material composition.

However, when the coloring agent containing these quinophthalone compounds is used as a color filter, the current situation is that the contrast value and insufficient coloring power cannot be completely improved.

Patent Document 5 discloses a quinoline yellow compound having a naphthalene ring in terms of coloring of a polymer material. However, these quinoline yellow compounds are intended for coloring plastics, and their suitability for use as color filters is not clear.

Further, it is known that an anthraquinone aluminum pigment can be used in terms of a coloring composition for a green color filter segment (Patent Documents 6 to 12). When using an anthraquinone aluminum pigment, it is necessary to use a yellow pigment in combination. However, since the quinoline yellow compound which has been known for yellow pigments has the above problems, it is not sufficient in terms of the contrast value and the coloring power of the color filter when used in combination.

Further, in order to achieve high luminance of the color filter and high contrast, the pigment contained in the color filter segment is subjected to miniaturization treatment. However, simply by making the pigment finer, the pigment tends to aggregate easily as the primary particles or the secondary particles are refined. Although it is desired to stabilize the pigment, it is extremely difficult to obtain a stable colored composition. Further, it is also known that the pigment which is subjected to the micronization treatment is extremely difficult to stably disperse at a high concentration in the pigment carrier, and causes various problems in the production step and in the product itself.

Therefore, a pigment dispersant is usually used in order to maintain a good dispersion state. Among them, the pigment dispersant is composed of a structure in which a pigment adsorption site and a portion having a high affinity with a solvent as a dispersion solvent are combined, and the performance is determined by the balance between the two sites. In terms of pigment dispersant, it is blended with the dispersed material. A pigment having a surface close to an acidic surface is used in the state of the surface of the pigment, and a dispersing agent having a basic functional group having electrostatic adsorption therein is generally used. In this case, the basic functional group becomes the adsorption site of the pigment. An example of a coloring composition for a color filter using a basic pigment dispersing agent having an amino group as a basic functional group is as described in Patent Documents 13 to 17.

However, these are substances which have a certain degree of dispersibility, and the ultrafine refining treatment pigment which is used as a coloring composition for color filters cannot be dispersed and stabilized as a coloring composition for a color filter.

Therefore, a coloring composition for a color filter is proposed, which is a pigment dispersing agent formed by reacting an isocyanate group having a urethane prepolymer having an isocyanate group at both ends with an amine compound to impart dispersibility, fluidity, and Excellent preservation stability (Patent Document 18).

However, even if the dispersing agent described in Patent Document 18 is used, the dispersing ability of the quinophthalone pigment is not sufficient, and high contrast and dispersion stability cannot be achieved.

Further, examples of the index indicating the display performance of the liquid crystal display device include a voltage holding ratio. When the liquid crystal-based material having extremely high insulating properties is dissolved in the liquid crystal cell by the polar compound remaining in the coloring composition for the color filter, the voltage between the electrodes is lowered, and the voltage holding ratio is lowered, so that occurrence of display spots occurs. Poor alignment, etc., causes a decrease in performance of the liquid crystal display device. Therefore, the coloring composition for a color filter is required to be insoluble to liquid crystal.

Patent Documents 19 to 21 disclose a structure containing various structures. The color filters of the phthalocyanine pigment and the quinoline yellow pigment are colored with a green color. However, these color filters use a green coloring composition, but have problems of insufficient brightness, heat resistance, and light resistance.

Patent Document 22 discloses a green coloring composition for a color filter, which is a means for improving brightness, and includes an anthraquinone zinc-based pigment and a quinoline yellow-based dye. However, the anthraquinone zinc-based pigment is easily extracted in the liquid crystal phase layered on the color filter layer because of its high acidity, and thus may cause a decrease in voltage holding ratio, generation of display spots, and poor alignment. A problem that the performance of the liquid crystal display element is lowered.

[Previous Technical Literature] Patent literature

Patent Document 1: Japanese Laid-Open Patent Publication No. 2002-179979

Patent Document 2: Japanese Patent Laid-Open Publication No. 2008-95007

Patent Document 3: Japanese Patent Laid-Open Publication No. 2008-81566

Patent Document 4: Japanese Laid-Open Patent Publication No. 2008-74985

Patent Document 5: Japanese Laid-Open Patent Publication No. 51-147544

Patent Document 6: Japanese Laid-Open Patent Publication No. 2002-131521

Patent Document 7: Japanese Laid-Open Patent Publication No. 2002-250812

Patent Document 8: Japanese Patent Laid-Open Publication No. 2003-4930

Patent Document 9: Japanese Patent Laid-Open Publication No. 2004-333817

Patent Document 10: Japanese Laid-Open Patent Publication No. 2000-301833

Patent Document 11: Japanese Laid-Open Patent Publication No. 2010-79247

Patent Document 12: Japanese Laid-Open Patent Publication No. SHO 57-90058

Patent Document 13: Japanese Laid-Open Patent Publication No. 09-176511

Patent Document 14: Japanese Patent Laid-Open No. Hei 10-213898

Patent Document 15: Japanese Laid-Open Patent Publication No. 2001-240780

Patent Document 16: Japanese Laid-Open Patent Publication No. 2002-31713

Patent Document 17: Japanese Laid-Open Patent Publication No. 2004-54213

Patent Document 18: Japanese Laid-Open Patent Publication No. 2010-39433

Patent Document 19: Japanese Laid-Open Patent Publication No. Hei 6-220339

Patent Document 20: Japanese Patent Laid-Open No. Hei 8-171201

Patent Document 21: Japanese Laid-Open Patent Publication No. 2009-51896

Patent Document 22: Japanese Laid-Open Patent Publication No. 2010-168531

An embodiment of the present invention relates to a coloring composition for a color filter, which comprises a coloring agent, a binder resin, and a solvent, and the coloring agent is a coloring agent represented by the formula (1).

In the 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 alkoxy group which may have a substituent, and an aryl group which may have a substituent. -SO ₃ H, -COOH, and a monovalent to trivalent metal salt of the acid group, an alkanolammonium salt, a sulfhydryl methyl group which may have a substituent, or an amine sulfonyl group which may have a substituent. Wherein, R ¹ to R ⁴ and/or adjacent groups of R ¹⁰ to R ^{13 are} bonded to form an aromatic ring which may have a substituent. That is, a group of at least one adjacent one of R ¹ to R ⁴ and/or a group of at least one adjacent one of R ¹⁰ to R ¹³ are bonded together to form a substituent. Aromatic ring.

The coloring agent represented by the formula (1) is preferably a coloring agent selected from the general formulae (1A) to (1C).

Wherein, in the general formulae (1A) to (1C), R ¹⁴ to R ²⁸ , R ²⁹ to R ⁴³ and R ⁴⁴ to R ⁶⁰ each independently represent a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, Alkoxy group which may have a substituent, an aryl group which may have a substituent, -SO ₃ H, -COOH, and a monovalent to trivalent metal salt of the acid group, an alkanolammonium salt, or a substituent An imine methyl group, or an amine sulfonyl group which may have a substituent.

The coloring agent may further contain one of the general formulas (8A) and (8B) The coloring agent.

Wherein, in the 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, and a substituent which may have a substituent a cyclic group, an alkoxy group which may have a substituent, 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 sulfhydryl methyl group which may have a substituent, or an amine sulfonyl 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, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, or an aromatic oxygen which may have a substituent Bases, the Rs may also be bonded to 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 , m ₄ + n ₄ each represent 0 to 4, Can be the same or different.

Wherein, in the formula (8B), X ₅ to X ₁₂ 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, and a substituent which may have a substituent a cyclic group, an alkoxy group which may have a substituent, 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 sulfhydryl methyl group which may have a substituent, or an amine sulfonyl 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 -OP(=O)R ₁₀ -O-; R ₆ to R ₁₀ Each independently represents a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy 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, m ₅ + n ₅ , m ₆ + n ₆ , m ₇ + n ₇ , m ₈ + n ₈ , m ₉ + n ₉ m ₁₀ + n ₁₀ , m ₁₁ + n ₁₁ , m ₁₂ + n ₁₂ each represent 0 to 4, which may be the same or different.

The coloring agent may further contain a dispersing agent. The dispersant may be an urethane having an isocyanate group at both ends thereof by reacting a hydroxyl group of an ethylene polymer (A) having two hydroxyl groups in a single terminal portion thereof with an isocyanate group of a diisocyanate (B). a pigment dispersant obtained by reacting an isocyanate group of the prepolymer (E) with one of the amine compounds containing at least the polyamine (C) and/or a secondary amine group, wherein the ethylene polymer (A) is co-available The poly composition includes at least one ethylenically unsaturated monomer (a1) having an ethylene oxide chain or a propylene oxide chain.

The coloring agent may further contain a coloring agent represented by the formula (6).

Wherein, in the 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 -OR ₇ . Wherein R ₇ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group. However, R ₁ to R _{6 are} not all hydrogen atoms.

An embodiment of the present invention relates to a coloring composition for a color filter, comprising: a coloring agent, a binder resin, and a solvent, wherein the coloring agent contains a coloring agent represented by the formula (6). Further, the coloring agent may further contain a coloring agent selected from the group consisting of the general formulae (8A) and (8B). The coloring agent may further contain a coloring agent represented by the formula (7).

Wherein, in the 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 -OR ₁₁ . Wherein R ₁₁ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group. Wherein R ₇ to R ₁₀ 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, a carboxyl group, a substituted or unsubstituted sulfonate. Amidino, substituted or unsubstituted heterocyclic residue, -SR ₁₂ , -OR ₁₂ , or -COO-R ₁₂ . Wherein R ₁₂ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group.

Meanwhile, an embodiment of the present invention relates to a coloring composition for a color filter, comprising: a coloring agent, a binder resin, and a solvent, wherein the coloring agent contains a coloring agent represented by the formula (7A).

The coloring agent represented by the above formula (7A) may be a coloring agent represented by the formula (7B).

Wherein, in the 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 -OR ₁₁ . Wherein R ₁₁ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group. Wherein R ₇ to R ₁₀ 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, a carboxyl group, a substituted or unsubstituted sulfonate. Amidino, substituted or unsubstituted heterocyclic residue, -SR ₁₂ , or -OR ₁₂ , or -COO-R ₁₂ . Wherein R ₁₂ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group. However, at least one of R ₇ to R ₁₀ is -OR ₁₂ .

Wherein in the formula (7B), R ₁₃ represents a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. Wherein 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 -OR ₁₈ or -COO-R ₁₂ . Wherein R ₁₈ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group. However, at least one of R ₁₄ to R ₁₇ is -OR ₁₈ .

Meanwhile, the above coloring agent may contain a yellow coloring agent. Among them, the yellow coloring agent is selected from the group consisting of: C.I. Pigment Yellow No. 138, C.I. Pigment Yellow No. 139, C.I. Pigment Yellow No. 150, and C.I. Pigment Yellow No. 185. good. The coloring agent may further contain a coloring agent selected from the group consisting of a green coloring agent, a blue coloring agent, and a red coloring agent. The color filter may be a coloring composition, and may further contain a photopolymerizable monomer and/or a photopolymerization initiator.

An embodiment of the present invention relates to a color filter comprising a color filter segment formed of the coloring composition for a color filter.

The present invention relates to the following embodiments I to VIII.

<Embodiment I>

The object of the present invention is to provide a coloring agent for a color filter, a coloring composition, and a color filter using the same, which have excellent coloring power and can be used in a color filter to obtain high brightness and high contrast value. .

The present inventors have found that when a coloring agent for a color filter containing a quinophthalone compound having a specific structure is used, a color filter excellent in dispersibility and coloring power and imparting high brightness and high contrast value can be produced. This embodiment is completed.

That is, this embodiment relates to a color filter comprising a quinophthalone compound represented by the formula (1). Among them, the quinophthalone compound represented by the formula (1) is preferably any of the formulae (1A) to (1C). In the general formulae (1A) to (1C), R ¹⁴ to R ²⁸ , R ²⁹ to R ⁴³ and R ⁴⁴ to R ⁶⁰ each independently represent a hydrogen atom or a halogen atom. At the same time, it is preferred that the coloring agent contains a yellow coloring agent. Further, among them, at least one selected from the group consisting of CI Pigment Yellow No. 138, CI Pigment Yellow No. 139, CI Pigment Yellow No. 150, and CI Pigment Yellow No. 185 is preferable. At the same time, the coloring composition for a color filter is preferably composed of at least the above coloring agent, a binder resin, and an organic solvent. Further, the coloring composition for the color filter may further contain a green coloring agent and/or a blue coloring agent. In addition to this, the coloring composition for a color filter may further contain a photopolymerizable monomer and/or a photopolymerization initiator. Further, a color filter including at least one of a red color filter segment, at least one green color filter segment, and at least one blue color filter segment, and at least one of the green color filter segments It is preferred that the coloring composition for the color filter described above is formed.

According to the present embodiment, a coloring agent for a color filter, a coloring composition, and a color filter using the same, wherein the coloring agent for the color filter is used in the quinophthalone compound represented by the above formula (1) When it is used as a coloring agent for color filters, it has high brightness and high contrast value, and is excellent in coloring power.

<Embodiment II>

Another object of the present invention is to provide a coloring composition for a color filter and a color filter using the coloring composition for the color filter, wherein the coloring composition for a color filter has excellent coloring power and dispersibility, and High brightness and high contrast values are obtained when used in color filters.

The present inventors have found that when a pigment containing a quinophthalone compound having a specific structure and an anthraquinone aluminum pigment are used as a coloring agent for a color filter, it can be produced in terms of dispersibility and coloring power, and is imparted thereto. This embodiment is completed with a high brightness and a contrast color filter.

That is, the present embodiment relates to a coloring composition for a color filter, characterized in that it contains a coloring agent, a binder resin, and an organic solvent, and the coloring agent contains the general formula (1A) and the general formula (1B). And one or more pigments selected from the quinoline yellow compounds represented by the formula (1C) and an anthraquinone aluminum pigment. Among them, the anthraquinone aluminum pigment is preferably one of the formula (8A) or the formula (8B). Meanwhile, the coloring composition for the color filter is preferably a photopolymerizable monomer and/or a photopolymerization initiator. Further, a color filter having a color filter segment formed of the coloring composition for the color filter described above may be provided on the substrate.

According to the present embodiment, it is possible to provide a coloring composition for a color filter and a color filter using the coloring composition for the color filter, wherein the coloring composition for the color filter is used in combination with the general formula (1A) and the general formula ( When one or more pigments selected from the group consisting of the quinoline yellow compounds represented by the formula (1C) and the anthraquinone aluminum pigment are used, high brightness and high contrast value are obtained, and the coloring power is excellent and the viscosity is low.

<Embodiment III>

An object of the present invention is to provide a coloring composition for a color filter excellent in dispersibility, fluidity, and storage stability, and a color filter using the composition.

In the present embodiment, a pigment dispersant composed of an ethylene polymer containing at least one of an ethylene oxide chain or a propylene oxide chain in a copolymerization composition is used for the quinophthalone pigment. The ethylenically unsaturated monomer (a1).

That is, the present embodiment relates to a coloring composition for a color filter, characterized by comprising a coloring agent, a pigment dispersing agent, and an organic solvent, wherein the coloring agent is a quinophthalone pigment; the pigment dispersing agent is made of An isocyanate group of a urethane prepolymer (E) having an isocyanate group at both ends thereof, which has a hydroxyl group of a hydroxyl group of an ethylene polymer (A) and an isocyanate group of a diisocyanate (B). a pigment dispersant obtained by reacting at least one of an amine compound containing at least a polyamine (C) and/or a secondary amine group, In the ethylene polymer (A), the copolymerizable composition contains an ethylenically unsaturated monomer (a1) having at least one of an ethylene oxide chain or a propylene oxide chain.

The total number of repeating units of the ethylene oxide chain and the propylene oxide chain of the ethylenically unsaturated monomer (a1) is preferably from 1 to 50. In particular, the content of the ethylenically unsaturated monomer (a1) is preferably from 10 to 90% by weight based on 100% by weight of the total copolymerization of the ethylene polymer (A). Meanwhile, the weight average molecular weight of the ethylene polymer (A) having two hydroxyl groups in the terminal portion of the single end is preferably from 500 to 20,000. The quinophthalone yellow pigment is preferably a quinophthalone compound containing C.I. Pigment Yellow No. 138 and/or Formula (1). Among them, the quinophthalone compound is preferably any of the formulae (1A) to (1C). Meanwhile, it may contain a photopolymerizable monomer and a photopolymerization initiator. Further, the color filter may be a color filter segment formed of the coloring composition for the color filter on the substrate.

According to this embodiment, it is possible to provide a coloring composition for a color filter, and a high contrast color filter using the composition, wherein the coloring composition is used in combination with a quinoline yellow pigment, and is composed of copolymerization. When a pigment dispersant comprising an ethylene polymer having at least one of an ethylene oxide chain or a propylene oxide chain is contained, it has high contrast and dispersion stability.

<Embodiment IV>

In order to solve the problem of the present invention, there is provided a coloring composition for a color filter, and a color filter using the same, wherein the coloring composition of the color filter is used in a color filter, brightness, contrast value, It has excellent coloring power and other characteristics (heat resistance, light resistance, sensitivity).

The present inventors have found that the coloring agent can solve the above problems by using a coloring composition for a color filter when a quinophthalone pigment [A] having a specific structure and a quinophthalone dye [B] having a specific structure are contained. This embodiment is completed.

That is, the present embodiment relates to a coloring composition for a color filter, which is characterized in that it contains a coloring agent, a binder resin, and a coloring composition for a color filter of an organic solvent; wherein the coloring agent contains the general formula (1A) One or more kinds of quinophthalone yellow pigments [A] selected from the formula (1B) and the formula (1 ° C), and the quinophthalone yellow dye [B] represented by the formula (6). In the general formulae (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 or a halogen atom. Meanwhile, it is preferred that at least one of R ¹ to R ⁶ in the formula (6) is -OR ⁷ . Further, a photopolymerizable monomer and/or a photopolymerization initiator may be further contained therein. At the same time, a color filter having a color filter segment formed of a coloring composition for a color filter on a substrate may be used.

By using the coloring composition for a color filter of the present embodiment, it is possible to provide a color filter which is excellent in brightness, contrast value, and coloring power, and which is excellent in heat resistance and light resistance.

<Embodiment V>

The object of the present embodiment is to provide a coloring matter (brightness) which is excellent in color properties (brightness), and which satisfies other physical properties (heat resistance, light resistance, solvent resistance), a coloring composition for blending the same, and color characteristics (brightness) ) Excellent color filter.

The present inventors have found a quinophthalone yellow pigment having excellent color characteristics (brightness), and have completed the present embodiment based on this knowledge.

That is, this embodiment relates to a quinoline yellow pigment, the characteristics of which are The formula (6) is shown. In particular, the coloring agent may be a coloring composition for a color filter containing the above-mentioned quinophthalone yellow pigment in at least a coloring composition for a color filter composed of a coloring agent and a binder resin. At the same time, the colorant may further contain a pigment. Further, in at least one of the color filters including the red color filter segment, the green color filter segment, and the blue color filter segment, at least one of the color filter segments is formed by the coloring composition for the color filter. Color.

In the present embodiment, quinoline yellow pigment which is excellent in color characteristics (brightness) and which satisfies other physical properties (heat resistance, light resistance, and solvent resistance) can be obtained. At the same time, the coloring composition for the color filter of the quinoline yellow pigment can be prepared to form a color filter, and a color filter excellent in color characteristics (brightness) can be formed. Among them, the formed color filter is also excellent in other physical properties (heat resistance, light resistance, and solvent resistance).

<Embodiment VI>

The object of the present invention is to provide a green coloring composition for a color filter which is excellent in brightness, heat resistance, light resistance, and voltage holding ratio, and a color filter using the same.

The present inventors have found that the green coloring composition for a color filter containing a specific structure of an anthraquinone dye and a quinoline yellow pigment having a specific structure can solve the above problems, and the present embodiment is completed.

In other words, the present embodiment relates to a green coloring composition for a color filter, which comprises a coloring agent, a binder resin, and an organic solvent, and the coloring agent contains indigo represented by the following formula (8C). A plain pigment and a quinoline yellow pigment represented by the formula (6).

[In the general formula (8C), A ¹ to A ¹⁶ each independently represent a hydrogen atom, a halogen atom, a nitro group, an alkyl group which may have a substituent, or an 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. . Wherein R ³ is an alkyl group which may have a substituent or an aryl group which may have a substituent. ]

Meanwhile, in the general formula (8C), at least one of R ¹ and R ² is preferably an aryl group which may have a substituent or -OR ³ . Further, the color filter may be a green coloring composition, and may further contain a photopolymerizable monomer and/or a photopolymerization initiator. At the same time, a color filter having a color filter segment formed of the green coloring composition for the color filter described above may be used as the substrate. Further, the general formula (8C) and the general formula (8A) have the same structure although the substituents are represented by different methods.

According to the green colored composition for a color filter of the present embodiment, a color filter excellent in brightness, heat resistance, light resistance, and voltage holding ratio can be provided.

<Embodiment VII>

In order to solve the problem of the present embodiment, a coloring composition for a color filter having excellent contrast values and coloring power, and a color filter using the composition are also provided.

The present inventors have found that the coloring composition for a color filter can solve the above problems when the quinophthalone yellow pigment [A1] having a specific structure and the quinoline yellow pigment [A2] having a specific structure are contained, and the present embodiment is completed.

In other words, the coloring composition for a color filter is characterized in that the coloring agent for a color filter containing a coloring agent, a binder resin, and an organic solvent contains the general formula (6). The quinoline yellow pigment [A1] shown and the quinoline yellow pigment [A2] represented by the following formula (7).

Wherein, in the 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 -OR ₁₁ . Wherein R ₁₁ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group. Further, R ₇ to R ₁₀ 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, a carboxyl group, a substituted or unsubstituted sulfonate. Amidino, substituted or unsubstituted heterocyclic residue, -SR ₁₂ , -OR ₁₂ , or -COO-R ₁₂ . Wherein R ₁₂ represents 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 a color filter of the present embodiment, it is possible to provide A color filter with excellent contrast value and tinting strength.

<Embodiment VIII>

The object of the present embodiment is to provide a coloring matter excellent in color characteristics (brightness), a coloring composition comprising the coloring matter, and a color filter excellent in color characteristics (brightness) using the coloring composition.

The present inventors have found a quinophthalone yellow pigment having excellent color characteristics (brightness), and have completed the present embodiment from this knowledge.

That is, this embodiment relates to a quinophthalone yellow pigment for a color filter, which is characterized by the following formula (7A).

Wherein, in the 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 -OR ₁₁ . Wherein R ₁₁ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group. Further, R ₇ to R ₁₀ 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, a carboxyl group, a substituted or unsubstituted sulfonate. Amidino, substituted or unsubstituted heterocyclic residue, -SR ₁₂ , -OR ₁₂ , or -COO-R ₁₂ . Wherein R ₁₂ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group. However, at least one of R ₇ to R ₁₀ is -OR ₁₂ .

The quinophthalone yellow pigment is preferably a compound represented by the following formula (7B).

In the formula (7B), R ₁₃ represents a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. Wherein 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 -OR ₁₈ . Wherein R ₁₈ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group. However, at least one of R ₁₄ to R ₁₇ is -OR ₁₈ .

Meanwhile, in the coloring composition for a color filter composed of a coloring agent and a binder resin, the coloring agent preferably contains the above quinophthalone yellow pigment. At the same time, the colorant may further contain a pigment. Further, in at least one of the color filters including the red color filter segment, the green color filter segment, and the blue color filter segment, at least one of the color filter segments is formed by the coloring composition for the color filter. Color.

In the present embodiment, quinophthalone yellow pigment for color filters excellent in color characteristics (brightness) can be obtained. At the same time, it is also possible to prepare a color filter having a coloring composition for the color filter of the quinoline yellow pigment to form a color filter having excellent color characteristics (brightness). Among them, the other physical properties (heat resistance, light resistance, and solvent resistance) of the formed color filter are also good.

The subject matter of the present invention is filed according to Japanese Patent Application No. 2011-60734 filed on March 18, 2011, and April 19, 2011. Japanese Patent Patent No. 2011-093515, Japanese Patent Application No. 2011-93705, filed on April 20, 2011, Japanese Patent Application No. 2011-118726, June 2011, June 2011 Japanese Patent Application No. 2011-143658, filed on the 29th, Japanese Patent Application No. 2011-150514, filed on July 7, 2011, and Japanese Patent Application No. 2011-156970, filed on July 15, 2011, Japanese Patent Application No. 2011-174656, filed on August 10, 2011, Japanese Patent Application No. 2011-181111, filed on August 23, 2011, and Japanese Patent Application 2011, filed on December 27, 2011 The descriptions of the No. 286172 are incorporated herein by reference in their entirety.

<colorant>

In the embodiment of the invention of the present application, the coloring composition for a color filter includes a quinophthalone compound represented by the formula (1), a quinoline yellow pigment represented by the formula (6), and a formula ( 7) Separate or a combination of selected coloring agents among the quinophthalone yellow pigments shown. Meanwhile, the coloring composition for the color filter may further contain an anthraquinone pigment represented by the formula (8A) or (8B), or another coloring agent. Each coloring agent will be described below.

(Quinoline yellow compound represented by the formula (1))

Hereinafter, it may also be referred to as a quinophthalone yellow pigment represented by the formula (1).

R ¹ to R ¹³ , R ¹⁴ to R ²⁸ , R ²⁹ to R ⁴³ and R ⁴⁴ to R ⁶⁰ of the formula (1) and the formulae (1A) to (1C), wherein the halogen atom is exemplified by: Fluorine, chlorine, bromine, iodine.

Further, the alkyl group which may have a substituent may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a neopentyl group, a n-hexyl group or a n-octyl group. a straight or branched alkyl group such as a stearyl group or a 2-ethylhexylhexyl group, and the others include: trichloromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, 2, 2-dibromoethyl, 2,2,3,3-tetrafluoropropyl, 2-ethoxyethyl, 2-butoxyethyl, 2-nitropropyl, benzyl, 4-methylbenzoate An alkyl group having a substituent such as 4-tert-butylbenzyl, 4-methoxybenzyl, 4-nitrobenzyl, 2,4-dichlorobenzyl or the like.

Further, the alkoxy group which may have a substituent may, for example, be a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group or a third butoxy group. a linear or branched alkoxy group such as neopentyloxy, 2,3-dimethyl-3-pentyloxy, n-hexyloxy, n-octyloxy, stearyloxy, 2-ethylhexyloxy, or the like, Others include: trichloromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 2,2,3,3-tetrafluoropropoxy, 2,2-di-trifluoro An alkoxy group having a substituent such as a methylpropoxy group, a 2-ethoxyethoxy group, a 2-butoxyethoxy group, a 2-nitropropoxy group or a benzyloxy group.

Further, the aryl group which may have a substituent may, for example, be an aryl group such as a phenyl group, a naphthyl group or a fluorenyl group, and the others include: p-tolyl group, p-bromophenyl group, p-nitrophenyl group, p-methoxybenzene. Base, 2,4-dichlorophenyl, pentafluorophenyl, 2-aminophenyl, 2-methyl-4-chlorophenyl, 4-hydroxy-1-naphthyl, 6-methyl-2-naphthalene An aryl group having a substituent of 4,5,8-trichloro-2-naphthyl, anthracenyl, 2-aminoindenyl or the like.

Further, examples of the acid group include -SO ₃ H and -COOH, and a monovalent to trivalent metal salt of the acid group, and examples thereof include a sodium salt, a potassium salt, a magnesium salt, a calcium salt, and iron. Salt, aluminum salt, etc. Further, the alkylammonium salt of the acid group may, for example, be an ammonium salt of a long-chain monoalkylamine such as octylamine, laurylamine or stearylamine, palm trimethylammonium, dilaurin, or bis-dimethyl methacrylate. a quaternary alkyl ammonium salt such as an ammonium salt.

a substituent which may have a substituent of an imine methyl group (C ₆ H ₄ (CO) ₂ N-CH ₂ -) and a substituted amine sulfonyl group (H ₂ NSO ₂ -) Examples thereof include the above-mentioned halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, and the like.

a group of at least one adjacent one of R ¹ to R ⁴ of the formula (1), and/or a group of at least one adjacent one of R ¹⁰ to R ¹³ are bonded together to form a The aromatic ring of the substituent. Examples of the aromatic ring include a hydrocarbon aromatic ring and a heteroaryl ring, and examples of the hydrocarbon aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and the like; and, among them, a heteroaromatic ring, for example, :pyridine ring, pyridyl Ring, pyrrole ring, quinoline ring, quin a porphyrin ring, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, An azole ring, a thiazole ring, an imidazole ring, a pyrazole ring, an anthracene ring, an indazole ring, and the like.

The quinophthalone compound used in the colorant for color filters is preferably any of the formulae (1A) to (1C). Wherein R ¹⁴ to R ²⁸ , R ²⁹ to R ⁴³ , and R ⁴⁴ to R ⁶⁰ are a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and a aryl group which may have a substituent a group of -SO ₃ H; -COOH; and a monovalent to trivalent metal salt, an alkanolammonium salt, a sulfhydryl methyl group which may have a substituent, or an amine sulfonamide which may have a substituent The base is synonymous with the group described in the formula (1).

Further, the quinophthalone compound used in the colorant for color filters, in the formulas (1A) to (1C), R ¹⁴ to R ²⁸ , R ²⁹ to R ⁴³ , R ⁴⁴ to R ⁶⁰ , wherein a hydrogen atom Or a halogen atom is preferred from the viewpoint of low viscosity of the dispersion.

Specific examples of the quinophthalone compound to be used in the coloring agent for a color filter include, but are not limited to, the quinoline yellow compounds (a) to (r) shown below.

(Method for producing quinoline yellow compound represented by general formula (1))

The quinophthalone compound is produced by the method described in Japanese Patent Publication No. 2930774. Hereinafter, a general production method of the quinophthalone compound represented by the formula (1) will be described. It is an equivalent of one equivalent of 8-aminomethylquinoline represented by the following formula (2), and 2 to 3 equivalents of phthalic anhydride represented by the following formula (3) in benzoic acid and a nitrogen atmosphere. Next, the condensation reaction is carried out by heating at 160 to 200 °C. In the reaction, before the reaction mixture reaches 160 to 200 ° C, it may be maintained at 140 to 160 ° C for 1 to 3 hours, and in a 2-stage step, a condensation reaction of phthalic anhydride is carried out.

[wherein, R ⁶¹ to R ^{65 are} synonymous with R ⁵ to R ⁹ in the formula (1). ]

[wherein, R ⁶⁶ to R ^{69 are} synonymous with R ¹ to R ⁴ and R ¹⁰ to R ¹³ in the formula (1). ]

In the reaction, 1 to 2 equivalents of the phthalic anhydride represented by the formula (3) are added with respect to 1 equivalent of the 8-aminomethylquinoline represented by the formula (2), and the mixture is heated and stirred at 140 to 160 ° C. After 3 hours, add 1 to 2 equivalents of the phthalic anhydride represented by the general formula (3) and heat at 160 ° C to 200 ° C to cause a condensation reaction, which can be carried out in 8-aminomethylquinoline. The amine side and the methyl side condense the different structures of phthalic anhydride.

At the same time, two or more structurally different quinophthalone compounds can be simultaneously synthesized by reacting two or more different structures of phthalic anhydride with respect to 8-aminomethylquinoline (hereinafter, referred to as "co-synthesis method" "). For example, when a condensation reaction is carried out with 1.8 equivalents of tetrachlorophthalic anhydride and 1.2 equivalents of other phthalic anhydride with respect to 1 equivalent of 8-aminomethylquinoline, CI Pigment Yellow No. 138 and a specific quinoline yellow can be simultaneously produced. Compound.

Meanwhile, the compound of the formula (5) can be synthesized from the quinophthalone compound represented by the compound (1) by the synthesis method described in Patent Document 3. Further, the phthalic anhydride represented by the formula (5) and the formula (3) can be subjected to a condensation reaction in benzoic acid at 160 to 200 ° C to synthesize the quinophthalone compound represented by the formula (1). However, the method for producing the quinoline yellow compound is not limited to these methods.

[wherein R ⁷⁰ to R ^{78 are} synonymous with R ⁵ to R ¹³ in the formula (1). ]

The coloring agent of this embodiment may contain two or more kinds of quinoline yellow compounds. In this case, the quinoline yellow compounds produced separately may be mixed, or two or more kinds of quinoline yellow compounds may be simultaneously produced by a co-synthesis method and used as a coloring agent.

When these quinoline yellow compounds produced separately are used, they may be simply mixed before the two kinds of pigments are dispersed, or may be pulverized and mixed by a salt milling treatment to be described later.

In particular, when the coloring agent contained therein is C.I. Pigment Yellow No. 138, it is preferably used after being pulverized and mixed by a co-synthesis method or a salt milling treatment. When the CI Pigment Yellow No. 138 having a quinoline yellow skeleton and the quinophthalone compound represented by the formula (1) are pulverized and mixed together, the obtained particles are finer than the respective salt-grinding treatments, and the comparative values are obtained. high.

The coloring composition containing the quinophthalone compound represented by the formula (1) has a hue itself which is yellow, and when other coloring agents are used in combination, it can be used as a yellow color filter segment of the same color or can be formed again. The color component of the green color filter segment and the red color filter segment. In the coloring composition of the present embodiment, when a green coloring agent and/or a blue coloring agent are used in combination, A colored composition for a green filter segment having high brightness and high contrast can be obtained.

(Quinoline yellow pigment represented by the formula (6))

The quinoline yellow pigment represented by the formula (6) is also referred to as "quinoline yellow dye" represented by the formula (6) in the present specification.

The substituted or unsubstituted alkyl group in R ₁ to R ₇ in the formula (6) may, for example, be a linear, branched, monocyclic or condensed polycyclic alkyl group having a carbon number of 1 to 30, or a carbon number of A linear, branched, monocyclic or condensed polycyclic alkyl group having from 2 to 30 and containing one or more ester bonds (-COO-) and/or ether bonds (-O-). Specific examples of the linear, branched, monocyclic or condensed polycycloalkyl group having 1 to 30 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and octyl groups. , mercapto, decyl, dodecyl, octadecyl, trifluoromethyl, isopropyl, isobutyl, isopentyl, 2-ethylhexylhexyl, second butyl, third Butyl, second pentyl, third pentyl, third octyl, neopentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, boronic acid Group), 4-fluorenylcyclohexyl, etc., but is not limited thereto.

Specific examples of the linear or branched alkyl group having 2 or more carbon atoms and having one or more ester bonds include, for example, -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 or the like, but is not limited thereto.

Further, specific examples of the linear or branched alkyl group having one or more ether bonds having 2 to 30 carbon atoms include, for example, -CH ₂ -O-CH ₃ and -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 (wherein m is 1 to 5), -CH ₂ -CH(CH ₃ )-O-CH ₂ -CH ₃ , -CH ₂ -CH-(OCH _{3 2,} etc., but is not limited to this.

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

Further, specific examples of the linear or branched alkyl group having one or more ester bonds (-COO-) and an ether bond (-O-) having 3 to 30 carbon atoms include, for example, -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 ₂ -CH ₂ -CH ₂ -CH ₃ , but is not limited thereto.

The substituted or unsubstituted alkenyl group in R ₁ to R ₇ may, for example, be a linear, branched, monocyclic or condensed polycyclic alkenyl group having 1 to 18 carbon atoms. The structure may also contain a plurality of carbon-carbon double bonds. Specific examples thereof include a vinyl group, a 1-propenyl group, an allyl group, a 2-butenyl group, a 3-butenyl group, an isopropenyl group, an isobutenyl group, a 1-pentenyl group, and a 2-pentenyl group. , 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, cyclopentenyl, cyclohexyl Alkenyl, 1,3-butadienyl, cyclohexadienyl, cyclopentadienyl, etc., but are not limited thereto.

The substituted or unsubstituted aryl group in R ₁ to R ₇ may, for example, be a monocyclic or condensed polycyclic aryl group having a carbon number of 6 to 18 substituted or unsubstituted, and examples thereof include a phenyl group, and 1 -naphthyl, 2-naphthyl, p-biphenyl, m-phenyl, 2-indenyl, 9-fluorenyl, 2-phenanthryl, 3-phenanthryl, 9-phenanthryl, 2-indenyl, 3- Indenyl, 9-fluorenyl, 1-indenyl, 2-indenyl, 3-indenyl, o-tolyl, m-tolyl, p-tolyl, 4-methylbiphenyl, triphenyl, 4- Methyl-1-naphthyl, 4-tert-butyl-1-naphthyl, 4-naphthyl-1-naphthyl, 6-phenyl-2-naphthyl, 10-phenyl-9-fluorenyl, A sulfonyl group, a 4-m-butylene diimide phenyl group, a 2-benzocyclobutenyl group or the like.

When at least one of R ₁ to R ₆ in the formula (6) is -OR ₇ , it is preferable from the viewpoint of brightness, heat resistance, and light resistance.

The quinophthalone yellow pigment represented by the formula (6) can be obtained by reacting the corresponding 2-methylquinoline with naphthalene dicarboxylic anhydride in benzoic acid at a high temperature as shown in the following reaction formula.

Further, the quinoline yellow pigment represented by the formula (6) also has tautomers of a structure such as the formula (6a) and the formula (6b), and such tautomers are within the scope of the invention.

Specific examples of the quinophthalone yellow pigment represented by the formula (6) include the following dyes, but the dye of the present invention is not limited thereto.

The quinophthalone yellow pigment represented by the formula (6) can also be used as a coloring material in the coloring of printing inks, IJ inks, plastics, paints, fibers, stationery, pens, cosmetics, and the like.

(Quinoline yellow pigment represented by the formula (7))

The halogen atom in R ₁ to R ₁₀ in the formula (7) and the formula (7A) may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, but is not limited thereto.

Examples of the substituted or unsubstituted alkyl group in R ₁ to R ₁₂ may, for example, be a linear, branched, monocyclic or condensed polycycloalkyl group having a carbon number of 1 to 30; or a carbon number of 2 to 30 and at least a linear, branched, monocyclic or condensed polycycloalkyl group containing at least one of a bond selected from an ester bond (-COO-), an ether bond (-O-), or a sulfur bond (-S-) . Specific examples of the linear, branched, monocyclic or condensed polycycloalkyl group having 1 to 30 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and octyl groups. , mercapto, decyl, dodecyl, octadecyl, trifluoromethyl, isopropyl, isobutyl, isopentyl, 2-ethylhexylhexyl, 2-hexyldodecyl , second butyl, tert-butyl, second pentyl, third pentyl, third octyl, neopentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, descending A mercapto group, a boronic acid group, a 4-fluorenylcyclohexyl group, etc. are not limited to this.

Specific examples of the linear or branched chain having 2 to 30 carbon atoms include, for example, -CH ₂ -CH ₂ -CH ₂ -COO-CH ₂ -CH ₃ and -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 (wherein n is 1 to 8), -(CH ₂ -CH ₂ -CH ₂ -O) _m -CH ₃ (where m is 1 to 5), -CH ₂ -CH(CH ₃ )-O-CH ₂ -CH ₃ -, -CH ₂ -CH-(OCH ₃ ) ₂ -CH ₂ -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 -CH ₃ , However, it is not limited to this.

The carbon number is 2 to 30, and depending on the case, at least one of at least one selected from the group consisting of an ester bond (-COO-), an ether bond (-O-), and a sulfur bond (-S-) is bonded. Specific examples of the monocyclic or condensed polycycloalkyl group include the following examples, but are not limited thereto.

The substituted or unsubstituted alkenyl group in R ₁ to R ₁₂ may, for example, be a linear, branched, monocyclic or condensed polycyclic alkenyl group having 1 to 18 carbon atoms. These structures may contain a plurality of carbon-carbon double bonds. Specific examples thereof include a vinyl group, a 1-propenyl group, an allyl group, a 2-butenyl group, a 3-butenyl group, an isopropenyl group, an isobutenyl group, a 1-pentenyl group, and a 2-pentenyl group. , 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, cyclopentenyl, cyclohexyl Alkenyl, 1,3-butadienyl, cyclohexadienyl, cyclopentadienyl, etc., but are not limited thereto.

The substituted or unsubstituted aryl group in R ₁ to R ₁₂ may, for example, be a monocyclic or condensed polycyclic aryl group which may have a carbon atom number of 6 to 30, which may be substituted or unsubstituted, and may contain a hetero atom. :phenyl, 1-naphthyl, 2-naphthyl, p-biphenyl, m-phenyl, 2-indenyl, 9-fluorenyl, 2-phenanthryl, 3-phenanthryl, 9-phenanthryl, 2- Indenyl, 3-indenyl, 9-fluorenyl, 1-indenyl, 2-indenyl, 3-indenyl, triphenylene, thienyl, benzothienyl, naphthylthio, furyl, piperazine A pyrrolyl group, an imidazolyl group, a pyridyl group, a decyl group, a thiazolyl group or the like.

Further, the substituted or unsubstituted alkyl group in R ₁ to R ₁₂ and the hydrogen atom of the substituted or unsubstituted aryl group may be further substituted with other substituents.

Such a substituent may, for example, be a halogen atom, a substituted or unsubstituted alkane A, substituted or unsubstituted aryl, nitro, hydroxy, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy.

The halogen atom, the substituted or unsubstituted alkyl group, and the substituted or unsubstituted aryl group are synonymous with the halogen atom in R ₁ to R ₁₂ , a substituted or unsubstituted alkyl group, and a substituted or unsubstituted aryl group. .

Meanwhile, in the case of the substituted or unsubstituted alkoxy group, the substituted or unsubstituted alkyl group in R ₁ to R ₁₂ is bonded to the oxygen atom.

Further, in the case of the substituted or unsubstituted aryloxy group, the substituted or unsubstituted aryl group in R ₁ to R ₁₂ is bonded to the oxygen atom.

Among the quinophthalone yellow pigments used in the color filter represented by the general formula (7A), in particular, the quinophthalone yellow pigment used in the color filter represented by the general formula (7B) is preferred.

a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, and a substituted or unsubstituted aryl group, and a group of R ₁ to R ₁₂ in R ₁₃ to R ₁₈ in the formula (7B); A halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, and a substituted or unsubstituted aryl group are synonymous.

The quinophthalone yellow pigment for the color filter represented by the formula (7) can be obtained by reacting the corresponding 2-methylquinoline with the corresponding phthalic anhydride in benzoic acid at a high temperature as shown in the following reaction formula.

Further, the quinoline yellow pigment represented by the formula (7) also has tautomers having the structures of the following formula (7a) and formula (7b), and the tautomers are Within the scope of the invention.

Specific examples of the quinophthalone yellow pigment represented by the formula (7A) include the following dyes, but the dye of the present invention is not limited thereto.

(Anthraquinone pigments represented by the general formulae (8A) and (8B))

The anthraquinone aluminum pigment used in the present embodiment is not particularly limited as long as it has a structure in which the center of the anthracycline ring is trivalent aluminum. Among the anthraquinone aluminum pigments, it is known that aluminum is trivalent and may be bonded to anthocyanin in addition to other bonds. Therefore, the monomer may have a structure of a dimer or a trimer. At the same time, it is known that the anthracycline ring can be chemically modified, and thus various structures can be obtained. The anthraquinone aluminum pigment in the present embodiment may be any form other than a monomer, a structure of another dimer or a trimer, or a chemically modified anthracycline ring.

Among them, the anthraquinone aluminum pigment is preferably a structure represented by the formula (8A) or the formula (8B) in terms of color characteristics and dispersibility.

In the general formula (8A), X ₁ to X ₄ may be the same or different, and specific examples thereof include an alkyl group which may have a substituent, an aryl group which may have a substituent, and a cycloalkyl group which may have a substituent A heterocyclic group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, and an arylthio group which may have a substituent. When the above-mentioned X ₁ to X ₄ has a substituent, the substituents thereof may be the same or different, and specific examples thereof include a halogen group such as fluorine, chlorine or bromine, an amine group, a hydroxyl group, a nitro group and the like. Other, such as alkyl, aryl, cycloalkyl, alkoxy, aryloxy, alkylthio, arylthio and the like. Further, these substituents may be plural.

Examples of the "alkyl group" in 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, and a linear or branched alkyl group such as an octyl group, a stearyl group or a 2-ethylhexylhexyl group; and a "alkyl group which may have a substituent" may, for example, be a trichloromethyl group, a trifluoromethyl group or a 2,2 , 2-trifluoroethyl, 2,2-dibromoethyl, 2,2,3,3-tetrafluoropropyl, 2-ethoxyethyl, 2-butoxyethyl, 2-nitropropyl, Benzyl, 4-methylbenzyl, 4-t-butylbenzyl, 4-methoxybenzyl, 4-nitrobenzyl, 2,4-dichlorobenzyl, and the like.

Examples of the "aryl group" in the aryl group which may have a substituent include a phenyl group, a naphthyl group, an anthracenyl group and the like; and the "aryl group which may have a substituent" may, for example, be a p-tolyl group or a p-bromophenyl group. Nitphenyl, p-methoxyphenyl, 2,4-dichlorophenyl, pentafluorophenyl, 2-aminophenyl, 2-methyl-4-chlorophenyl, 4-hydroxy-1-naphthyl, 6-Methyl-2-naphthyl, 4,5,8-trichloro-2-naphthyl, anthracenyl, 2-aminoindenyl, and the like.

The "cycloalkyl group" in the cycloalkyl group which may have a substituent may, for example, be a cyclopentyl group, a cyclohexyl group or an adamantyl group; and the "cycloalkyl group having a substituent" may be exemplified Such as: 2,5-dimethylcyclopentyl, 4-tert-butylcyclohexyl and the like.

The "heterocyclic group" in the heterocyclic group which may have a substituent may, for example, be a pyridyl group or a pyridyl group. a group, an N-hexahydropyridyl group, a piperidyl group, an N-norfosino group, an acridinyl group, etc.; a "heterocyclic group which may have a substituent" may, for example, be a 3-methylpyridyl group or a N group. -methylhexahydropyridyl, N-methylpyrrolyl and the like.

The "alkoxy group" in the alkoxy group which may have a substituent may, for example, be a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group or a third butoxy group. Linear or branched alkoxy groups such as benzyl, neopentyloxy, 2,3-dimethyl-3-pentyloxy, n-hexyloxy, n-octyloxy, stearyloxy, 2-ethylhexyloxy, etc. Base: "alkoxy group which may have a substituent" may, for example, be trichloromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 2,2,3,3-tetrafluoro Propyloxy, 2,2-di-trifluoromethylpropoxy, 2-ethoxyethoxy, 2-butoxyethoxy, 2-nitropropoxy, benzyloxy and the like.

Examples of the "aryloxy group" in the aryloxy group which may have a substituent include a phenoxy group, a naphthyloxy group, a decyloxy group and the like: "the aryloxy group which may have a substituent" may, for example, be a p-methylbenzene group. Oxyl, p-nitrophenoxy, p-methoxyphenoxy, 2,4-dichlorophenoxy, pentafluorophenoxy, 2-methyl-4-chlorophenoxy and the like.

The "alkylthio group" in the alkylthio group which may have a substituent may, for example, be a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group, an octylthio group or a thiol group. , dodecylthio group, octadecylthio group, etc.: "alkylthio group which may have a substituent" may, for example, be a methoxyethylthio group, an amine ethylthio group, a benzylaminoethylthio group or a methyl carbonyl group. Aminoethylthio group, phenylcarbonylaminoethylthio group and the like.

Examples of the "arylthio group" in the arylthio group which may have a substituent include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, a 9-fluorenylthio group and the like: Examples of the sulfur group include a chlorophenylthio group, a trifluorotolylthio group, a cyanophenylthio group, a nifedipine group, a 2-aminophenylthio group, a 2-hydroxyphenylthio group, and the like.

Next, specific examples of Y ₁ to Y ₄ include a halogen atom, a nitro group, a sulfhydryl methyl group (C ₆ H ₄ (CO) ₂ N-CH ₂ -) which may have a substituent, and an amine sulfonate. Mercapto group (H ₂ NSO ₂ -). Wherein, the imine methyl group which may have a substituent is a structure in which a hydrogen atom in the quinone imine methyl group is substituted with a substituent; and an amine sulfonyl group which may have a substituent represents an amine sulfonyl group The hydrogen atom in the structure is a structure substituted by a substituent. The Y is preferably a halogen atom or an amine sulfonate group. Anthraquinone compounds in which m ₁ to m ₄ are 0 (i.e., without Y ₁ to Y ₄ ) are also suitable. Examples of the halogen atom include fluorine, chlorine, bromine, and iodine. The "substituent" in the imine methyl group which may have a substituent and the amine sulfonyl group which may have a substituent is synonymous with the substituent in X ₁ to X ₄ .

Z represents a hydroxyl group, a chlorine atom, -OP(=O)R ₁ R ₂ , or -O-Si R ₃ R ₄ R ₅ ; wherein R ₁ and R ₂ each represent a hydrogen atom, a hydroxyl group, and may have a substituent. An alkyl group, a aryl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, and R ₁ and R ₂ may be bonded to each other to form a ring.

Wherein the alkyl group in R ₁ and R ₂ may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a neopentyl group, a n-hexyl group or a n-octyl group. a straight-chain or branched alkyl group such as a stearyl group or a 2-ethylhexylhexyl group; and a substituent in the case where the alkyl group is an alkyl group having a substituent, and examples thereof include a halogen atom such as chlorine, fluorine or bromine. An alkoxy group such as a methoxy group, an aryl group such as a phenyl group or a tolyl group, or a nitro group. Further, the substituents therein may be plural. The alkyl group having a substituent may, for example, be trichloromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, 2,2-dibromoethyl, 2-ethoxyethyl, 2- Butoxyethyl, 2-nitropropyl, benzyl, 4-methylbenzyl, 4-tert-butylbenzyl, 4-methoxybenzyl, 4-nitrobenzyl, 2 , 4-dichlorobenzyl and the like.

Examples of the aryl group in R ₁ and R ₂ include a phenyl group, a naphthyl group, an anthracenyl group and the like; and a substituent group in the case where the aryl group has a substituent, and examples thereof include a fluorine atom such as chlorine, fluorine or bromine, and an alkyl group. , alkoxy, amine, nitro, and the like. Further, the substituents therein may be plural. Examples of the aryl group having a substituent include p-tolyl, p-bromophenyl, p-nitrophenyl, p-methoxyphenyl, 2,4-dichlorophenyl, pentafluorophenyl, and 2-dimethylaminobenzene. , 2-methyl-4-chlorophenyl, 4-methoxy-1-naphthyl, 6-methyl-2-naphthyl, 4,5,8-trichloro-2-naphthyl, anthracene Base.

Examples of the alkoxy group in R ₁ and R ₂ include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, a third butoxy group, and a neopentyl group. a linear or branched alkoxy group such as an oxy group, a 2,3-dimethyl-3-pentyloxy group, a n-hexyloxy group, a n-octyloxy group, a stearoxy group or a 2-ethylhexyloxy group: Examples of the substituent of the alkoxy group of the substituent include a halogen atom such as chlorine, fluorine or bromine; an aryl group such as an alkoxy group, a phenyl group or a tolyl group; and a nitro group. Further, the substituents therein may be plural. Examples of the alkoxy group which may have a substituent include trichloromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 2,2,3,3-tetrafluoropropoxy. 2,2-Di-trifluoromethylpropoxy, 2-ethoxyethoxy, 2-butoxyethoxy, 2-nitropropoxy, benzyloxy and the like.

Examples of the aryloxy group in R ₁ and R ₂ include a phenoxy group, a naphthyloxy group, a decyloxy group and the like; and a substituent of the aryloxy group in the case of having a substituent, for example, chlorine, fluorine, bromine, or the like a halogen atom, an alkyl group, an alkoxy group, an amine group, a nitro group or the like. Further, the substituents therein may be plural. Examples of the aryloxy group having a substituent include p-tolyloxy, p-nitrophenoxy, p-methoxyphenoxy, 2,4-dichlorophenoxy, pentafluorophenoxy, and 2-methyl. -4-Chlorophenoxy and the like.

The anthraquinone aluminum pigment represented by the formula (8A) is an optionally substituted aryl group or a aryl group which may have a substituent, from the viewpoint of dispersibility and color characteristics, and at least one of R ₁ and R ₂ . It is better. Among them, R ₁ and R ₂ are each an aryl group or an aryloxy group. Among them, R ₁ and R ₂ are each a phenyl group or a phenoxy group.

In the formula (8A), R ₃ , R ₄ and R ₅ each independently represent an alkyl group having 1 to 18 carbon atoms or an aryl group having 4 or less rings. When it is within the above range, the light absorption coefficient per unit weight is sufficient, so that the pigment concentration in the colored composition can be made to an appropriate range.

The alkyl group in R ₃ , R ₄ and R ₅ may be a straight chain or another branch or a ring, and may have a functional group when the total number of hetero atoms is in the range of 3 or less. Examples thereof include methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, octadecyl group, isopropyl group, isobutyl group, second butyl group, and the like. Tributyl, 1-ethylpentyl, cyclopentyl, cyclohexyl, trifluoromethyl, 2-ethylhexylethylhexyl, benzamidine methyl, 1-naphthoquinonemethyl, 2-naphthyl醯Methyl, 4-methylsulfanyl benzamidine methyl, 4-phenylsulfanyl benzhydrylmethyl, 4-dimethylaminobenzimidylmethyl, 4-cyanobenzoic acid Methyl, 4-methylbenzimidylmethyl, 2-methylbenzimidylmethyl, 3-fluorobenzhydrylmethyl, 3-trifluoromethylbenzimidylmethyl, and 3-nitrobenzene Hyperthyroidism and so on.

The aryl group in R ₃ , R ₄ and R ₅ may contain a hetero atom in the aromatic ring, and the number of hetero atoms contained in each aromatic ring may be in the range of 2 or less, and may contain a functional group. Examples thereof include a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-fluorenyl group, a 9-phenanthryl group, a 1-fluorenyl group, a 5-fused tetraphenyl group, and a 1-fluorenyl group. 2-indenyl, 9-fluorenyl, triphenyl, tetraphenyl, o-, m-, and p-tolyl, xylyl, o-, m-, and p-cumyl, Mesityl, cyclopentadienyl, binaphthyl, exemplified trinaphthyl, biphenyl, heptene, heptylphenyl, dicyclopentadienyl , propylene (di) fluorenyl, fluorenyl, decyl, fluorenyl, fluorenyl, fluorenyl, fluorenyl, hydrazino, hydrazino, anthraquinonyl , phenanthryl, co-triphenyl, anthracenyl, fluorenyl, fused tetraphenyl, pleiadenyl, fluorenyl, fluorenyl, tetraphenyl, and fluorenyl.

4. The anthraquinone compound represented by the formula (8A) is composed of heat resistance. From the viewpoint of light resistance, Z is preferably -OP(=O)R ₁ R ₂ .

In the general formula (8B), X ₅ to X ₁₂ may be the same or different, and specific examples thereof include an alkyl group which may have a substituent, an aryl group which may have a substituent, and a cycloalkyl group which may have a substituent. a heterocyclic group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, and an arylthio group which may have a substituent. When the above-mentioned X ₅ to X ₁₂ has a substituent, the substituents may be the same or different, and specific examples thereof include a halogen group such as fluorine, chlorine or bromine, and a characteristic group such as an amine group, a hydroxyl group or a nitro group. Others such as alkyl, aryl, cycloalkyl, alkoxy, aryloxy, alkylthio, arylthio and the like. Further, these substituents may be plural.

Examples of the "alkyl group" in 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, and a linear or branched alkyl group such as an octyl group, a stearyl group or a 2-ethylhexylhexyl group; and a "alkyl group which may have a substituent" may, for example, be a trichloromethyl group, a trifluoromethyl group or a 2,2 , 2-trifluoroethyl, 2,2-dibromoethyl, 2,2,3,3-tetrafluoropropyl, 2-ethoxyethyl, 2-butoxyethyl, 2-nitropropyl, Benzyl, 4- Methylbenzyl, 4-tert-butylbenzyl, 4-methoxybenzyl, 4-nitrobenzyl, 2,4-dichlorobenzyl, and the like.

Examples of the "aryl group" of the aryl group which may have a substituent include a phenyl group, a naphthyl group, a fluorenyl group, and the like, and examples of the "aryl group which may have a substituent" include, for example, p-tolyl and p-bromobenzene. Base, p-nitrophenyl, p-methoxyphenyl, 2,4-dichlorophenyl, pentafluorophenyl, 2-aminophenyl, 2-methyl-4-chlorophenyl, 4-hydroxy-1- Naphthyl, 6-methyl-2-naphthyl, 4,5,8-trichloro-2-naphthyl, anthracenyl, 2-aminoindenyl, and the like.

Examples of the "cycloalkyl group" of the cycloalkyl group which may have a substituent include, for example, a cyclopentyl group, a cyclohexyl group, an adamantyl group, and the like, and a "cycloalkyl group having a substituent", and examples thereof include: 5-dimethylcyclopentyl, 4-tert-butylcyclohexyl and the like.

The "heterocyclic group" of the heterocyclic group which may have a substituent may, for example, be a pyridyl group or a pyridyl group. Examples of the hexahydropyridyl group, the hexahydropyridine, the piperidyl group, the N-fosfolinyl group, the acridine group, and the like; the "heterocyclic group which may have a substituent" may, for example, be a 3-methylpyridyl group or an N-methyl group. Hexahydropyridyl, N-methylpyrrolyl and the like.

The "alkoxy group" which may have a substituent alkoxy group may, for example, be a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group or a third butoxy group. Linear or branched alkoxy groups such as benzyl, neopentyloxy, 2,3-dimethyl-3-pentyloxy, n-hexyloxy, n-octyloxy, stearyloxy, 2-ethylhexyloxy, etc. Examples of the "alkoxy group which may have a substituent" include, for example, trichloromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 2,2,3,3. -tetrafluoropropoxy, 2,2-di-trifluoromethylpropoxy, 2-ethoxyethoxy, 2-butoxyethoxy, 2-nitropropoxy, benzyloxy and the like.

The "aryloxy group" which may have an aryloxy group of a substituent may, for example, be a phenoxy group. Examples of the "aryloxy group which may have a substituent" include, for example, p-methylphenoxy, p-nitrophenoxy, p-methoxyphenoxy, 2, 4-Dichlorophenoxy, pentafluorophenoxy, 2-methyl-4-chlorophenoxy and the like.

The "alkylthio group" which may have a substituent alkylthio group may, for example, be a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group, an octylthio group or a thiol group. And dodecylthio group, octadecylthio group, etc.; examples of the "alkylthio group which may have a substituent" include, for example, methoxyethylthio group, amine ethylthio group, benzylaminoethylthio group, Methylcarbonylaminoethylthio, phenylcarbonylaminoethylthio and the like.

Examples of the "arylthio group" of the arylthio group which may have a substituent include, for example, a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, a 9-fluorenylthio group, and the like; Examples of the group include chlorophenylthio group, trifluoromethylphenylthio group, cyanophenylthio group, nifedipine group, 2-aminophenylthio group, 2-hydroxyphenylthio group and the like.

Next, specific examples of Y ₅ to Y ₁₂ include, for example, a halogen atom, a nitro group, a sulfhydryl methyl group (C ₆ H ₄ (CO) ₂ N-CH ₂ -) which may have a substituent, and an amine sulfonate. Mercapto group (H ₂ NSO ₂ -). Wherein the imine imino group which may have a substituent represents a structure in which a hydrogen atom in the quinone imine methyl group is substituted with a substituent; the aminesulfonyl group which may have a substituent represents a hydrogen atom in the amine sulfonyl group A structure substituted for a substituent. Among them, Y is preferably a halogen atom or an amine sulfonyl group. An anthraquinone compound having m ₁ to m ₄ of 0 (i.e., no Y ₅ to Y ₁₂ ) is suitable. Examples of the halogen atom include fluorine, chlorine, bromine, and iodine. The "substituent" of the imine methyl group which may have a substituent and the amine sulfonyl group which may have a substituent is synonymous with the substituent of X ₅ to X ₁₂ .

In the formula (8B), L represents: -O-SiR ₆ R ₇ -O-, -O-SiR ₆ R ₇ -O-SiR ₈ R ₉ -O-, or -OP(=O)R ₁₀ -O R ₆ to R _{10 are} each independently represented by a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, or an aromatic oxygen which may have a substituent base.

Examples of the alkyl group in R ₆ to R ₁₀ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, neopentyl group, n-hexyl group, and n-octyl group. a straight-chain or branched alkyl group such as a stearyl group or a 2-ethylhexylhexyl group; and the alkyl group may be a substituent which may have a substituent, and examples thereof include chlorine, fluorine, bromine, and the like. An alkoxy group such as a halogen atom or a methoxy group, an aryl group such as a phenyl group or a tolyl group, or a nitro group. Further, the substituents therein may be plural. Examples of the alkyl group which may have a substituent include, for example, trichloromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, 2,2-dibromoethyl, 2-ethoxy Ethyl, 2-butoxyethyl, 2-nitropropyl, benzyl, 4-methylbenzyl, 4-t-butylbenzyl, 4-methoxybenzyl, 4-nitrobenzene Methyl, 2,4-dichlorobenzyl and the like.

Examples of the aryl group in R ₆ to R ₁₀ include a phenyl group, a naphthyl group, a fluorenyl group and the like; and a substituent in the case where the aryl group may have a substituent, and examples thereof include a halogen such as chlorine, fluorine or bromine. Atom, alkyl, alkoxy, amine, nitro, and the like. Further, the substituents therein may be plural. The aryl group which may have a substituent may, for example, be p-tolyl, p-bromophenyl, p-nitrophenyl, p-methoxyphenyl, 2,4-dichlorophenyl, pentafluorophenyl, 2-di Methylaminophenyl, 2-methyl-4-chlorophenyl, 4-methoxy-1-naphthyl, 6-methyl-2-naphthyl, 4,5,8-trichloro-2-naphthalene Base, base, etc.

Examples of the alkoxy group in R ₆ to R ₁₀ include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, and a third butoxy group. a linear or branched alkoxy group such as neopentyloxy, 2,3-dimethyl-3-pentyloxy, n-hexyloxy, n-octyloxy, stearyloxy, 2-ethylhexyloxy; Examples of the substituent of the alkoxy group which may have a substituent include a halogen atom such as chlorine, fluorine or bromine; an aryl group such as an alkoxy group, a phenyl group or a tolyl group; and an amine group. Further, the substituents therein may be plural. Examples of the alkoxy group which may have a substituent include trichloromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 2,2,3,3-tetrafluoropropoxy. 2,2-Di-trifluoromethylpropoxy, 2-ethoxyethoxy, 2-butoxyethoxy, 2-nitropropoxy, benzyloxy and the like.

Examples of the aryloxy group in R ₆ to R ₁₀ include a phenoxy group, a naphthyloxy group, a decyloxy group and the like; and a substituent when the aryloxy group has a substituent, and examples thereof include chlorine, fluorine, and bromine. Or a halogen atom, an alkyl group, an alkoxy group, an amine group, a nitro group or the like. Further, the substituents therein may be plural. Examples of the aryloxy group having a substituent include p-methylphenoxy, p-nitrophenoxy, p-methoxyphenoxy, 2,4-dichlorophenoxy, pentafluorophenoxy, and 2- Methyl-4-chlorophenoxy and the like.

The indocyanin compound represented by the formula (8B) has 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 viscosity and color characteristics of the dispersion. An aryl group or an aryloxy group which may have a substituent is preferred. More preferably, any of R ₆ to R ₇ , R ₆ to R ₉ and R ₁₀ is an aryl group or an aryloxy group. More preferably, any of R ₆ to R ₇ , R ₆ to R ₉ and R ₁₀ is a phenyl group or a phenoxy group.

(other coloring agents)

The coloring composition containing the coloring agent represented by the general formula (1), (6) or (7) has a yellow color tone, so that it can be used in combination with other pigments to become yellow or other. The green and red colored compositions are excellent in color resistance and color reproducibility and color reproducibility. A green colorant used in a green color filter segment having high brightness can be obtained by using a green pigment and/or a blue pigment. Use red pigments (may also be used if necessary) Orange pigment), which is a red colorant used in red color filter segments with high brightness. Further, with a yellow pigment, a yellow colorant used for a yellow color filter segment which maintains high brightness while having excellent resistance and having a coloring power is obtained. At the same time, in the above color filter segments, a dye may be used in combination. Hereinafter, pigments and dyes are exemplified.

Among them, the green pigment is preferably a polyhalogenated ruthenium pigment. The polyhalogenated anthraquinone pigment represents an indocyanin pigment containing at least two halogen atoms. Specifically, for example, C.I. Pigment Green No. 7, No. 10, No. 36, No. 37, No. 58 and the like can be cited. Among them, C.I. Pigment Green No. 36 and No. 58 are preferred.

Blue pigments are preferred to use anthraquinone aluminum pigments. The anthraquinone aluminum pigment is preferably a pigment having a higher coloring power than a halogenated anthraquinone pigment. Thereby, the amount of addition of the pigment or the film thickness of the color filter can be reduced. At the same time, the viewpoint of not containing a halogen atom is also preferable in consideration of environmental safety.

Examples of yellow pigments include, for example, CI Pigment Yellow No. 1, No. 2, No. 3, No. 4, No. 5, No. 6, No. 10, No. 12, No. 13, No. 14, No. 15, No. 16, No. 17 , 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43 No., 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 No., 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187 Yellow pigments such as 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, or 221. Among them, from the viewpoints of heat resistance, light resistance, and brightness, C.I. Pigment Yellow No. 138, No. 139, No. 150, No. 185 is preferred.

Examples of red pigments can be used, such as: CI Pigment Red No. 7, No. 14, No. 41, No. 48: No., No. 48:2, No. 48:3, No. 48:4, No. 57:1, No. 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 No., No. 276, No. 277, No. 278, No. 279, No. 280, No. 281, No. 282, No. 283, No. 284, No. 285, No. 286, or No. 287. Among them, C.I. Pigment Red No. 177, No. 179, No. 254 is preferred. Further, a red dye such as a xanthene system, an azo system, a disazo system or a fluorene system may be used. Specific examples thereof include a salt forming compound of a dibenzopyrano acid dye such as C.I. Acid Red No. 52, No. 87, No. 92, No. 289, No. 338, and the like. Among them, C.I. Pigment Red No. 177 and No. 254 are particularly preferred.

Examples of orange pigments include: C.I. Pigment Orange No. 38, No. 43, No. 71, Or 73 and so on.

The yellow dye may, for example, be an azo dye, an azo metal stinky dye, an anthraquinone dye, an indigo dye, a thioindigo dye, an anthraquinone dye, a diphenylmethane dye, a triphenylmethane dye, a dibenzopyran dye, Thio Dyes, cationic dyes, cyanine dyes, nitro dyes, quinoline dyes, naphthoquinone dyes, dye.

Specific examples of the yellow dye include, for example, CI Acid Yellow 2, 3, 4, 5, 6, 7, 8, 9, 9, 1:, 10, 11, and 11: 1, 1, 12, 13, 14, 15, 15, 16, 17, 17 29, 30, 31, 33, 34, 36, 38, 39, 40, 40:1, 41, 42, 42:1, 43, 44, 46 No. 48, No. 51, No. 53, No. 55, No. 56, No. 60, No. 63, No. 65, No. 66, No. 67, No. 68, No. 69, No. 72, No. 76, No. 82, No. 83, No. 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 No., No. 190, No. 191, No. 192, No. 199, etc.

Others, such as: CI Direct Dye Yellow No. 1, No. 2, No. 4, No. 5, No. 12, No. 13, No. 15, No. 20, No. 24, No. 26, No. 26, No. 32, No. 33, No. 34, No. 34, 35, 41, 42, 44, 44:1, 45, 46, 48, 49, 50, 51, 61, 66, Nos. 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, etc.

Others, such as: CI alkaline yellow 1, 2, 5, 11, 13, 14, 15, 15, 21, 24, 25, 28, 29, 37 , 40, 45, 49, 51, 57, 79, 87, 90, 96, 103, 105, 106, etc.

Others, such as: CI Solvent Yellow 2, 3, 4, 7, 8, 10, 11, 12, 13, 14, 15, 15, 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 No., 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 , No. 184, No. 185, No. 186, No. 187, No. 188, No. 190, No. 191, No. 192, No. 194, No. 195, etc.

Others, such as: CI Disperse Dye Yellow No. 1, No. 2, No. 3, No. 5, No. 7, No. 8, No. 10, No. 11, No. 13, No. 13, No. 23, No. 27, No. 33, No. 34 , No. 42, No. 45, No. 48, No. 51, No. 54, No. 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 , No. 248, No. 249, No. 250, No. 251, etc.

The content of the preferred coloring agent among the all-nonvolatile components of the colored composition produced in the present embodiment is preferably from 10 to 90% by weight from the viewpoint of sufficient color reproducibility and stability, 15 More preferably, it is 85% by weight, and most preferably 20 to 80% by weight.

When the yellow pigment is used in combination, the weight ratio of the yellow pigment / the anthraquinone aluminum pigment represented by the formula (8A) and/or (8B) is preferably from 80/20 to 10/90. When this range is satisfied, a green color filter segment excellent in luminance and wide in chromaticity range can be formed.

When the quinophthalone compound represented by the formula (1) and the quinoline yellow compound represented by the formula (6) are used in combination, the quinoline compound represented by the formula (1) is passed through 100 parts by weight. The quinophthalone yellow pigment represented by the formula (6) is preferably in the range of 10 to 1,500 parts by weight, more preferably in the range of 100 to 1200 parts by weight. The quinophthalone yellow pigment represented by the formula (6) exhibits an effect of improving the brightness when it is more than 10 parts by weight. When the amount is less than 1,500 parts by weight, the contrast value and the sensitivity when used as a photosensitive coloring composition are improved, which is preferable.

When the coloring agent (or coloring composition) of the green color filter segment is formed, the ratio of the green pigment and/or the blue pigment to the anthraquinone pigment represented by the formula (6) is relative to 100 parts by weight of the pigment. , anthraquinone represented by the formula (6) The pigment is preferably from 1 to 1200 parts by weight, more preferably from 5 to 600 parts by weight. When the amount of the anthraquinone dye represented by the formula (6) is 1 part by weight or more, the chromaticity field which can be reproduced becomes wider; and when it is 1200 parts by weight or less, the color tone does not change.

At the same time, as a coloring agent (or a coloring composition) for forming a green color filter segment, green pigment and/or blue pigment and yellow coloring are used when a yellow pigment and an anthraquinone pigment represented by the general formula (6) are used in combination. The use ratio of the agent (mixture of the yellow pigment and the anthraquinone pigment represented by the formula (6)) is preferably 1 to 1200 parts by weight, and 5 to 600 parts by weight, based on 100 parts by weight of the pigment. good. When the amount of the yellow colorant added is 1 part by weight or more, the reproducible chromaticity field is broadened, and when it is 1200 parts by weight or less, there is no change in color tone.

As a coloring agent (or a coloring composition) for forming a green color filter segment, when a yellow pigment and an anthraquinone dye represented by the general formula (6) are used in combination, a yellow pigment and a general formula (6) are considered in consideration of color composition thereof. The blending ratio of the content of the anthraquinone pigment shown is preferably from 1 to 400 parts by weight, and from 5 to 300 parts by weight, based on 100 parts by weight of the yellow pigment, of the anthraquinone pigment represented by the formula (6). good.

As a coloring agent (or a coloring composition) for forming a red color filter segment, a ratio of a red pigment to an anthraquinone dye represented by the general formula (6) is compared with 100 parts by weight of a red pigment, and the general formula (6) The anthraquinone pigment shown is preferably from 1 to 800 parts by weight, more preferably from 5 to 400 parts by weight. When the amount of the anthraquinone dye represented by the formula (6) is 1 part by weight or more, the reproducible chromaticity field is broadened, and when it is 800 parts by weight or less, there is no change in color tone. Further, when considering the color constitution, the red pigment and the anthraquinone pigment represented by the formula (6) The blending ratio is preferably from 1 to 400 parts by weight, more preferably from 5 to 300 parts by weight, per 100 parts by weight of the red pigment.

When the anthraquinone dye represented by the formula (8A) or (8B) and the anthraquinone dye represented by the formula (6) are used in combination, 100 parts by weight of the anthraquinone represented by the formula (6) The pigment, the anthraquinone pigment represented by the formula (6) is preferably in the range of 3 to 1200 parts by weight, more preferably in the range of 5 to 800 parts by weight. When the amount of the anthraquinone represented by the formula (8A) or (8B) is more than 3 parts by weight, the effect of improving the brightness can be sufficiently exhibited. When it is less than 1200 parts by weight, heat resistance and light resistance can be improved, which is preferable.

When the anthraquinone dye represented by the formula (6) and the anthraquinone dye represented by the formula (7) are used in combination, the formula of the anthraquinone dye represented by the formula (6) is 100 parts by weight. The anthraquinone pigment shown in (7) is preferably in the range of 11 to 900 parts by weight. It is more preferably in the range of 27 to 650 parts by weight, and more preferably in the range of 43 to 400 parts by weight. When the amount of the anthraquinone dye represented by the formula (7) is 11 parts by weight or more, the fluorescence of the anthraquinone dye represented by the formula (6) can be sufficiently eliminated, so that the comparative value is improved; at 900 parts by weight In the following, the coloring power can be made practical, and therefore it is preferable.

The use ratio of the green pigment and/or the blue pigment to the anthraquinone pigment represented by the general formulae (6) and (7) is preferably 5 to 1000 parts by weight based on 100 parts by weight of the pigment. More preferably 17 to 600 parts by weight. When the amount of the anthraquinone dye represented by the general formulae (6) and (7) is 5 parts by weight or more, the reproducible chromaticity field is broadened, and when it is 1000 parts by weight or less, there is no change in color tone.

When a yellow pigment and an anthraquinone pigment represented by the general formulae (6) and (7) are used in combination, a green pigment and/or a blue pigment and a yellow colorant (a yellow pigment and the formulas (6) and (7) are shown. The use ratio of the mixture of the anthraquinone pigments is preferably from 5 to 1,000 parts by weight, more preferably from 17 to 600 parts by weight, per 100 parts by weight of the green pigment and/or the blue pigment. When the amount of the yellow colorant added is 5 parts by weight or more, the reproducible chromaticity field is broadened, and when it is 600 parts by weight or less, there is no change in color tone.

When a yellow pigment and an anthraquinone pigment represented by the general formulae (6) and (7) are used in combination, the yellow pigment and the anthraquinone pigment represented by the general formulae (6) and (7) are considered in consideration of the color constitution thereof. The blending ratio of the content is preferably from 1 to 400 parts by weight, more preferably from 5 to 300 parts by weight, per 100 parts by weight of the yellow pigment, of the anthocyanin dyes represented by the formulae (6) and (7).

As a coloring agent (or a coloring composition) for forming a red color filter segment, the ratio of the red pigment to the anthocyanin pigment represented by the general formulas (6) and (7) is relative to 100 parts by weight of the red pigment. The anthraquinone dyes represented by the general formulae (6) and (7) are preferably from 1 to 100 parts by weight, more preferably from 5 to 50 parts by weight. When the amount of the anthraquinone dye represented by the general formulae (6) and (7) is 1 part by weight or more, the reproducible chromaticity field is broadened, and when it is 100 parts by weight or less, there is no change in color tone. .

Wherein the ratio of the green pigment and/or the blue pigment to the quinoline yellow pigment represented by the formula (7A) is from 1 to 1200 with respect to 100 parts by weight of the pigment of the anthraquinone pigment represented by the formula (7A). The parts by weight are preferably from 5 to 600 parts by weight. When the amount is more than 1 part by weight, the reproducible chromaticity field is broadened, and when it is 1200 parts by weight or less, there is no change in color tone.

Further, when a yellow pigment and an anthraquinone dye represented by the formula (7A) are used in combination, a green pigment and/or a blue pigment and a yellow colorant (a yellow pigment and an anthraquinone pigment represented by the formula (7A)) The proportion of the mixture used is preferably from 1 to 1200 parts by weight, more preferably from 5 to 600 parts by weight, per 100 parts by weight of the pigment. When the amount is 1 part by weight, the reproducible chromaticity field is broadened, and when it is 1200 parts by weight or less, there is no change in color tone.

When a yellow pigment and a quinoline yellow pigment represented by the general formula (7A) are used as the pigment for the green color filter segment, the yellow pigment and the quinoline yellow pigment represented by the general formula (7A) are considered in consideration of the color constitution thereof. The blending ratio of the content is preferably from 1 to 400 parts by weight based on 100 parts by weight of the yellow pigment, and the formula (7A) is based on 100 parts by weight of the yellow pigment. The anthraquinone pigment is preferably in the range of 5 to 300 parts by weight.

The ratio of the yellow pigment to the anthocyanin dye represented by the formula (7A) when used as a coloring agent (or a coloring composition) for forming a yellow color filter segment, with respect to 100 parts by weight of the yellow pigment The anthraquinone pigment shown in (7A) is preferably from 1 to 1200 parts by weight, more preferably from 5 to 600 parts by weight. When the color composition is considered, the blending ratio of the yellow pigment to the anthraquinone pigment represented by the formula (7A) is 1 to 100% by weight of the yellow pigment, and the anthraquinone dye represented by the formula (7A) is 1 to It is preferably 400 parts by weight, more preferably in the range of 5 to 300 parts by weight.

The ratio of the red pigment used as the coloring agent (or coloring composition) for forming the red color filter segment to the anthocyanin dye represented by the general formula (7A) is relative to 100 parts by weight of the red pigment. Indigo as shown in (7A) The pigment is preferably from 1 to 800 parts by weight, more preferably from 5 to 400 parts by weight. When the amount of the anthraquinone dye represented by the formula (7A) is 1 part by weight or more, the reproducible chromaticity field is broadened, and when it is 800 parts by weight or less, there is no change in color tone. When the color composition is considered, the blending ratio of the red pigment to the anthraquinone pigment represented by the formula (7A) is 1 to the anthocyanin dye represented by the formula (7A) with respect to 100 parts by weight of the red pigment. It is preferably 400 parts by weight, more preferably in the range of 5 to 300 parts by weight.

Any combination of the above may be appropriately adjusted and used in consideration of heat resistance, light resistance, and brightness of the colorant.

<fineness of pigment>

When the colorant is a pigment, it is preferably used after being refined. The method of miniaturization is not particularly limited. For example, wet milling, dry milling, and dissolution precipitation can be used, and the salt milling treatment can be performed by a kneading method which is one of wet milling. The primary particle diameter of the pigment is preferably 5 nm or more from the viewpoint of good dispersion in the colorant carrier. From the viewpoint of a color filter segment which can form a high contrast value, it is preferably 100 nm or less. A particularly preferred range is in the range of 10 to 80 nm. The primary particle diameter of the pigment is determined by an electron micrograph of a TEM (transmission electron microscope) of the pigment by a direct measurement method. Specifically, the short axis diameter and the major axis diameter of the primary particles of each pigment are measured, and the average is used as the particle diameter of the pigment particles.

Salt grinding treatment refers to a mixture of a pigment and a water-soluble inorganic salt and a water-soluble organic solvent: a kneader, a 2-axis roll mill, a 3-axis roll mill, a ball mill, an attritor, a sand mill, Planetary mixer A batch or continuous kneader such as a planetary mixer is subjected to mechanical mixing while heating, and then washed with water to remove the water-soluble inorganic salt and the water-soluble organic solvent. Among them, the water-soluble inorganic salt acts as a pulverization auxiliary, and the salt grinding uses a high hardness pulverizing pigment of an inorganic salt. Therefore, by optimizing the conditions of the pigment during the salt milling treatment, the primary particle diameter can be made very fine, and the distribution range thereof is small, and a pigment having a concentrated particle size distribution can be obtained.

As the water-soluble inorganic salt, sodium chloride, cesium chloride, potassium chloride, sodium sulfate or the like can be used, and sodium chloride (salt) is preferably used in terms of price. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by weight, more preferably 300 to 1000 parts by weight, based on the total weight of 100 parts by weight of the pigment, in terms of both treatment efficiency and production efficiency.

The water-soluble organic solvent has a function of moistening the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it is soluble (mixed) in water and substantially does not dissolve the inorganic salt. However, when the salt is milled, the temperature rises and the solvent is easily evaporated. Therefore, it is preferable to use a high boiling point solvent having a boiling point of 120 ° C or higher from the viewpoint of safety. For example, 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol can be used. Alcohol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, and the like. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by weight, more preferably 50 to 500 parts by weight, per 100 parts by weight of the total weight of the pigment.

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

<Binder resin>

The binder resin is a material which disperses a coloring agent, or dyes and permeates it, and examples thereof include a conventionally known thermoplastic resin and a thermosetting resin. In terms of the binder resin, in the full wavelength range of 400 to 700 nm in the visible light range, the spectral transmittance is preferably 80% or more, more preferably 95% or more. At the same time, since the binder resin has a chemical interaction with the quinoline yellow pigment represented by the formula (6), it is preferable because the effect of improving the contrast value is obtained by the elimination of the fluorescence.

Examples of the thermoplastic resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, and the like. Polyvinyl acetate, polyurethane resin, polyester resin, polyethylene resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, cellulose, Polyethylene (HDPE, LDPE), polybutadiene, and polyimide resin.

Moreover, when it is used in the form of an alkali-developing type coloring photoresist, it is preferred to use an alkali-soluble resin copolymerized with an acid group-containing ethylenically unsaturated monomer. At the same time, in order to improve the light sensitivity, it is also possible to use ethylene. An active energy ray-curable resin having an unsaturated double bond.

In particular, when an active energy ray-curable resin containing an ethylenically unsaturated double bond in a side chain is used in an alkali-developing resist for a color filter, no foreign matter of the coating film is formed after the colorant is applied, and light can be improved. The stability of the coloring agent in the resist material is therefore preferred. When a linear resin containing no ethylenic unsaturated double bond in its side chain is used, the coloring agent in the solution in which the resin and the coloring agent are mixed is not easily trapped by the resin and has a degree of freedom, so that the colorant component is easily aggregated. It is precipitated that when an active energy ray-curable resin having an ethylenically unsaturated double bond in its side chain is used, the colorant is easily trapped by the resin in a solution in which the resin and the colorant are mixed, and therefore, in the solvent resistance test Because the pigment is not easily dissolved, the colorant component is not easy to aggregate. When a film is formed by exposure of an active energy ray, the resin is formed into a three-dimensional crosslink to fix the colorant molecules, and therefore it can be presumed that even if the solvent is removed in the subsequent developing step, the colorant component will not easily aggregate. . Precipitate.

Examples of the alkali-soluble resin to which the acid group-containing ethylenically unsaturated monomer is copolymerized include a resin containing an acid group such as a carboxyl group or a mercapto group. Specific examples of the alkali-soluble resin include, for example, an acid group-containing acrylic resin, an α-olefin/maleic anhydride copolymer, a styrene/styrenesulfonic acid copolymer, and a styrene/(meth)acrylic acid copolymer. Or an isobutylene/maleic acid (anhydride) copolymer or the like. Among them, at least one resin selected from the group consisting of an acid group-containing acrylic resin and a styrene/styrenesulfonic acid copolymer, particularly an acid group-containing acrylic resin, is more suitable for use because of its high heat resistance and transparency. .

Meanwhile, the alkali-soluble resin is preferably a hydrophilic functional group different from an acid group such as acrylic acid from the viewpoint of dispersibility of the quinophthalone yellow pigment. The introduction of the hydrophilic functional group is preferably carried out using an ethylenically unsaturated monomer having a hydroxyl group and/or a (poly)alkylene oxide structure and having no aromatic ring. Specific examples of such ethylenically unsaturated monomers include, for example, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. a hydroxyl group-containing (meth) acrylate such as glycerol mono(meth)acrylate, 4-hydroxyvinylbenzene, and 2-hydroxy-3-phenoxypropyl acrylate; (meth)acrylic acid- 2-methoxyethyl ester, 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 (methyl 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, polyethylene Alcohol monostearyl ether (meth) acrylate, and octoxy polyethylene glycol / polypropylene (poly)alkylene glycol monoalkyl ether (meth) acrylates such as (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, ( 2-Methoxyethyl methacrylate, diethylene glycol monoethyl ether (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate, polypropylene glycol monomethyl ether (meth) acrylate .

The content of the above-mentioned hydroxyl group and/or (poly)alkylene oxide, and the content of the ethylenically unsaturated monomer having no aromatic ring can be appropriately selected insofar as the solubility in the synthetic solvent is not impaired, but propylene glycol monomethyl ether B When the acid ester is used in a synthetic solvent, it is preferably 5 to 50% by weight, preferably 10 to 35% by weight. The scope is more appropriate.

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. The number average molecular weight (Mn) is preferably in the range of 2,500 to 50,000, and the value of Mw/Mn is preferably 10 or less.

Further, the glass transition temperature of the alkali-soluble resin (hereinafter sometimes expressed by Tg) is preferably from -40 to 70 ° C from the viewpoint of dispersion stability, more preferably from -30 to 30 ° C, and further from -20 to 10 ° C. good.

The Tg of the alkali-soluble resin is a value calculated by the following formula of Fox.

1/Tg=W1/Tg1+W2/Tg2+. . . +Wn/Tgn

Wherein W1 to Wn represent the weight fraction of each monomer used; and Tg1 to Tgn represent the glass transition temperature (unit: absolute temperature "K") of each homopolymer obtained from each monomer.

The Tg of the main homopolymer used in the calculation is as shown in the following examples.

Methacrylic acid: 130 ° C (403K)

Butyl acrylate: -54 ° C (219 K)

Benzyl methacrylate: 55 ° C (328 K)

P-Phenylphenol phenol ethylene oxide modified acrylate (manufactured by Japan East Asia Synthetic Co., Ltd., M-110): 35 ° C (308 K)

4-hydroxybutyl methacrylate: -80 ° C (193 K)

2-Hydroxyethyl methacrylate: 55 ° C (328 K)

Methoxy polyethylene glycol methacrylate (manufactured by Nippon Oil & Fats Co., Ltd., PME-400): -60 ° C (213 K)

Butyl methacrylate: 20 ° C (293 K)

In the method for producing an active energy ray-curable resin having an ethylenically unsaturated active double bond, the above resin precursor may be, for example, prepared in a linear form having a reactive substituent such as a hydroxyl group, a carboxyl group or an amine group. The polymer is reacted with a (meth)acrylic compound containing a reactive substituent such as an isocyanate group, an aldehyde group or an epoxy group, and cinnamic acid to obtain a (meth)acrylonyl group or a styryl group. a method of introducing a photocrosslinkable group into a resin of the linear polymer; and a linear polymer comprising an anhydride of a styrene-maleic anhydride copolymer and an α-olefin/maleic anhydride copolymer a method of semi-esterifying a hydroxyl group-containing (meth)acrylic compound such as a hydroxyalkyl (meth)acrylate; and a copolymerized linear group of a hydroxyl group-containing (meth)acrylic acid compound such as a hydroxyalkyl (meth)acrylate a method of adding an isocyanate group-containing (meth)acrylic compound such as (meth)acryloyloxyethyl isocyanate to a polymer; and adding to a linear polymer containing a carboxyl group such as (meth)acrylic acid (methyl An epoxy group such as glycidyl acrylate Yl) acrylic acid compound of the method.

In the case of the thermoplastic resin, it is preferable to use a material having both an alkali-soluble energy and an energy-line hardening property as a coloring composition for a color filter.

The monomer constituting the thermoplastic resin described above can be exemplified as follows. Examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, (a) Isobutyl acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, hard (meth)acrylate Fatty ester, lauryl (meth)acrylate, tetrahydrofuran methyl (meth)acrylate, isodecyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, (methyl) Phenyloxyethyl acrylate, phenoxy diethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth) acrylate, or ethoxypolyethylene glycol (meth) acrylate, etc. Acrylates; or (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl ( Methyl) acrylamide, diacetone (meth) acrylamide, or (meth) acrylamide such as propylene hydrazino; styrene such as styrene or α-methyl styrene a vinyl ether such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether or isobutyl vinyl ether; vinyl acetate such as vinyl acetate or vinyl propionate; Esters and the like.

Also exemplified are: cyclohexyl maleimide, phenyl maleimide, methyl maleimide, ethyl maleimide, 1,2-double Maleic acid imide ethane, 1,6-bis-s-butylene diimide hexane, propionic acid-3-succinimide, coumarin-6,7-methylenedioxy 4-methyl-3-maleimidoimine, diphenylmethane-4,4'-bis-s-butylene diimide, methane bis(3-ethyl-5-methyl-4- Maleimide phenyl), N,N'-1,3-phenylenebissuccinimide, N,N'-1,4-phenylene dimethylenebutene Imine, N-(1-indenyl) maleimide, N-(2,4,6-trichlorophenyl) maleimide, N-(4-aminophenyl) cis Butyleneimine, N-(4-nitrophenyl)maleimide, N-benzylmethyleneimine, N-bromomethyl-2,3-dichloro Butylenediimide, N-succinimide-3-butanediamine benzoate, N-succinimide-3- Maleimide propionate, N-succinimide-4-butylimide butyrate, N-succinimide-6-m-butyleneimine N-substituted maleicylenes such as esters, N-[4-(2-benzimidazolyl)phenyl]-m-butyleneimine, 9-maleimide, acridine and the like Amines.

Examples of the thermosetting resin include epoxy resin, benzoguanamine resin, rosin modified maleic acid resin, rosin modified fumaric acid resin, melamine resin, urea resin, and phenol resin. Wait. Among them, from the viewpoint of improving heat resistance, it is preferred to use an epoxy resin or a melamine resin.

The weight average molecular weight (Mw) of the binder resin is preferably in the range of 5,000 to 100,000 for the colorant to be well dispersed, and more preferably in the range of 5,000 to 80,000, 10,000 to 80,000, 7,000 to 50,000, 8,000 to 50,000. range. The number average molecular weight (Mn) is preferably in the range of 2,500 to 50,000, more preferably in the range of 5,000 to 50,000, and 2,500 to 40,000. The value of Mw/Mn is also preferably 10 or less. Among them, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are in the gel permeation chromatography "HLC-8120GPC" manufactured by Tosoh Corporation of Japan, and are connected in series by four separate columns, and the filler is sequentially "TSK-GEL SUPER H5000", "H4000", "H3000", and "H2000" manufactured by Tosoh Corporation of Japan, and the molecular weight of the converted polystyrene measured by the mobile phase of tetrahydrofuran.

At the same time, the weight of the binder resin is used when the device uses HLC-8220GPC (manufactured by Tosoh Corporation of Japan), the column is connected by TSK-GEL SUPER HZM-N, and the molecular weight of the converted polystyrene is measured when the solvent is THF. The average molecular weight (Mw) is preferably in the range of 5,000 to 80,000, more preferably in the range of 7,000 to 50,000, in order to allow the colorant to be well dispersed. with The number average molecular weight (Mn) is preferably in the range of 2,500 to 40,000, and the value of Mw/Mn is preferably 10 or less.

When the binder resin is used as a coloring composition for a color filter, a carboxyl group acting as an alkali adsorbing group for a coloring agent adsorption group and development, and an aliphatic group and an aryl group acting as an affinity group for a colorant carrier and a solvent The balance is important for the dispersibility, permeability, developability, and durability of the colorant, and therefore it is preferred to use a resin having an acid value of 20 to 300 mgKOH/g. When the acid value is less than 20 mgKOH/g, the solubility in the developing solution is deteriorated, so that it is difficult to form a fine image. When it is higher than 300 mgKOH/g, fine images cannot be left in development.

The binder resin is preferably used in an amount of 20 to 500 parts by weight, more preferably 30 to 500 parts by weight, per 100 parts by weight of the color former. When it is 20 parts by weight or more, the film formability and various resistances are good, and when it is 500 parts by weight or less, the color characteristics are excellent. Further, from the viewpoint of eliminating the fluorescence, it is preferably used in an amount of from 20 parts by weight to 400 parts by weight. When it is 20 parts by weight or more, the fluorescence thereof can be sufficiently eliminated. When it is 400 parts by weight or less, self-extinction occurring between the quinoline yellow pigments represented by the general formula (6) is not inhibited. At the same time, it is preferable to contain an aromatic ring from the viewpoint of elimination of fluorescence in the structure of the binder resin. In particular, the more the aromatic ring is contained, the better.

<organic solvent>

In the coloring composition of the present embodiment, in order to sufficiently disperse and infiltrate the coloring agent in the colorant carrier, it is possible to easily form a color filter having a dried film thickness of 0.2 to 5 μm after coating on a substrate such as a glass substrate. The fragment contains an organic solvent. The organic solvent, in addition to the coloring composition In addition to good coatability, it is selected in consideration of solubility and safety of each component of the coloring composition.

Examples of the organic solvent include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butanediol, and diacetic acid-1,3. -butylene glycol ester, 1,4-two Alkane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclo Hexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, acetic acid-3-methoxy -3-methylbutyl ester, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-di Methylacetamide, N,N-dimethylformamide, n-butanol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chloro Toluene, p-diethylbenzene, second butylbenzene, terphenylbenzene, γ-butyrolactone, isobutanol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl Ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, Ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoiso Dipropyl ether, diethylene glycol monoethyl ether acetate, two Glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether Acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol Monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol 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 single Methyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid ester, etc. .

Among them, in view of good dispersibility, permeability, and coatability of the coloring composition, an alkyl lactate such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, or B is used. A glycol diol ester such as diol monomethyl ether acetate or ethylene glycol monoethyl ether acetate, an alcohol such as benzyl alcohol or diacetone alcohol, or a ketone such as cyclohexanone is preferred.

The organic solvent may be used alone or in combination of two or more kinds in any ratio as necessary. At the same time, the organic solvent can also adjust the coloring composition to a suitable viscosity to form a uniform film thickness of the color filter segment, so it is preferable to use 500 to 4000 parts by weight with respect to 100 parts by weight of the coloring agent, 800. More preferably, it is 4,000 parts by weight.

<Dispersing adjuvant>

An embodiment of the colored composition of the present invention may further comprise a dispersion auxiliary. In other words, when the colorant is dispersed in the colorant carrier, a dispersion auxiliary such as a dye derivative, a resin type dispersant, or a surfactant may be suitably used. The dispersing auxiliary agent has a large effect on the prevention of re-aggregation of the dispersing coloring agent. Therefore, the coloring composition formed by dispersing the coloring agent in the coloring agent carrier with a dispersing auxiliary agent can improve brightness and viscosity stability.

At the same time, when the quinoline yellow pigment is fluorescent, the chemical interaction between the quinoline yellow pigment and the pigment derivative or the resin dispersant causes the fluorescence of the quinoline yellow pigment to be eliminated, so that the contrast value is obtained. Better.

(pigment derivative)

Examples of the pigment derivative include organic pigments, hydrazine, acridone, or in three In the above, a compound having a basic substituent, an acidic substituent, or a sulfhydryl methyl group which may have a substituent may be introduced, and examples thereof include those disclosed in JP-A-63-305173 and JP-A-57- Japanese Unexamined Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. 2004-091497, Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 2008-094. The articles described in Japanese Patent No. 4,585, 871, and the like can be used alone or in combination of two or more. When a dye derivative is used, it is preferable to contain a quinoline yellow skeleton or an azo skeleton from the viewpoint of brightness.

Meanwhile, when the quinoline yellow pigment is fluorescent, it is preferable to contain a fluorene skeleton, an acridone skeleton, and an anthraquinone skeleton from the viewpoint of eliminating fluorescence. Meanwhile, the substituent is preferably a guanamine.

The content of the dye derivative is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, and still more preferably 3 parts by weight or more based on 100 parts by weight of the coloring agent. Meanwhile, from the viewpoint of heat resistance and light resistance, it is preferably 40 parts by weight or less, more preferably 35 parts by weight or less.

(resin type dispersant)

Resin type dispersant, which contains the color of the property of adsorbing colorant The affinity portion of the agent and the portion having compatibility with the coloring agent carrier have a function of being adsorbed to the coloring agent to stabilize the dispersibility of the coloring agent to the coloring agent carrier. Specific examples of the resin-type dispersant include polycarboxylates such as polyurea and polyacrylate; unsaturated polyamines, polycarboxylic acids, polycarboxylic acid (partial) amine salts, and ammonium polycarboxylates. a salt, a polycarboxylic acid alkylamine salt, a polyoxyalkylene oxide, a long-chain polyamine phthalamide phosphate, a hydroxyl group-containing polycarboxylic acid ester, and a modified substance thereof, from poly(lower alkyleneimine) and having An oily dispersant such as a guanamine or a salt thereof formed by the reaction of a free carboxyl group-containing polyester; (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylate copolymer, styrene - a maleic acid copolymer, a polyvinyl alcohol, a polyvinylpyrrolidone or the like, a water-soluble resin, a water-soluble polymer compound, a polyester system, a modified polyacrylate system, an ethylene oxide/propylene oxide additive A compound, a phosphate ester or the like may be used, and these may be used alone or in combination of two or more kinds, but are not limited thereto.

When the quinophthalone compound represented by the formula (1) is used, from the viewpoint of dispersibility, fluidity, and storage stability, the resin-type dispersant is used in the copolymerization composition to have ethylene oxide. A dispersing agent of the ethylenically unsaturated monomer (a1) of at least one of a chain or a propylene oxide chain is preferred. This resin type dispersant is described in the following items of the pigment dispersant.

Among the above-mentioned resin-type dispersants, a polymer dispersant containing a basic functional group is preferable because a small amount of the additive can reduce the viscosity of the coloring composition and exhibit a high contrast value, and a nitrogen atom is contained therein. a graft copolymer and a polyacrylic block copolymer containing a nitrogen atom and an amine having a functional group having a tertiary amino group, a quaternary ammonium salt group, a nitrogen-containing hetero ring or the like An ester polymer dispersant or the like is preferred.

Examples of the commercially available resin type dispersant include, for example, Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165 manufactured by BYK Japan. , 166, 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163 , 2164 or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, 21116, 21324, 21407, 21715 or Lactimon, Lactimon-WS or Bykumen, etc.; SOLSPERSE-3000 manufactured by Lubrizol, Japan, 9000, 13000, 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, 55000, 56000, 76500, etc.; EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401 manufactured by Ciba Japan. 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560 4800,5010,5065,5066,5070,7500,7554,1101,120,150,1501,1502,1503 like; manufacture of Ajinomoto Company Unitech AJISPER-PA111, PB711, PB821, PB822, PB824 and the like.

The content of the resin type dispersant is preferably 0.1 to 55 parts by weight, more preferably 0.1 to 45 parts by weight, per 100 parts by weight of the color former. When the content of the resin type dispersant is 0.1 part by weight or more, sufficient When the content is added at 55 parts by weight or less, the dispersion can be made extremely excellent.

Alternatively, the resin-type dispersant is preferably used in an amount of from 5 to 200% by weight based on the total amount of the pigment, and is preferably used in an amount of from 10 to 100% by weight from the viewpoint of film formability.

<Pigment Dispersant>

In the case of the pigment dispersant, the copolymerizable composition contains an ethylenically unsaturated monomer (a1) having at least one of an ethylene oxide chain or a propylene oxide chain, and an ethylene having two hydroxyl groups in a single terminal portion. a hydroxyl group of the polymer (A), an isocyanate group of a urethane prepolymer (E) having an isocyanate group at both terminals and an isocyanate group of a diisocyanate (B), and a polyamine (C) The amine compound is synthesized by reacting one of the primary and/or secondary amine groups.

The ethylene polymer portion derived from the ethylene polymer (A) having two hydroxyl groups at the terminal end portion has an excellent affinity for a wide range of pigment carriers and dispersion solvents by selecting an ethylenically unsaturated monomer thereof. It can be expressed as a solvent affinity part. On the other hand, the amine group and the urea bond site introduced through the hydroxyl group present in the single terminal portion of the ethylene polymer portion can exhibit the function as an adsorption site for the surface of the acid-adsorbed pigment.

Hereinafter, each constituent element of the pigment dispersant will be described.

(Ethylene polymer (A) having two hydroxyl groups at the end portion)

An ethylene polymer (A) having two hydroxyl groups in a single terminal portion constituting the pigment dispersant (hereinafter sometimes referred to as an ethylene polymer (A)) is contained An ethylenically unsaturated monomer (a1) of at least one of an ethylene oxide chain or a propylene oxide chain, and an ethylenically unsaturated monomer (a2) copolymerizable with (a1), having two in the molecule In the presence of a hydroxyl group and a thiol group-containing compound (a3), it is preferably obtained by radical polymerization. The radical polymerization is preferably carried out by using a polymerization initiator and a polymerization solvent.

(Ethylene unsaturated monomer (a1) containing 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 contains at least one of an ethylene oxide chain or a propylene oxide chain, and conventional monomers can be used. Specific examples thereof include: 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-methoxypropyl (meth)acrylate, and diethyl Glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol mono-2-ethylhexyl ether (meth) acrylate, dipropylene glycol monomethyl ether ( Methyl) acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, tripropylene glycol monomethyl ether (meth) acrylate, tetraethylene glycol single Methyl ether (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate, polypropylene glycol monomethyl ether (meth) acrylate, polyethylene glycol monolauryl ether (meth) acrylate, poly a (poly)alkylene glycol monoalkyl ether (meth) acrylate such as ethylene glycol monostearyl ether (meth) acrylate or octyloxy polyethylene glycol-polypropylene glycol (meth) acrylate; Phenyloxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyethylene glycol (meth)acrylate, ( Phenyloxypolyethylene glycol methacrylate, (methyl) P-cumylphenoxyethyl acrylate, p-cumylbenzene (meth)acrylate Oxyethylene glycol ester, p-cumylphenoxy poly(ethylene glycol) (meth) acrylate, decyl phenoxy ethoxylate (meth) acrylate, decyl phenoxy propylene glycol (meth) acrylate An (cyclo) (poly) (alkyl) alkylene glycol ester of an aromatic ring such as an ester or a nonylphenoxy poly(ethylene glycol-propylene glycol) (meth)acrylate. 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 above ethylenically unsaturated monomer (a1) can be used for the purpose of improving the dispersibility of the quinophthalone pigment. The ethylenically unsaturated monomer (a1) preferably contains at least one of an ethylene oxide chain and/or a propylene oxide chain, and more preferably contains at least an ethylene oxide chain. The dispersibility of the quinophthalone pigment is the addition mole number of the ethylene oxide chain and/or the propylene oxide chain in the ethylenically unsaturated monomer (a1) forming the ethylene polymer (A), and The blending ratio of the ethylenically unsaturated monomer (a1) in the ethylene polymer (A) is affected. The preferred range is that, depending on the quinophthalone yellow pigment and the pigment dispersant, the molar number of the ethylene oxide chain and/or the propylene oxide chain in the ethylenically unsaturated monomer (a1) is increased. Preferably, it is preferably from 1 to 50, more preferably from 1 to 20, particularly preferably from 4 to 13. When the addition molar number is 50 or less, the compatibility and dispersibility with a solvent are good, and the viscosity at the time of dispersion is hard to rise. Further, the blending ratio of the ethylenically unsaturated monomer (a1) is preferably from 10 to 90% by weight, more preferably from 20 to 80% by weight, based on 100% by weight based on the total of the ethylenically unsaturated monomer (a2) to be described later. Preferably, it is particularly preferably 30 to 70% by weight. When it is 10% by weight or more, the dispersibility is good, and when it is 90% by weight or less, the compatibility with a solvent is excellent, the dispersibility is good, and the viscosity at the time of dispersion is also good.

(ethylenically unsaturated monomer (a2))

The ethylenically unsaturated monomer (a2) is a monomer other than the ethylenically unsaturated monomer (a1), and is not particularly limited as long as it is a monomer copolymerizable with the ethylenically unsaturated monomer (a1). It can be appropriately selected according to the use, and for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, (meth)acrylic acid can be used. Butyl ester, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, isoamyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, (A) 2-ethylhexyl acrylate, hexadecyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, (methyl) a linear or branched alkyl (meth)acrylate such as tridecyl acrylate, isomyristyl (meth) acrylate, stearyl (meth) acrylate, and isostearyl (meth) acrylate; Cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, isophthalide (meth)acrylate Ester Heterocyclic (meth) acrylates such as (meth)acrylic acid cycloalkyl esters; (meth)acrylic acid tetrahydrofuran methyl ester and (meth)acrylic acid-3-methyl-3-oxetanyl ester Benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, aromatic ring-containing (meth) acrylates; (meth)acrylic acid trifluoroethyl ester, (meth)acrylic acid octafluoropenta Ethyl esters, perfluorooctyl ethyl (meth)acrylate, and fluoroalkyl (meth)acrylates such as tetrafluoropropyl (meth)acrylate; (methyl) propylene oxime modified polydimethyl hydrazine Oxane (polyoxyl macromonomer); (meth)acrylic acid-N,N-dimethylaminoethyl ester, (meth)acrylic acid-N,N-diethylaminoethyl ester, (methyl) a (meth) acrylate containing a tertiary amino group such as N-N-dimethylaminopropyl acrylate or N,N-diethylaminopropyl (meth)acrylate; (meth) acrylate醯 Amine, dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide And N-substituted (meth) acrylamides such as acrylonitrile-N-formin; and nitriles such as (meth)acrylonitrile. Others, styrenes such as styrene and α-methylstyrene; ethylene such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether Ethers; and vinyl acetates such as vinyl acetate and vinyl propionate.

Further, a carboxyl group-containing ethylenically unsaturated monomer may also be used in combination. 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-(methyl)propene oxime ethyl phthalate, 2-(methyl) propylene oxime phthalate, 2-(methyl) propylene oxiranyl hexahydrophthalate, hexahydroanthracene Acid-2-(methyl)propene oxime, (meth)acrylic acid-β-carboxyethyl ester, and ω-carboxypolycaprolactone (meth) acrylate.

One or two or more kinds of the above-mentioned ethylenically unsaturated monomers may be selected, and from the viewpoint of solubility to a solvent and resistance, at least partially used: methyl (meth)acrylate, (A) Ethyl acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and (meth) acrylate The ethylenically unsaturated monomer selected among the butyl esters is preferred.

(Compound (a3) containing two hydroxyl groups and one thiol group in the molecule)

The compound (a3) having two hydroxyl groups and one thiol group in the molecule (hereinafter sometimes referred to as the compound (a3)) may be a compound having two hydroxyl groups and one thiol group in the molecule, and There is no particular limitation, and examples thereof include: 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2-propanediol (thioglycerol), 2-mercapto-1,2-propane Glycol, 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, and 2-mercaptoethyl-2-ethyl-1,3-propanediol. Among these, 3-mercapto-1,2-propanediol is preferred.

The molecular weight of the ethylene polymer (A) having two hydroxyl groups in the terminal end portion of the compounding purpose, the compound (a3), the ethylenically unsaturated monomer (a1), and the ethylenically unsaturated monomer (a2), and any The polymerization initiator is mixed and heated to obtain an ethylene polymer (A). The compound (a3) is preferably used in an amount of from 0.5 to 30 parts by weight based on 100 parts by weight of the total of the ethylenically unsaturated monomers (a1) and (a2), and is obtained by bulk polymerization or solution polymerization. More preferably, it is 1 to 20 parts by weight, more preferably 2 to 15 parts by weight, still more preferably 2 to 10 parts by weight.

When the compound (a3) is used in the above preferred range, the molecular weight of the ethylene polymer (A) can be adjusted to an appropriate range. The weight average molecular weight (Mw) of the converted polystyrene of the ethylene polymer (A) in gel permeation chromatography (GPC) is preferably from 500 to 20,000, more preferably from 1,000 to 10,000, particularly from 2,000 to 7,500. good. When it is 20,000 or less, the molecular weight of the ethylene polymer portion can be in an appropriate range, so that the effect of dispersibility is excellent; when it is 500 or more, the molecular weight of the ethylene polymer portion can be made to an appropriate range, and the pigment carrier and The affinity portion of the solvent has a sufficient effect of steric repulsion, so that aggregation of the pigment can be sufficiently suppressed.

(polymerization initiator)

In the polymerization, 0.001 to 5 parts by weight of a polymerization initiator can be used arbitrarily with respect to 100 parts by weight of the total of the 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 thereof include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), and 1,1'-azobis ( Cyclohexane-1-carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2-azobis(2,4-dimethyl-4-methoxy Valeronitrile, 2,2'-azobis(2-methylpropionic acid) dimethyl ester, 4,4'-azobis(4-cyanovaleric acid), 2,2'-azodi (2-hydroxymethylpropionitrile), and 2,2'-azobis[2-(2-imidazolin-2-yl)propane]. Examples of the organic peroxides include, for example, benzamidine peroxide, tert-butyl peroxybenzoate, cumene hydroperoxide, diisopropyl peroxydicarboxylate, di-n-diperoxydicarboxylate Ester, di(2-ethoxyethyl)peroxydicarboxylate, tert-butyl peroxy neodecanoate, tert-butyl peroxytrimethylacetate, peroxidation (3,5,5-trimethyl醯), dipropene peroxide, and diethyl ruthenium peroxide. These polymerization initiators may be used singly or in combination of two or more.

(polymerization solvent)

In the solution polymerization, the polymerization solvent may be used, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, hexane, acetone, hexane, methyl ethyl ketone, methyl isobutylene. The ketone, cyclohexanone, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether are not particularly limited. In terms of such a polymerization solvent, two or more kinds may be used in combination, but a solvent used in the end use is preferred.

(diisocyanate (B))

As the diisocyanate (B) constituting the pigment dispersant, conventionally known ones can be used, and examples thereof include an aromatic diisocyanate (b1), an aliphatic diisocyanate (b2), and an aromatic-aliphatic diisocyanate. (b3), an alicyclic diisocyanate (b4), or the like.

Examples of the aromatic diisocyanate (b1) include, for example, diphenyl phthalocyanate, 1,3-phenylene diisocyanate, and 4,4'-diphenyl diisocyanate. , diisocyanate-1,4-phenylene ester, diisocyanate-4,4'-diphenylmethane, 2,4-toluene diisocyanate, diisocyanate-2,6- Toluene ester, 4,4'-toluidine diisocyanate, naphthyl diisocyanate, and 1,3-bis(isocyanatemethyl)benzene.

Examples of the aliphatic diisocyanate (b2) include, for example, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, and 1,2-extension. Propyl diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate.

Examples of the aromatic-aliphatic diisocyanate (b3) include, for example, ω,ω'-diisocyanate-1,3-xylene, ω,ω'-diisocyanate-1,4-xylene, ω, Ω'-diisocyanate-1,4-diethylbenzene, diisocyanate-1,4-tetramethylxylene, and diisocyanate-1,3-tetramethylxylene.

Examples of the alicyclic diisocyanate (b4) include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI), 1,3-cyclopentane diisocyanate, and 1, 3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, and methyl-2,6-cyclohexane Alkane diisocyanate or the like.

The diisocyanate (B) exemplified above is not necessarily limited thereto, and two or more kinds thereof may be used in combination.

In terms of the diisocyanate (B), an aliphatic diisocyanate (b2), an aromatic-aliphatic diisocyanate (b3), or an alicyclic diisocyanate (b4) is preferred from the viewpoint of difficulty in yellowing, and an alicyclic system is preferred. The diisocyanate (b4) is more preferred, and 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (alias: isophorone diisocyanate, IPDI) is preferred.

Further, in addition to the above-mentioned diisocyanate, a polyvalent isocyanate having three or more isocyanate groups in one molecule may be partially used in the range in which the pigment dispersant is produced without colloidalization. Examples of such materials include a trimeric isocyanate compound, a trimethylolpropane addition type, and a biuret type of the diisocyanate (B) exemplified above.

(urethane prepolymer (E))

The urethane prepolymer (E) is obtained by reacting a hydroxyl group of an ethylene polymer (A) having two hydroxyl groups in a single terminal portion with a diisocyanate group of a diisocyanate (B).

For example, when the molar number of the ethylene polymer (A) is α and the number of moles of the diisocyanate (B) is β, when α/β=α/(α+1), theoretically, both ends thereof can be obtained. Part of a urethane prepolymer having a diisocyanate group. When α is a positive integer, the larger the α, the larger the molecular weight will be.

In the synthesis of the urethane prepolymer (E), generally known synthetic catalysts such as a tertiary amine compound and an organometallic compound can be used.

Examples of the tertiary amine compound include, for example, triethylamine, triethylenediamine, N,N-dimethylbenzylamine, N-methylmorphine, and diazabicycloundecene ( DBU) and so on.

Examples of the organometallic compound include a tin-based compound and a non-tin-based compound.

Examples of the tin-based compound include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTDL), and diacetate. Tin-tin, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyltin acetate, triethyltin oxide, tributyltin oxide, dioctyl tin oxide, tributyltin chloride, trichloroacetic acid Ding tin, and tin 2-ethylhexanoate.

Examples of the non-tin-based compound include titanium such as dibutyl titanium dichloride, tetrabutyl titanate, and titanyl titanium trichloride; lead oleate; lead 2-ethylhexanoate and lead benzoate; And a lead system such as lead naphthenate; an iron system such as iron 2-ethylhexanoate or iron acetonate pyruvate; cobalt such as cobalt benzoate and cobalt 2-ethylhexanoate; naphthenic acid A zinc system such as zinc or zinc 2-ethylhexanoate; and a zirconium system such as zirconium naphthenate.

Among the above catalysts, dibutyltin dilaurate (DBTDL) and tin 2-ethylhexanoate are preferred in terms of reactivity and hygienic properties.

The catalyst such as the above-described tertiary amine compound or organometallic compound may be used singly or in combination.

The organometallic compound catalyst used in the synthesis of the urethane prepolymer (E) can significantly promote the reaction in a further reaction with an amine described later.

A commonly known solvent is preferably used in the synthesis of the urethane prepolymer (E). The use of a solvent also has the effect of making the control of the reaction easy.

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

Further, the concentration in the urethane prepolymer reaction system when the solvent is used is converted to the concentration of the solid component of the urethane prepolymer, preferably 30 to 95% by weight from the viewpoint of reaction control. Further, from the viewpoint of viscosity control, it is preferably from 40 to 90% by weight. When it is 30% by weight or more, the reaction can be made rapid without leaving unreacted materials. When the amount is 95% by weight or less, the reaction does not proceed to a rapid portion, so that the control of the molecular weight or the like can be easily performed.

Various methods are available for the urethanation reaction of the hydroxyl group of the ethylene polymer (A) with the isocyanate group of the diisocyanate (B) to form the urethane prepolymer (E). It is generally divided into: 1) a method of adding the total amount to the reaction, and 2) adding the ethylene polymer (A) and a solvent according to necessity to the flask, and then dropping the diisocyanate (B) and then adding as necessary. The method of the catalyst is preferably 2) in the case where the reaction can be precisely controlled.

The temperature at which the reaction of the urethane prepolymer (E) is obtained is preferably 120 ° C or lower. More preferably at 50 to 110 ° C. When the temperature is higher than 110 ° C, the control of the reaction rate is difficult, and thus the urethane prepolymer having a predetermined molecular weight and structure cannot be obtained. Aminoation reaction to the catalyst It is preferably carried out in the presence of 50 to 110 ° C for 1 to 20 hours.

The molar ratio of the diisocyanate (B) to the ethylene polymer (A) is preferably from 1.01 to 3.00, and further from the viewpoint of the productivity of the urethane prepolymer. The viewpoint of the design (the balance of the pigment adsorption site and the solvent affinity site) is preferably from 1.30 to 2.30, and further from the viewpoint of the dispersion stability of the pigment dispersion using the dispersant of the final composition, from 1.50 to 2.00. optimal. When the above-mentioned blending molar ratio is too small, the dispersing agent of the final product becomes a high molecular weight, and thus the use of the pigment dispersion, and the coating material and the ink using the same have a practical problem that the viscosity becomes high. Further, as described above, when the blending molar ratio is higher than 3.00, the diisocyanate (B) having no ethylene polymerization site derived from the ethylene polymer (A) and the uric acid derived therefrom may be used. The increase in the ester site deteriorates the performance of the dispersant of the final product.

(polyamine (C))

The polyamine (C) constituting the pigment dispersant is a compound having at least two primary and/or secondary amine groups, and is used by reacting with an isocyanate group to form a urea bond. The first example of such an amine is a diamine (c1).

Examples of the diamine (c1) include, for example, a diamine (c1-1) containing two primary amino groups, a diamine (c1-2) containing two secondary amino groups, and a primary and secondary amine. Base diamine (c1-3).

As the diamine (c1-1) having two primary amino groups, generally known ones can be used, and specific examples thereof include ethylenediamine and propylenediamine [alias: 1,2-diaminopropane or 1, 2-propanediamine], trimethylenediamine, [alias: 1,3-diaminepropane or 1,3-propanediamine], tetramethylenediamine, [alias: 1,4-diamine Butane], 2-methyl-1,3-propanediamine, pentamethylenediamine, [alias: 1,5-diamine pentamane], hexamethylenediamine, [alias: 1,6-two Aliphatic ketone, such as hexane, 2,2-dimethyl-1,3-propanediamine, 2,2,4-trimethylhexamethylenediamine, and toluenediamine; An alicyclic diamine such as a diamine or a dicyclohexylmethane-4,4'-diamine; and an aromatic diamine such as a phenylenediamine or a xylylenediamine.

Further, as the diamine (c1-2) having two secondary amino groups, generally known ones can be used, and specific examples thereof include N,N-dimethylethylenediamine and N,N-diethyl. Ethylenediamine, and N,N'-di-t-butylethylenediamine.

Further, as the diamine (c1-3) containing the primary and secondary amine groups, generally known ones can be used, and specific examples thereof include N-methylethylenediamine, [alias: methylamine), N-ethylethylenediamine, [alias: ethylamine), N-methyl-1,3-propanediamine, [alias: N-methyl-1,3-diaminopropane or methamamine ], N, 2-methyl-1,3-propanediamine, N-isopropylethylenediamine, [alias: isopropylamine ethylamine], N-isopropyl-1,3-diaminopropane, [alias: N-isopropyl-1,3-propanediamine or isopropylamine propylamine], and N-lauryl-1,3-propanediamine, [alias: N-lauryl-1,3-diamine Propane or laurylamine propylamine] and the like.

The polyamine constituting the pigment dispersant is a compound containing at least two primary and/or secondary amine groups, and the primary and/or secondary amine groups react with an isocyanate group to form a urea group, and the urea group forms a pigment adsorption site. When the polyamine (C) is a compound having two primary and/or secondary amine groups at both terminals and having a secondary and/or tertiary amine group at both ends, the adsorption property to the quinoline yellow pigment can be improved. Therefore it is especially good.

In the aspect of the polyamine (C), the following may be mentioned at both ends thereof. There are two primary and/or secondary amine groups, and a polyamine (c2) having a secondary and/or tertiary amine group at both ends.

Examples of the polyamine (c2) include a polyamine (c2-1) having a secondary amino group at both ends, and a polyamine (c2-2) having a tertiary amino group at both ends.

Examples of the polyamine (c2-1) having a secondary amino group other than both ends may, for example, be an imine dipropylamine [alias: N,N-bis(3-aminopropyl)amine], N,N'- Diaminopropyl-1,3-propanediamine, and N,N'-diaminopropyl-1,4-butanediamine.

Examples of the polyamine (c2-2) having a tertiary amino group other than both ends may, for example, be methylimidodipropylamine [alias: N,N-bis(3-aminopropyl)methylamine], laurel Aminoimidodipropylamine [alias: N,N-bis(3-aminopropyl)laurylamine] and the like.

As the polyamine (C) constituting the pigment dispersant, a polymer (c3) having two or more primary and/or secondary amine groups and having a molecular weight distribution may also be used.

a first- and/or second-amine-containing polymer (c3) comprising an ethylenically unsaturated monomer having a primary amine group and an ethylenically unsaturated monomer having a secondary amine group, such as a vinylamine and an allylamine Homopolymer (so-called polyvinylamine and polyacrylamide), or a copolymer of these and other ethylenically unsaturated monomers, and a ring-opening polymer of ethyleneimine and vinyl chloride and B Diamine polycondensate and Among the ring-opening polymers of the oxazolone-2 (so-called polyethylenimine), it is preferred to select.

Among the (c1), (c2), and (c3) exemplified in the above polyamine (C), it is preferable that (c1) and (c2) are controlled by the synthesis, and the dispersion property is More preferably, it is (c2), and it is preferably a polyamine (c2-1) having a secondary amine group at both ends.

As the amine compound constituting the pigment dispersant, other monoamines may be used in addition to the polyamine (C). In the case of a monoamine, a monoamine compound having one primary or secondary amine group in the molecule, and the monoamine can inhibit excessive molecular weight in the reaction of the diisocyanate (B) and the polyamine (C), and thus can be used as a monoamine. The reaction stopper is used. The monoamine may contain other polar functional groups other than the primary or secondary amine groups in the molecule. Examples of such a polar functional group include a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, a cyano group, and a nitroxyl group.

Examples of the monoamine include conventional ones, and specific examples thereof include: amine methane, amine ethane, 1-amine propane, 2-aminopropane, 1-amine butane, 2-amine butane, and 1-amine. Pentane, 2-amine pentane, 3-amine pentane, isoamylamine, N-ethylisoamylamine, 1-amine hexane, 1-amine heptane, 2-amine heptane, 2-octylamine, 1-amine decane, 1-amine decane, 1-amine dodecane, 1-amine tridecane, 1-amine hexadecane, stearylamine, amine cyclopropane, amine cyclobutane, amine cyclopentane , amine cyclohexane, amine cyclododecane, 1-amino-2-ethylhexane, 1-amino-2-methylpropane, 2-amino-2-methylpropane, 3-amino group 1-propane, 3-aminomethylheptane, 3-isopropoxypropylamine, 3-butoxypropylamine, 3-isobutoxypropylamine, 2-ethylhexyloxypropylamine, 3-oxopropanamine, 3- Lauric propylamine, 3-myristyloxypropylamine, 2-aminomethyltetrahydrofuran, dimethylamine, diethylamine, N-methylethylamine, N-methylisopropylamine, N-methylhexylamine, diisopropylamine, two N-propylamine, di-n-butylamine, di-second butylamine, N-ethyl-1,2-dimethylpropylamine, hexahydropyridine, 2-methylpiperidine, 3-methylpiperidine, 4-methyl Piperidine, 2,4-dimethylpiperidine, 2,6-dimethyl Pyridine, 3,5-dimethylpiperidine, 3-hexahydropyridine methanol, piperidinecarboxylic acid, 4-piperidinic acid, methyl 4-piperidinecarboxylate, ethyl 4-piperidinecarboxylate, 2 - hexahydropyridine ethanol, 4-hexahydropyridine ethanol, 4-hexahydropyridyl Pyridinium hydrochloride, 4-piperidinol, pyrrolidine, 3-aminopyrrolidine, 3-pyrrolidinol, porphyrin, aniline, N-butylaniline, o-amine toluene, m-aminotoluene, Amine toluene, o-toluidine, p-toluidine, 1-anilinaphthalene, 1-amine oxime, 2-amine oxime, 1-amine oxime, 2-amine oxime, 5-amine isoquinoline, orthoamine Biphenyl, 4-aminodiphenyl ether, β-aminoethylbenzene, 2-amine diphenyl ketone, 4-amine diphenyl ketone, o-amine acetophenone, m-aminoacetophenone, p-aminoacetophenone, Benzylamine, N-toluidineamine, 3-benzylamine hydrochloride ethyl ether, 3-benzyltrihydropyridine, α-phenylethylamine, phenethylamine, p-methoxyphenethylamine, furanmethylamine, Amine azobenzene, meta-aminophenol, p-aminophenol, allylamine, and diphenylamine.

Among them, a monoamine compound having no aliphatic amine and having only a secondary amine group is preferred because of its good dispersibility.

Examples of the aliphatic monoamine compound containing only the secondary amine group include dimethylamine, diethylamine, N-methylethylamine, N-methylisopropylamine, N-methylhexylamine, diisopropylamine, and di-n-butyl Propylamine, di-n-butylamine, di-second-butylamine, N-ethyl-1,2-dimethylpropylamine, hexahydropyridine, 2-methylpiperidine, 3-methylpiperidine, 4-methylperazine Pyridine, 2,4-dimethylpiperidine, 2,6-dimethylpiperidine, 3,5-dimethylpiperidine, 3-hexahydropyridine methanol, 2-hexahydropyridine ethanol, 4-hexahydrogen Pyridineethanol, 4-piperidinol, pyrrolidine, 3-aminopyrrolidine, and 3-pyrrolidinol.

Further, since the tertiary amine group does not contain an active hydrogen reactive with an isocyanate group, a diamine containing a primary or secondary amine group and a tertiary amine group can be used as a monoamine constituting a pigment dispersant, which is used. A tertiary amine group having an effect of improving the adsorption ability of the pigment can be introduced at the end of the polymer of the dispersant.

Examples of the diamine having a primary or secondary amino group and a tertiary amino group include, for example, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N-di A a 1,3-propanediamine, and a primary amine such as N,N,2,2-tetramethyl-1,3-propanediamine, and a tertiary amine of a tertiary amine; and N, N, N '-Trimethylethylenediamine, a diamine containing a secondary amine group and a tertiary amine group.

These monoamines may be used alone or in combination of two or more. Further, the urea-bonded active hydrogen after the primary amine group and the isocyanate group are reacted with the isocyanate group at a lower reactivity and under the polymerization conditions of the dispersant, so that the molecular weight is not increased.

(Manufacturing method of pigment dispersant)

The pigment dispersant is preferably produced in the following three steps: the first step is an ethylene group represented by the formula (1) in the presence of a compound (a3) having two hydroxyl groups and one thiol group in the molecule. The unsaturated monomer (a1) and the ethylenically unsaturated monomer (a2) are subjected to radical polymerization to produce an ethylene polymer (A) having two hydroxyl groups in a single terminal portion; and the second step has two single terminal portions The hydroxyl group of the hydroxyl group ethylene polymer (A) is reacted with the isocyanate group of the diisocyanate (B) to produce a urethane prepolymer (E) having an isocyanate group at both terminals; and the third step is carried out at both ends The isocyanate group of the urethane prepolymer (E) having an isocyanate group is reacted with the primary and/or secondary amine groups of the polyamine (C).

In order to obtain a polyurethane reaction from a urethane prepolymer (E), a polyamine (C), or a urea reaction of a polyurethane having a primary or secondary amine group at the terminal, The above is divided into: 1) a method of adding a urethane prepolymer (E) solution to a flask, and then dropping a polyamine (C) therein; 2) a polyamine (C) And a solution of a solvent consisting of the necessary solvent is added to the flask, and a solution of the urethane prepolymer (E) solution is added thereto. It is possible to use any of these methods, but in the method of 2), it is preferred at the point of dispersion of the synthetic pigment dispersant.

The temperature of the urea reaction is preferably 100 ° C or less. More preferably below 70 °C. In the case where the reaction rate is still large at 70 ° C and cannot be controlled, it is more preferably 50 ° C. When the ratio is higher than 100 ° C, it is difficult to control the reaction rate, so that it is difficult to obtain a urethane urea resin having a predetermined molecular weight and structure.

Further, the blending ratio of the urethane prepolymer (E) and the polyamine (C) is not particularly limited and may be arbitrarily selected depending on the type of the pigment.

The end point of the reaction can be judged from the disappearance of the isocyanate peak by the measurement of the titrated isocyanate % or the IR measurement.

The color filter has a weight average molecular weight (Mw) of a polystyrene converted by a gel permeation chromatography (GPC) of a pigment dispersant contained in a coloring composition, preferably from 1,000 to 100,000, more preferably from 1,500 to 50,000, and from 1,500 to 1,500. 20,000 is even better.

When the weight average molecular weight is 1,000 or more, the stability of the pigment composition is good, and when it is 100,000 or less, the interaction between the resins is in a favorable range, so that the viscosity of the pigment composition does not occur. Further, the amine valence of the obtained dispersant is preferably from 1 to 100 mgKOH/g, more preferably from 2 to 80 mgKOH/g, still more preferably from 3 to 60 mgKOH/g. When the amine value is 1 mgKOH/g or more, the pigment and the functional group to be adsorbed are sufficient, so that the dispersion of the pigment is good; when it is 100 mgKOH/g or less, aggregation between the pigments does not occur, and the effect of lowering the viscosity is sufficient. The appearance is good.

The pigment dispersant is preferably used in an amount of from 5 to 70% by weight, more preferably from 10 to 50% by weight, based on the quinophthalone pigment. When it is 5% by weight or more, a good pigment dispersion effect can be obtained, and when it is 70% by weight or less, in addition to dispersibility, it does not adversely affect, for example, heat resistance.

(surfactant)

Examples of the surfactant include sodium laurate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, and alkyl naphthalenesulfonate. Sodium, sodium alkyl diphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene oxide An anionic surfactant such as ether phosphate; polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene phthalic ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, a nonionic surfactant such as polyethylene glycol monolaurate; a cationic surfactant such as an alkyl quaternary ammonium salt and an ethylene oxide adduct; an alkyl dimethylaminoacetate betaine, etc. An amphoteric surfactant such as an alkylbetaine or an alkylimidazoline may be used singly or in combination of two or more kinds, but is not necessarily limited thereto.

The content of the surfactant is preferably from 0.1 to 55 parts by weight, more preferably from 0.1 to 45 parts by weight, per 100 parts by weight of the color former. When the content of the resin-type dispersant is 0.1 part by weight or more, the effect of addition can be sufficiently obtained, and when it is 55 parts by weight or less, the dispersion can be made very good.

<Photopolymerizable monomer>

An embodiment of the coloring composition may further comprise a photopolymerizable single body. The photopolymerizable monomer may be a monomer or an oligomer which is cured by ultraviolet rays, heat, or the like to form a transparent resin, and these may be used alone or in combination of two or more. The content of the photopolymerizable monomer is preferably from 5 to 400 parts by weight based on 100 parts by weight of the color former, and more preferably from 10 to 300 parts by weight from the viewpoint of photocurability and developability.

Examples of the monomer or oligomer which are cured by ultraviolet rays, heat, or the like to form a transparent resin include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, and 2-hydroxyethyl (meth)acrylate. Ester, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, di(a) Acrylic acid-1,6-hexanediol ester, triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, trimethylolpropane tri(methyl)acrylate, three Pentaerythritol (meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diepoxypropyl Ether di(meth)acrylate, neopentyl glycol diglycidyl di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate Various esters of esters, tricyclodecyl (meth)acrylate, acrylates, (meth)acrylates of methylolated melamine, epoxy (meth)acrylates, urethane acrylates, etc. Acrylate; (meth)acrylic acid , styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, neopentyl alcohol trivinyl ether, (meth) acrylamide, N-methylol (meth) acrylamide, N-vinylformamide, acrylonitrile, EO modified bisphenol A di(meth)acrylate, di(meth)acrylic acid-1,4-butanediol ester, di(meth)acrylic acid diethylene glycol Alcohol ester, neopentyl glycol di(meth)acrylate, polyester (meth) acrylate, Tris(propylene oxyethyl)trimeric isocyanate, tris(methacrylium oxyethyl)trimeric isocyanate, caprolactone modified dipentaerythritol hexaacrylate, di-trishydroxytetrakis(meth)acrylate Methylpropane ester, neopentyl tetra(meth)acrylate, mono-carboxy-polycaprolactone mono-acrylate, ω-carboxy-polycaprolactone mono- methacrylate, 2-propene oxime Ethyl succinate, 2-methacryloxyethyl succinate, 2-propenyl propyl succinate, 2-methyl propylene oxypropyl succinate, methoxy acrylate Ester, methoxyethylene glycol methacrylate, methoxy diethylene glycol acrylate, methoxy diethylene glycol methacrylate, methoxy triethylene glycol acrylate, methoxy methacrylate Triethylene glycol ester, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, 2-hydroxy-3-benzene acrylate Oxypropyl propyl ester, 2-hydroxy-3-phenoxypropyl methacrylate, and 2-propenyl oxyethyl succinate (trade name M-5300), etc., which are commercially available, However, it is not necessarily limited to these.

<Photopolymerization initiator>

The coloring composition of the present embodiment may further contain a photopolymerization initiator. When the composition is cured by irradiation with ultraviolet rays and a color filter segment is formed by photolithography, a photopolymerization initiator or the like may be added to prepare a solvent development type or an alkali development type photosensitive coloring composition. The content of the photopolymerization initiator is preferably 2 to 200 parts by weight, more preferably 3 to 150 parts by weight, based on 100 parts by weight of the color former, and more preferably 3 to 150 parts by weight. 5 to 150 parts by weight, 5 to 200 parts by weight, and 10 to 150 parts by weight.

As an example of the photopolymerization initiator, for example, 4-phenoxydichloroacetophenone, 4-tert-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-cumene) can be used. )-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-N-formin Propane-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone Or an acetophenone-based compound such as 2-benzyl-2-dimethylamino-1-(4-N-morphinylphenyl)-butan-1-one; benzoin, benzophenone a benzoin-based compound such as a methyl ether, a benzoin ethyl ether, a benzoin isopropyl ether, or a benzyl dimethyl acetal; a diphenyl ketone, a benzamidine benzoic acid, or a benzamidine benzoic acid Ester, 4-phenyldiphenyl ketone, hydroxydiphenyl ketone, acrylated diphenyl ketone, 4-benzylidene-4'-methyldiphenyl sulfide, or 3,3',4, a diphenyl ketone compound such as 4'-tetrakis(t-butylperoxycarbonyl)diphenyl ketone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, and isopropyl a thioxanthone compound such as thioxanthone, 2,4-diisopropylthioxanthone or 2,4-diethylthioxanthone; 2,4, 6-trichloro-s-three 2-phenyl-4,6-di(trichloromethyl)-s-three , 2-(p-methoxyphenyl)-4,6-di(trichloromethyl)-s-three , 2-(p-tolyl)-4,6-di(trichloromethyl)-s-three , 2-piperidin-4,6-di(trichloromethyl)-s-three 2,4-di(trichloromethyl)-6-styryl-s-three ,2-(naphthalen-1-yl)-4,6-di(trichloromethyl)-s-three , 2-(4-methoxy-naphthalen-1-yl)-4,6-di(trichloromethyl)-s-three 2,4-trichloromethyl-(piperidinyl)-6-three Or 2,4-trichloromethyl-(4'-methoxystyryl)-6-three Three a compound; 1-[4-(phenylthio)]-1,2-octanedione 2-(O-benzamide), or O-(ethinyl)-N-(1-phenyl 2-nonyloxy-2-(4'-methoxy-naphthyl)ethylene)hydroxylamine or the like oxime ester compound; bis(2,4,6-trimethylbenzylidene)phenyl a phosphine-based compound such as phosphine oxide or 2,4,6-trimethylbenzimidyldiphenylphosphine oxide; an oxime compound such as 9,10-phenanthrenequinone, camphorquinone, acetamidine or the like; a compound; an oxazole compound; an imidazole compound; or a titanocene compound. These photopolymerization initiators may be used alone or in combination of two or more kinds in any ratio as necessary.

<sensitizer>

One embodiment of the coloring composition may further contain a sensitizer. Examples of the sensitizer include, for example, an unsaturated ketone represented by a chalcone derivative or a diphenylmethylene acetonone; and a 1,2- represented by a benzil and a camphorquinone. Diketone derivatives, benzoin derivatives, anthracene derivatives, naphthoquinone derivatives, anthracene derivatives, dibenzopyran derivatives, thioxanthene derivatives, dibenzopyran A ketone (xanthone) derivative, a thioxanthone derivative, a coumarin derivative, a ketocoumarin derivative, an anthocyanin derivative, a merocyanin derivative, a phthalocyanine ( Polymethine dyes, acridine derivatives, oximes such as oxonol derivatives (azine) derivative, thio derivative, Derivatives, porphyrin derivatives, anthracene derivatives, anthracene derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoxene Porphyrin derivative, tetrapyridyl And tetrapyrazinoporphyrazines derivatives, anthraquinone derivatives, tetrazoporphyrin derivatives, tetraquine And a tetraquinoxalinoporphyrazine derivative, a naphthalocyanine derivative, an astaxanthin derivative, a pyrylium derivative, a thiopyranidine derivative, a tetraphylline derivative, a round Annulene derivative, spiropyran derivative, spiro (spiroxazine) derivative, thiospiropyran derivative, aromatic metal complex, organic ruthenium complex, or rice ketone derivative, biimidazole derivative, α-oxime ester, ruthenium phosphine oxide , toluene glyoxylate, benzil, 9,10-phenanthrenequinone, camphorquinone, ethylhydrazine, 4,4'-diethylisoindole, 3,3'-, Or 4,4'-tetrakis(t-butylperoxycarbonyl)diphenyl ketone, 4,4'-diethylaminodiphenyl ketone or the like.

More specifically, for example, the "Pigment Handbook" (Taiwan, 1986) edited by Ohara Shinko, and the "Functional Pigment Chemistry" (produced by CMC Corporation, 1981); and Chi Senzhong Sanlang et al. The sensitizer described in "Special Functional Materials" (CMC, 1986) is not limited thereto. At the same time, others may also contain a sensitizer which exhibits absorption of light from the ultraviolet to the near infrared range.

The sensitizer may be used alone or in combination of two or more kinds in any ratio as necessary. The content of the sensitizer is preferably from 3 to 60 parts by weight, based on 100 parts by weight of the photopolymerization initiator contained in the coloring composition, and from 5 to 50 from the viewpoint of photocurability and development. The weight is better.

<Multifunctional thiol>

An embodiment of the coloring composition may further comprise a polyfunctional thiol having a chain transfer agent.

The polyfunctional thiol may be a compound containing two or more thiol groups, and examples thereof include hexanedithiol, decanedithiol, and 1,4-butanediol dithiopropane. Acid ester, 1,4-butanediol dithioglycolate, ethylene glycol dithioglycolate, ethylene glycol dithiopropionate, trimethylolpropane thioglycolate, three Hydroxymethylpropane thiopropionate, trimethylolpropane ginseng (3-mercaptobutyrate), pentaerythritol thioglycolate, pentaerythritol thiopropionate, tridecyl propionic acid Reference (2-hydroxyethyl) trimeric isocyanic acid, 1,4-dimethylphenylbenzene, 2,4,6-trimethyl-s-three , 2-(N,N-dibutylamino)-4,6-dimercapto-s-three Wait. These polyfunctional thiols may be used alone or in combination of two or more kinds in any ratio as necessary.

The content of the polyfunctional thiol is preferably from 0.1 to 30% by weight, more preferably from 1 to 20% by weight, based on the total solids of the coloring composition (100% by weight). When the content of the polyfunctional thiol is more than 0.1% by weight, the effect of adding a polyfunctional thiol can be sufficiently exhibited, and when it is less than 30% by weight, the sensitivity can be improved and the resolution can be improved.

<antioxidant>

An embodiment of the present colored composition may further contain an antioxidant. In the antioxidant, the photopolymerization initiator and the thermosetting compound contained in the coloring composition can prevent yellowing caused by oxidation of the heating step during thermal curing and ITO annealing, thereby increasing the transmittance of the coating film. Therefore, the antioxidant is contained to prevent yellowing caused by oxidation at the heating step, and a high coating film transmittance is obtained.

The "antioxidant" may be a compound having an ultraviolet absorbing function, a radical trapping function, or a peroxide decomposition function, and specific examples of the antioxidant include a hindered phenol type, a hindered amine type, and a phosphorus type. , sulfur, benzotriazole, diphenyl ketone, hydroxylamine, salicylate, and As the compound, a conventional ultraviolet absorber, an antioxidant or the like can be used.

Among these antioxidants, a hindered phenol-based antioxidant, a hindered amine-based antioxidant, a phosphorus-based antioxidant, or a sulfur-based antioxidant is preferable from the viewpoint of both the transmittance and the sensitivity of the coating film. At the same time, a hindered phenol-based antioxidant, a hindered amine-based antioxidant, or a phosphorus-based antioxidant is more preferable.

These antioxidants may be used singly or in combination of two or more kinds in any ratio as necessary. Further, the content of the antioxidant is preferably from 0.5 to 5.0% by weight based on the solid content of the coloring composition, and is excellent in brightness and sensitivity.

<Amine compound>

An embodiment of the colored composition may further contain an amine compound having an action of reducing oxygen in the dissolved state.

Examples of the amine compound include, for example, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-di Isoamyl methylaminobenzoate, 2-dimethylamine ethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, and N,N-dimethyl-p-toluidine.

<coating agent>

In one embodiment of the coloring composition, the composition on the transparent substrate can have good flatness, and a leveling agent can be further added. The leveling agent is preferably one having a polyether structure or a polyester structure of dimethyl oxirane in its main chain. Specific examples of the main chain having a polyether structure of dimethyloxane can be exemplified by: Toray, Japan. FZ-2122 manufactured by Dow-Corning, BYK-333 manufactured by BYK Chemical Co., Ltd., etc. Its main chain has a polyester construction Specific examples of the dimethyloxane include, for example, BYK-310 and BYK-370 manufactured by BYK Chemical Co., Ltd., Japan. Further, a dimethyl methoxy olefin having a polyether structure in its main chain and a dimethyl methoxy olefin having a polyester structure in its main chain may be used in combination. The content of the leveling agent is generally preferably from 0.003 to 0.5% by weight based on the total weight of the coloring composition (100% by weight).

A particularly preferred leveling agent is one of a so-called surfactant which contains a hydrophobic group and a hydrophilic group in the molecule. Specifically, even if the solubility of the hydrophilic group in water is small, the ability to lower the surface tension when added to the colored composition is low, and the glass sheet is wet even though the ability to lower the surface tension is low. Since the properties are good, it is preferable that the chargeability can be sufficiently suppressed without increasing the amount of the coating film due to foaming. A leveling agent having such a preferred property is preferably a dimethylpolysiloxane having a polyalkylene oxide unit. Among them, the polyalkylene oxide unit is a polyethylene oxide unit or a polypropylene oxide unit, and the dimethyl polyoxyalkylene may have a polyethylene oxide unit and a polypropylene oxide unit.

Further, the bonding form of the polyalkylene oxide unit of dimethyl polyoxyalkylene may be a pendant type in which a polyalkylene oxide unit is bonded in a repeating unit of dimethyl polyoxyalkylene, and the bond is bonded to a dimethyl group. The terminal end-modification type of the polyoxyalkylene and the linear block copolymerization type which is repeatedly bonded to the dimethyl polyoxane. The dimethyl polyoxyalkylene containing polyalkylene oxide units is from Toray, Japan. The Dow-Corning company sells, for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, and FZ-2207, but is not limited thereto.

In the leveling agent, an anionic, cationic, nonionic or amphoteric surfactant may also be added. The surfactant can be mixed Two or more types are used.

Examples of the anionic surfactant include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of a styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, and alkyl diphenyl. Sodium ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, poly Oxyethylene alkyl ether phosphate and the like.

Examples of the cationic surfactant include an alkyl quaternary ammonium salt and an ethylene oxide adduct. Examples of the nonionic surfactant include polyoxyethylene ether ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, and polyoxyethylene sorbitan monostearate. Acid ester, polyethylene glycol monolaurate; alkyl betaine such as alkyl dimethylaminoacetate betaine, amphoteric surfactant such as alkyl imidazoline, or surfactant of fluorine and oxime .

<hardener, hardening accelerator>

In one embodiment of the coloring composition, the curing of the thermosetting resin is assisted, and a curing agent, a curing accelerator, or the like may be further contained as necessary. The curing agent is effective as a phenol resin, an amine compound, an acid anhydride, an active ester, a carboxylic acid compound, a sulfonic acid compound, etc., but is not particularly limited thereto, and may be a reaction with a thermosetting resin. Any hardener can be used. Moreover, a preferred example thereof is a compound containing two or more phenolic hydroxyl groups in one molecule, and an amine-based curing agent. As an example of the hardening accelerator, for example, an amine compound (e.g., dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methyl can be used. Oxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc.), quaternary ammonium salt compound (eg, triethylbenzylammonium chloride, etc.) , blocked isocyanate compounds (such as: dimethylamine, etc.), imidazole derivatives, bicyclic guanidine compounds and salts thereof (eg, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methyl) Imidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, etc., Phosphorus compounds (such as triphenylphosphine, etc.), guanamine compounds (such as: melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-three Derivatives (eg 2,4-diamino-6-methylpropenyloxyethyl-S-three) 2-vinyl-2,4-diamino-S-three 2-vinyl-4,6-diamino-S-three . Trimeric isocyanate adduct, 2,4-diamino-6-methylpropenyloxyethyl-S-three . Trimeric isocyanate adduct, etc.). These may be used alone or in combination of two or more. The content of the hardening accelerator is preferably 0.01 to 15 parts by weight based on 100 parts by weight of the thermosetting resin.

<Other additive ingredients>

In one embodiment of the coloring composition, other additive components may be further contained as necessary. For example, in order to stabilize the viscosity of the composition over time, the stabilizer may be further stored. Further, in order to improve the adhesion to the transparent substrate, a further improver such as a decane coupling agent may be further contained.

Examples of the stabilizer can be exemplified by quaternary ammonium chloride such as benzyltrimethylammonium chloride or diethylhydroxylamine; organic acids such as lactic acid and oxalic acid, and methyl ether; and tert-butyl catechol; , organic phosphines such as tetraethylphosphine and tetraphenylphosphine, phosphites, and the like. The stabilizer is stored in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the coloring agent.

Examples of the modifying agent include vinyl hydride such as ethylene tris(β-methoxyethoxy) decane, ethylene ethoxy decane, and ethylene trimethoxy decane; γ-methyl propylene oxypropyl trimethoxy decane, and the like. (meth)acrylic acid decane; β-(3,4-epoxycyclohexyl)ethyltrimethoxy decane, β-(3,4-epoxycyclohexyl)methyltrimethoxy decane, β-(4- Epoxycyclohexyl)ethyltriethoxy decane, β-(3,4-epoxycyclohexyl)methyltriethoxy decane, γ-glycidoxypropyltrimethoxy decane, γ-glycidoxypropane Epoxy decanes such as triethoxy oxane; N-β-(aminoethyl)-γ-aminopropyltrimethoxy decane, N-β-(aminoethyl)-γ-aminopropyltriethoxy decane , N-β-(Aminoethyl)-γ-aminopropylmethyldiethoxy decane, γ-aminopropyltriethoxy decane, γ-aminopropyltrimethoxy decane, N-phenyl-γ-amine Amino decane such as propyltrimethoxy decane or N-phenyl-γ-aminopropyltriethoxy decane; thiononane such as γ-mercaptopropyltrimethoxy decane or γ-mercaptopropyltriethoxy decane; A decane coupling agent. Next, the modifier is preferably used in an amount of from 0.01 to 10 parts by weight, more preferably from 0.05 to 5 parts by weight, per 100 parts by weight of the coloring agent.

<Method for Producing Colored Composition>

In one embodiment of the colored composition (hereinafter, also referred to as a pigment dispersion), the colorant may be preferably used together with a dispersion aid in a color carrier carrier and/or a solvent such as a binder resin. It is manufactured by finely dispersing various kinds of dispersing means such as a kneader, a 2-axis roll mill, a 3-axis roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, a ring bead mill, or an attritor. Meanwhile, when two or more kinds of coloring agents are contained, two or more coloring agents may be simultaneously dispersed in the coloring agent carrier, or may be separately in the coloring agent carrier. The dispersed materials are mixed. Further, when the solubility of the colorant is high, it is particularly required because it has high solubility in the solvent to be used, and when it is dissolved by stirring to determine that no foreign matter is present, it is not necessary to be finely dispersed and produced as described above.

When a photosensitive coloring composition (photoresist material) for a color filter is used, a solvent development type or an alkali development type coloring composition can be prepared. The solvent-developing type or the alkali-developing type coloring composition, the pigment dispersion, the photopolymerizable monomer and/or the photopolymerization initiator, and the solvent and other dispersing auxiliary agent, It is adjusted by mixing with additives and the like. The photopolymerization initiator may be added at a stage in which the coloring composition is prepared, or may be added after being prepared into a coloring composition.

<Removal of coarse particles>

In one embodiment of the coloring composition, a centrifugal separation, a sintering filter, and a filtration membrane filtration may be employed, and coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more are preferable. And the dust particles mixed in are removed. Such a coloring composition is preferably one containing substantially no particles of 0.5 μm or more. It is more preferable to contain particles of 0.3 μm or less.

<color filter>

Next, the color filter will be described. The color filter is provided with a color filter segment formed by an embodiment of the present colored composition. The color filter is provided with, for example, a red color filter segment, a green color filter segment, and a blue color filter segment. In addition, the color filter may further include: a magenta color filter segment, a cyanine color filter segment, and a yellow color filter segment.

One embodiment of the coloring composition is used in red, green, Preferably, the formation of a yellow color filter segment is preferred, and it is preferably used in a green color filter segment. The color filter may be formed by a colored composition of an embodiment of the present invention, as long as at least one of the color filter segments is formed by using the coloring composition of one embodiment of the present invention. For the coloring agent used for the formation of the color filter segments of other colors, conventionally known ones can be used.

Examples of the coloring agent used in the red color filter segment include, for example, CI Pigment Red No. 7, No. 14, No. 41, No. 48:1, No. 48:2, No. 48:3, No. 48:4. 57:1, 81, 81:1, 81:2, 81:3, 81:4, 122, 146, 149, 166, 168, 169, 176, 177 No., No. 178, No. 179, No. 184, No. 185, No. 187, No. 200, No. 202, No. 208, No. 210, No. 221, No. 242, No. 246, No. 254, No. 255, No. 264, No. 270, Red pigments Nos. 272, 273, 274, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, or 287. Further, a red dye such as a dibenzopipelane, an azo system, a disazo system or a guanidine system may also be used. Specific examples thereof include a salt forming compound of a dibenzopyrano acid dye such as C.I. Acid Red No. 52, No. 87, No. 92, No. 289, No. 338, and the like.

Meanwhile, in the red color filter segment, an orange colorant and/or a yellow colorant may be used in combination. Examples thereof include orange pigments such as CI Pigment Orange No. 38, No. 43, No. 71, and No. 73, and/or CI Pigment Yellow No. 1, No. 2, No. 3, No. 4, No. 5, No. 6, No. 10, No. 12, No. 13, No. 14, No. 15, No. 16, No. 17, No. 18, No. 23, No. 31, No. 32, No. 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 No., 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171 , 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 198, 199 Yellow pigments such as No. 213, No. 214, No. 218, No. 219, No. 220, or No. 221. Further, an orange dye and/or a yellow dye such as a quinoline system, an azo system, a disazo system or a methine group may also be used.

Examples of the coloring agent used in the green color filter segment include green pigments such as C.I. Pigment Green No. 7, No. 36, No. 37, No. 58 and the like. In addition, a blue pigment such as an anthraquinone aluminum pigment can also be used. In the case of a green color filter segment, a yellow colorant may also be used in combination, specifically, for example, a yellow colorant as described in the description of the red color filter segment.

Examples of the coloring agent used in the blue color filter segment include, for example, CI Pigment Blue No. 1, No. 1: 2, No. 9, No. 14, No. 15, No. 15, No. 1: 15, No. 15, 15 : Blue pigments such as No. 3, No. 15, No.: No. 15, No. 16, No. 16, No. 22, No. 60, No. 64, etc. In addition, a purple pigment can also be used in combination. can Examples of the purple pigment used together include, for example, CI Pigment Violet No. 1, No. 1, No. 1, No. 2, No. 2, No. 3, No. 3, No. 1, No. 3, No. 3, No. 5, No. 5: No. , 14, 15, 15, 16, 19, 23, 27, 29, 30, 31, 32, 37, 39, 40, 42, 44, 47, 49 No. 50, purple pigment such as 50. In addition, other salt-forming compounds of basic dyes and acid dyes which are blue and purple may also be used. When a dye is used, a triarylmethane dye or a dibenzopyran dye is preferred in terms of brightness.

<Method of Manufacturing Color Filter>

An embodiment of the color filter can be manufactured by a printing method or a photolithography method.

In the formation of the color filter by the printing method, since the printing ink prepared by the coloring composition is repeatedly printed and dried to be imaged, the color filter manufacturing method is low in cost and excellent in mass productivity. . In addition, the development of printing technology enables the printing of fine images with higher dimensional fineness and smoothness. When printing is performed, it is preferable to constitute a composition which does not allow the ink to be dried and solidified on the printing plate or the felt. In addition, the control of the fluidity of the ink on the printing press is also important, which allows the dispersant and the filling pigment to adjust the ink viscosity.

When the color filter segment is formed by photolithography, the above-mentioned solvent developing type or alkaline developing type colored resist material can be prepared into a colored composition, and on a transparent substrate, a spray coater or a spin coater can be used. A coating method such as an extrusion coater or a roll coater is applied so as to form a dry film thickness of 0.2 to 5 μm. According to the necessary dry film, it can be designed to be in contact with or non-contact with the film. Ultraviolet exposure is performed by a photomask having a predetermined image. After that, the uncured portion is removed by immersion in a solvent or an alkali developing solution or by a sprayer or the like to form a desired image, and then the same operation is repeated for other colors to manufacture a color filter. . Among them, in order to promote the polymerization of the colored photoresist, it is also possible to carry out a heating operation as necessary. By the photolithography method, a color filter having a high degree of fineness can be produced by the above printing method.

In the case of development, an alkali solution such as sodium carbonate or sodium hydroxide may be used as the alkali imaging solution, and an organic base such as dimethylbenzylamine or triethanolamine may also be used. Among them, an antifoaming agent and a surfactant may be further added to the developing solution. In addition, in order to increase the sensitivity of ultraviolet exposure, after the above-mentioned colored photoresist material is coated and dried, it may be coated with a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble alkali resin to prevent oxidation. After blocking the polymerized film, ultraviolet exposure is performed.

The color filter may be produced by an electrodeposition method, a transfer method, an inkjet method or the like in addition to the above methods. The electrodeposition method is a method of manufacturing a color filter by electrodeposition of color filter segments of respective colors on a transparent conductive film by electrophoresis of colloidal particles by using a transparent conductive film formed on a substrate. Further, the transfer method is a method in which a color filter segment is formed in advance on the surface of the peelable transfer base tab, and the color filter segment is transferred onto a desired substrate.

A black matrix may be formed before the color filter segments are formed on the transparent substrate or the reflective substrate. The black matrix is a multilayer film of chromium or chromium/chromium oxide, an inorganic film such as titanium nitride, or a resin film in which a photomask is dispersed, but is not limited thereto. Further, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then color filter segments of the respective colors may be formed. Simultaneously In an embodiment of the color filter, a protective film, a transparent conductive film, or the like may be formed as necessary.

The color filter is bonded to the counter substrate by a sealant, and the liquid crystal is injected after the liquid crystal is injected from the injection port provided in advance from the sealing portion, and then the polarizing film or the retardation film is bonded to the outer side of the substrate as necessary. , can be manufactured into a liquid crystal display panel

The liquid crystal display panel uses a color filter such as a twisted nematic (TN), a super twisted nematic (STN), a planar switching (IPS), a vertical alignment (VA), or an optically compensated bending (OCB). Used in the colorful LCD module.

Example

Hereinafter, each of the embodiments I to VIII will be described by way of examples, but the invention is not limited thereto. In the examples and the reference examples, "%" means "% by weight" unless otherwise specified. Further, the measurement of the average primary particle diameter and the identification of the compound were carried out as follows.

<Average primary particle size of colorant>

The average primary particle diameter of the colorant was measured by a method of directly measuring the size of primary particles using an electron microscope photograph using a transmission type (TEM) electron microscope. Specifically, the minor axis diameter and the major axis diameter of the primary particles of each coloring agent are measured, and the average is used as the particle diameter of the primary particle of the coloring agent. Next, for 100 or more colorant particles, the volume (weight) of each particle is determined by a cube having an approximate particle diameter, and the volume average particle diameter is an average primary particle diameter.

<identification of compounds>

The compound was identified by the MALDI mass spectrometer autoflex III (hereinafter referred to as TOF-MS) manufactured by Bruker Daltonics, and the molecular ion wave of the obtained mass spectrum was identified in accordance with the calculated mass.

"Implementation I"

Prior to the examples, a method for producing the pigment derivative (1) and the blue colorant 1 (B-1) used in the colored composition will be described.

(Manufacture of pigment derivative (1))

The dye derivative (1) was obtained according to the synthesis method described in Japanese Patent No. 4585781.

(Manufacture of blue colorant 1 (B-1))

First, 225 parts of phthalonitrile and 78 parts of anhydrous aluminum chloride were added to 1250 parts of n-pentanol in a reaction vessel, followed by stirring. Thereafter, 266 parts of DBU (1,8-diazabicyclo[5.4.0]-7-undecene) was added thereto and the temperature was raised, and the mixture was refluxed at 136 ° C for 5 hours. The reaction solution cooled to 30 ° C under stirring, mixed solvent of 5000 parts of methanol and 10000 parts of water It was added under stirring to obtain a blue slurry. The slurry was further filtered, washed with a mixed solvent of 2000 parts of methanol and 4000 parts of water, and dried to obtain 135 parts of chloroaluminium anthraquinone (A1Pc-C1). Thereafter, 100 parts of chloroaluminum in the reaction vessel was gradually added to 1200 parts of concentrated sulfuric acid at room temperature. After further stirring at 40 ° C for 3 hours, the sulfuric acid solution was poured into 24,000 parts of 3 ° C cold water. The blue precipitate was filtered, washed with water and dried to obtain 102 parts of hydroxyaluminum (A1Pc-OH).

Then, 100 parts of hydroxyaluminum phthalocyanine (A1Pc-OH), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were added to a stainless steel one-gallon kneader (manufactured by Inoue, Ltd.), and Mix at 60 ° C for 6 hours. The mixture was poured into 3000 parts of warm water, heated to 70 ° C while stirring for 1 hour to make it into a slurry form, repeatedly filtered, washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. One night, 98 parts of a blue colorant (B-1) was obtained. Its average primary particle size was 31.2 nm.

[Example 1] (Manufacture of yellow colorant 1 (Y-1))

The compound (1) is obtained according to the synthesis method described in JP-A-2008-81566.

100 parts of the compound (1), 300 parts of methyl benzoate, 70 parts of 2,3-naphthalene dicarboxylic anhydride and 143 parts of benzoic acid were heated to 180 ° C for 4 hours. Then, the formation of the quinophthalone compound (a) and the disappearance of the compound (1) of the starting material were determined by TOF-MS. Thereafter, 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 further separated by filtration, washed with methanol, and dried to obtain 120 parts of the quinoline compound (a). The result of mass analysis by TOF-MS was identified as the quinophthalone compound (a).

Next, 100 parts of the above quinophthalone compound (a), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a 1-gallon kneader made of stainless steel (manufactured by Inoue, Japan) at 60 ° C. The mixture was mixed for 6 hours and subjected to salt milling. Next, the mixture was put into 3 liters of warm water, heated to 70 ° C while stirring for 1 hour to make a slurry, repeated filtration, washing with water to remove sodium chloride and diethylene glycol, and then at 80 ° C After drying overnight, 98 parts of yellow colorant 1 (Y-1) were obtained. Its average primary particle size is 31.3 nm.

[Embodiment 2] (Manufacture of yellow colorant 2 (Y-2))

First, 70 parts of quinoline yellow compound (a), 30 parts of CI Pigment Yellow No. 138 ("Paliotol Yellow K0960-HD" manufactured by BASF Corporation), 1200 parts of sodium chloride, and 120 parts of diethylene glycol are added. A 1 gallon kneader (Kneader) made of stainless steel (manufactured by Inoue, Japan) was mixed at 60 ° C for 8 hours. Next, the mixture is put into warm water, heated to about 70 ° C while stirring for 1 hour to make it into a slurry, repeatedly filtered, washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. One night, 97 parts of yellow colorant 2 (Y-2) were obtained. Its average primary particle diameter was 30.4 nm.

[Example 3] (Manufacture of yellow colorant 3 (Y-3))

In addition to 70 parts of quinoline yellow compound (a) and 30 parts of CI Pigment Yellow No. 138 ("Paliotol Yellow K0960-HD" manufactured by BASF Corporation), 50 parts of quinoline yellow compound (a) and 50 parts each were changed. The yellow coloring agent 3 (Y-3) was obtained in the same manner as in the production of the yellow coloring agent 2 (Y-2) except for CI Pigment Yellow No. 138 ("Paliotol Yellow K0960-HD" manufactured by BASF Corporation). Its average primary particle diameter was 29.6 nm.

[Example 4] (Manufacture of yellow colorant 4 (Y-4))

In addition to 70 parts of quinoline yellow compound (a) and 30 parts of CI Pigment Yellow No. 138 ("Paliotol Yellow K0960-HD" manufactured by BASF Corporation), each was changed to 20 parts of quinoline yellow compound (a) and 80 parts. The yellow coloring agent 4 (Y-4) was obtained in the same manner as in the production of the yellow coloring agent 2 (Y-2) except for CI Pigment Yellow No. 138 ("Paliotol Yellow K0960-HD" manufactured by BASF Corporation). Its average primary particle diameter was 31.8 nm.

[Example 5] (Manufacture of yellow colorant 5 (Y-5))

In addition to 70 parts of 2,3-naphthalenedicarboxylic anhydride, changed to 42 parts of a mixture of 2,3-naphthalenedicarboxylic anhydride and 60 parts of tetrachlorophthalic anhydride, in addition to yellow coloring agent (Y-1) The same operation was carried out to obtain a yellow coloring agent 5 (Y-5) obtained from a mixture of the quinophthalone yellow compound (a) and the pigment yellow 138. Average The primary particle size was 28.0 nm. As a result of measurement by TOF-MS, it was found that the composition ratio of the quinoline yellow compound (a) to the pigment yellow-138 in the yellow coloring agent 5 was 5:5.

[Embodiment 6] (Manufacture of yellow colorant 6 (Y-6))

First, in 200 parts of methyl benzoate, 35 parts of 8-aminomethylquinoline, 33 parts of 2,3-naphthalene dicarboxylic anhydride, and 47 parts of tetrachlorophthalic anhydride, 154 parts of benzoic acid are added. Heat to 180 ° C and react for 2 hours. Next, 95 parts of tetrachlorophthalic anhydride and 50 parts of benzoic acid were further added, followed by stirring at 180 ° C for 3 hours. Thereafter, 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 further separated by filtration, washed with methanol, and dried to give 125 parts of quinoline compound. The result of measurement by TOF-MS was confirmed to be a yellow coloring agent 6, wherein the main component is a quinophthalone compound (a) and the pigment yellow-138 was composed of a composition ratio of about 5:5. At the same time, since it is also observed that the molecular ion wave of the quinoline yellow compound (c) is in a trace amount, it is shown that the quinoline yellow compound (c) also contains a very small amount.

Then, 100 parts of the obtained quinophthalone compound, 1200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a stainless steel one-gallon kneader (manufactured by Inoue, Ltd.) at 60 ° C. Mix under 8 hours. Next, the mixture is put into warm water, heated to about 70 ° C while stirring for 1 hour to make it into a slurry, repeatedly filtered, washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. One night, 98 parts of yellow colorant 6 (Y-6) were obtained. Its average primary particle diameter was 29.0 nm.

[Embodiment 7] (Manufacture of yellow colorant 7 (Y-7))

First, 40 parts of 8-aminomethylquinoline, 150 parts of 2,3-naphthalenedicarboxylic anhydride, and 154 parts of benzoic acid were added to 200 parts of methyl benzoate, and the mixture was heated to 180 ° C and stirred for 4 hours. Thereafter, 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 further separated by filtration, washed with methanol, and dried to obtain 116 parts of quinoline compound (c). The result of mass analysis by TOF-MS was identified as the quinoline yellow compound (c).

Thereafter, 100 parts of the obtained quinoline yellow compound (c), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a 1-gallon kneader (manufactured by Inoue, Ltd.) made of stainless steel, and Mix for 8 hours at 60 °C. Next, the mixture is put into warm water, heated to about 70 ° C while stirring for 1 hour to make it into a slurry, repeatedly filtered, washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. One night, 97 parts of yellow colorant 7 (Y-7) were obtained. Its average primary particle diameter was 34.1 nm.

[Embodiment 8] (Manufacture of yellow colorant 8 (Y-8))

The compound (2) is obtained by the same method as the synthesis of the compound (1), using the quinoline yellow compound (c) as a raw material, and the synthesis method described in JP-A-2008-81566.

To 300 parts of methyl benzoate, 100 parts of the compound (2), 108 parts of tetrachlorophthalic anhydride, and 143 parts of benzoic acid were added, and the mixture was further heated to 180 ° C to carry out a reaction for 4 hours. Then, the formation of the quinophthalone compound (b) and the disappearance of the compound (2) of the starting material were determined by TOF-MS. Thereafter, 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 further subjected to filtration separation, methanol washing, and drying to obtain 120 parts of quinoline yellow compound (b). As a result of mass analysis by TOF-MS, it can be identified as a quinophthalone compound (b).

Thereafter, 100 parts of the obtained quinophthalone compound (b), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a 1-gallon kneader (manufactured by Inoue, Ltd.) made of stainless steel, and Mix for 8 hours at 60 °C. Next, the mixture is put into warm water, heated to about 70 ° C while stirring for 1 hour to make it into a slurry, repeatedly filtered, washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. One night, 98 parts of yellow colorant 8 (Y-8) were obtained. Its average primary particle size was 31.1 nm.

[Embodiment 9] (Manufacture of yellow colorant 9 (Y-9))

The same operation as the manufacture of the yellow coloring agent 3 (Y-3) except that 50 parts of the quinophthalone compound (a) was changed to 50 parts of the quinophthalone compound (b). This gave yellow colorant 9 (Y-9). Its average primary particle diameter was 30.2 nm.

[Embodiment 10] (Manufacture of yellow colorant 10 (Y-10))

A quinoline yellow compound was obtained in the same manner as in the production of yellow colorant 1 (Y-1) except that 70 parts of 2,3-naphthalene dicarboxylic anhydride was changed to 70 parts of 1,2-naphthalene dicarboxylic anhydride. (d) Yellow colorant 10 (Y-10). Its average primary particle diameter was 31.6 nm.

[Example 11] (Manufacture of yellow colorant 11 (Y-11))

First, 200 parts of the compound (2), 176 parts of tetrabromophthalic anhydride, and 143 parts of benzoic acid were added to 300 parts of methyl benzoate, and the mixture was further heated to 180 ° C to carry out a reaction for 6 hours. Then, the formation of the quinophthalone compound (h) and the disappearance of the compound (2) of the starting material were determined by TOF-MS. Thereafter, 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 further separated by filtration, washed with methanol, and dried to obtain 138 parts of quinoline compound (h). As a result of mass analysis by TOF-MS, it was identified as a quinophthalone compound (h).

Thereafter, 100 parts of the obtained quinoline yellow compound (h), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a 1-gallon kneader (manufactured by Inoue, Ltd.) made of stainless steel, and Mix for 8 hours at 60 °C. Next, the mixture is put into warm water, heated to about 70 ° C while stirring for 1 hour to make it into a slurry, repeatedly filtered, washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. One night, 97 parts of yellow colorant 11 (Y-11) were obtained. Its average primary particle diameter was 28.3 nm.

[Embodiment 12] (Manufacture of yellow colorant 12 (Y-12))

First, 52 parts of the quinoline yellow compound (a) was dissolved in 428 parts of 98% sulfuric acid and 472 parts of 25% fuming sulfuric acid, and further stirred at 85 ° C for 2 hours to carry out a sulfonation reaction. Next, the reaction solution was further dropped into 6000 parts of ice water, and the quinoline yellow compound precipitated therein was filtered, and after washing with water, the paste was obtained. The resulting paste was then redispersed in 8000 parts of water and stirred at room temperature for 1 hour. After separating by filtration and washing with water, it was dried overnight at 80 ° C to obtain 54 parts of quinoline yellow compound (k). As a result of mass analysis by TOF-MS, it was identified as a quinophthalone compound (k).

Thereafter, 50 parts of the obtained quinoline yellow compound (k) and 50 parts of CI Pigment Yellow No. 138 ("Paliotol Yellow K0960-HD" manufactured by BASF Corporation), 1200 parts of sodium chloride, and 120 parts were further added. Diethylene glycol was placed in a 1-gallon kneader made of stainless steel (manufactured by Inoue, Ltd.), and mixed at 60 ° C for 8 hours. Next, the mixture is put into warm water, heated to about 70 ° C while stirring for 1 hour to make it into a slurry, repeatedly filtered, washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. One night, 95 parts of yellow colorant 12 (Y-12) were obtained. Its average primary particle size is 36.8 nm.

[Example 13] (Manufacture of yellow colorant 13 (Y-13))

First, 44 parts of the quinophthalone compound (b) was dissolved in 540 parts of 95% sulfuric acid, and then 38 parts of N-methylol phthalamide was added thereto, followed by stirring at 85 ° C for 7 hours. After cooling, the reaction solution was dropped into 3600. In a portion of ice water, the quinophthalone compound which is precipitated and separated by filtration is washed, and the paste is obtained. The resulting paste was then redispersed in 5000 parts of water and stirred at room temperature for 1 hour. After separating by filtration and washing with water, it was dried overnight at 80 ° C to obtain 53 parts of quinoline yellow compound (r). As a result of mass analysis by TOF-MS, it was identified as a quinoline yellow compound (r).

Thereafter, 50 parts of the obtained quinoline yellow compound (r) and 50 parts of CI Pigment Yellow No. 138 ("Paliotol Yellow K0960-HD" manufactured by BASF Corporation), 1200 parts of sodium chloride, and 120 parts were further added. Diethylene glycol was placed in a 1-gallon kneader made of stainless steel (manufactured by Inoue, Ltd.), and mixed at 60 ° C for 8 hours. Next, the mixture is put into warm water, heated to about 70 ° C while stirring for 1 hour to make it into a slurry, repeatedly filtered, washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. One night, 98 parts of yellow colorant 13 (Y-13) were obtained. Its average primary particle diameter was 35.4 nm.

[Embodiment 14] (Manufacture of yellow colorant 14 (Y-14))

In addition to 50 parts of CI Pigment Yellow No. 138 ("Paliotol Yellow K0960-HD" manufactured by BASF Corporation), changed to 50 parts of CI Pigment Yellow No. 150 ("E4GN" manufactured by Lanxess Co., Ltd.), in addition to yellow coloring agent 3 ( The same operation as in the production of Y-3) gave yellow colorant 14 (Y-14). Its average primary particle diameter was 36.5 nm.

[Reference Example 1] (Manufacture of yellow colorant 15 (Y-15))

100 parts of C.I. Pigment Yellow No. 138 (manufactured by BASF) "Paliotol Yellow K0960-HD"), 1200 parts of sodium chloride, and 120 parts of diethylene glycol, added to a stainless steel 1 gallon kneader (manufactured by Inoue, Japan), and mixed at 60 ° C for 8 hours. . Next, the mixture is put into warm water, heated to about 70 ° C while stirring for 1 hour to make it into a slurry, repeatedly filtered, washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. One night, 98 parts of yellow colorant 15 (Y-15) were obtained. Its average primary particle size is 35.8 nm.

[Reference Example 2] (Manufacture of yellow colorant 16 (Y-16))

In addition to 100 parts of CI Pigment Yellow No. 138 ("Paliotol Yellow K0960-HD" manufactured by BASF Corporation), changed to 100 parts of CI Pigment Yellow No. 150 ("E4GN" manufactured by Lanxess Co., Ltd.), in addition to yellow coloring agent 15 ( The same operation as in the production of Y-15) gave yellow colorant 16 (Y-16). Its average primary particle diameter was 36.5 nm.

[Reference Example 3] (Manufacture of yellow colorant 17 (Y-17))

In addition to 100 parts of CI Pigment Yellow No. 138 ("Paliotol Yellow K0960-HD" manufactured by BASF), changed to 50 copies of CI Pigment Yellow No. 138 ("Paliotol Yellow K0960-HD" manufactured by BASF) and 50 CIs A yellow coloring agent 17 (Y-17) was obtained in the same manner as in the production of yellow coloring agent 15 (Y-15) except for a mixture of Pigment Yellow No. 150 ("E4GN" manufactured by Lanxess Co., Ltd.). Its average primary particle size was 37.2 nm.

The contents of the yellow colorants 1 to 17 (Y-1 to 17) produced by the present invention are shown in Table 1. "PY138" and "PY150" described in Table 1 are each C.I. Pigment Yellow No. 138 and C.I. Pigment Yellow No. 150.

<Method for Producing Binder Resin Solution> (modulation of acrylic resin solution 1)

196 parts of cyclohexanone was placed in a reaction vessel equipped with a thermometer, a condenser, a nitrogen introduction tube, a dropping tube, and a stirring device in a separable 4-necked flask, and the temperature was raised to 80 ° C, and the reaction vessel was replaced. After nitrogen gas, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, and 20.7 parts of p-isopropylidene phenol were epoxy-coated via a dropping tube. A mixture of ethane-modified acrylate ("Aronix M110" manufactured by Japan East Asia Synthetic Co., Ltd.) and 1.1 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After the completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a solution of an acrylic resin. After cooling to room temperature, sample about 2 parts of the tree. The fat solution was dried by heating at 180 ° C for 20 minutes to measure a nonvolatile matter, and methoxypropyl acetate was added so as to have a nonvolatile content of 20% by mass in the previously synthesized resin solution to prepare an acrylic resin solution 1. Its weight average molecular weight (Mw) was 26,000.

(modulation of acrylic resin solution 2)

207 parts of cyclohexanone was placed in a reaction vessel equipped with a thermometer, a condenser, a nitrogen introduction tube, a dropping tube, and a stirring device in a separable 4-necked flask, and the temperature was raised to 80 ° C, and the reaction vessel was replaced. After nitrogen gas, 20 parts of methacrylic acid, 20 parts of p-isopropylidene phenol oxirane modified acrylate ("Aronix M110" manufactured by Japan East Asia Synthesis Co., Ltd.), and 45 parts of methyl group were dropped by a dropping tube. A mixture of methyl acrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 1.33 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After the completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a copolymer resin solution. Next, the total amount of the copolymer solution was further 6.5 parts of isocyanate-2-methylpropenyloxyethyl ester after cooling to room temperature after stopping nitrogen gas and stirring with dry air for 1 hour. A mixture of Karenz MOI, 0.08 parts of dibutyltin laurate, and 26 parts of cyclohexanone was added dropwise at 70 ° C for 3 hours. After the completion of the dropwise addition, the reaction was further 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 dried by heating at 180 ° C for 20 minutes, and the nonvolatile matter was measured, and cyclohexanone was added in such a manner that the nonvolatile content was 20% by mass in the previously synthesized resin solution. It was prepared into an acrylic resin solution 2. Its weight average molecular weight (Mw) was 18,000.

(weight average molecular weight of binder resin)

The weight average molecular weight of the acrylic resin is the weight average molecular weight of the converted polystyrene measured by GPC (gel permeation chromatography).

<Production of yellow coloring composition> [Example 15] (Production of yellow coloring composition 1 (YP-1))

After the mixture of the following components was stirred and mixed to be uniform, zirconia beads having a diameter of 0.5 mm were used, and dispersed by an Eiger polishing disperser ("Mini Model M-250 MK II" manufactured by Eiger Japan Co., Ltd.) for 5 hours. The mixture was filtered through a 5 μm sieve to prepare a yellow colored composition 1 (YP-1).

[0383]

[Examples 16 to 28, Reference Examples 4 to 6] (Production of yellow coloring compositions 2 to 14, 20 to 22 (YP-2 to 14, 20 to 22))

The yellow coloring composition 1 (Y-1) was changed to the yellow coloring agent as described in Table 2, and yellow colored compositions 2 to 14 were produced in the same manner as in the yellow colored composition 1 (YP-1). 20 to 22 (YP-2 to 14, 20 to 22).

[Example 29] (Production of yellow coloring composition 15 (YP-15))

After the mixture of the following components was stirred and mixed to be uniform, zirconia beads having a diameter of 0.5 mm were used, and dispersed by an Eiger polishing disperser ("Mini Model M-250 MK II" manufactured by Eiger Japan Co., Ltd.) for 5 hours. The mixture was filtered through a 5 μm sieve to prepare a yellow colored composition 15 (YP-15).

[0386]

[Examples 30 to 33, Reference Examples 7 to 9] (Production of yellow coloring compositions 16 to 19, 23 to 25 (YP-16 to 19, 23 to 25))

In addition to changing the yellow coloring agent 1 (Y-1) to the yellow coloring agent as described in Table 2, yellow colored compositions 16 to 19 were produced in the same manner as in the yellow colored composition 15 (YP-15). 23 to 25 (YP-16 to 19, 23 to 25).

<Evaluation of yellow coloring composition>

The yellow coloring composition was evaluated by making a coating film with a yellow coloring composition, and then measuring the brightness, film thickness, and contrast value for evaluation. The evaluation method is shown below.

(evaluation of brightness)

Coloring composition in yellow, in 100mm × 100mm, 1.1mm thick glass The glass substrate was coated with a spin coater, and then heated at 230 ° C for 20 minutes to obtain a coating film. At this time, the film thickness of the coating film was applied to the coating condition of x=0.440 (rotation number and time of the spin coater) in the C light source after heat treatment at 230° C., and was applied as appropriate. The obtained coating film was measured for its brightness (Y) by a microspectrophotometer ("OSP-SP100" manufactured by Olympus, Japan), and was judged according to the following criteria.

○: 89.0 or more

△: 87.5 or more and less than 89.0

×: not up to 87.5

(assessment of tinting strength)

The film thickness at the chromaticity of x (C) = 0.440 was measured by the same coating film as the brightness evaluation, and was determined according to the following criteria. The smaller the film thickness imparting the chromaticity of x(C) = 0.440, the larger the coloring power is, which is preferable.

○: less than 2.0 [μm]

△: 2.0 or more and less than 3.0 [μm]

×: 3.0 or more [μm]

(evaluation of comparison value)

The light emitted from the backlight unit for the liquid crystal display device is polarized by the polarizing plate, and passes through the coating film of the colored composition coated on the glass substrate to reach the other polarizing plate. At this time, if the polarizing plate is parallel to the polarizing surface of the polarizing plate, the light passes through the polarizing plate, but the light is blocked by the polarizing plate when the vertical polarizing surface is formed. However, when the light which is polarized by the polarizing plate passes through the coating film of the coloring composition, light scattering occurs due to the colorant particles, and a part of the polarizing surface occurs. The amount of light transmitted by the offset and the parallel to the polarizing plate is reduced, or only a part of the light is transmitted perpendicular to the polarizing plate. The transmitted light is measured as the luminance on the polarizing plate, and the luminance of the polarizing plate is parallel, and the ratio of the luminance in the vertical direction is calculated as the contrast value.

(comparative value) = (luminance in parallel) / (luminance in vertical)

Therefore, when light scattering occurs due to the coloring agent in the coating film, the luminance in parallel is lowered, and the luminance in the vertical direction is increased, so that the contrast value can be lowered.

Further, the luminance meter is a color luminance meter ("BM-5A" manufactured by Topcon Japan Co., Ltd.), and a polarizing plate ("NPF-G1220DUN" manufactured by Nitto Denko Corporation) is used as the polarizing plate. At the time of the measurement, it was measured by a black mask which was opened by a 1 cm square hole in the measurement part. Among them, the same coating film as that used for the evaluation of the brightness was used, and it was judged according to the following criteria.

○: 3000 or more

△: 2000 or more and less than 3000

×: not up to 2000

The yellow colored composition prepared in the examples and the reference examples was combined with the type of the yellow coloring agent used in the yellow colored composition, and the evaluation results are shown in Table 2.

As is clear from Table 2, the yellow colored compositions of Examples 15 to 33 which were used as the coloring agent of the quinophthalone compound represented by the formula (1) were excellent in both brightness and comparative value, and showed high coloring power. On the other hand, the yellow colored composition of Reference Examples 4 to 9 using the conventionally used yellow coloring agent was inferior in any of the brightness, the contrast value, and the coloring power, and it was found that the brightness, the contrast value, and The overall coloring power is satisfied at the same time fruit.

Further, in comparison with the yellow colored compositions of Examples 16 to 18, it was confirmed that there were differences in brightness, contrast value, and coloring power under changing the ratio of the quinophthalone compound (a) to the C.I. Pigment Yellow No. 138. When the proportion of the quinophthalone compound (a) is larger, it is confirmed that there is a tendency to become higher in brightness and coloring power, and in comparison, the yellow coloring composition of Example 17 (quinoline yellow compound (a) /CI Pigment Yellow No. 138 = 5/5) shows the best results.

Further, in comparison with the yellow colored compositions of Examples 17, 19, and 20, it was found that the coloring agent obtained by mixing the quinophthalone compound (a) and the CI Pigment Yellow No. 138 and then subjected to a salt milling treatment was used. Almost equivalent results can be obtained in terms of the yellow coloring composition of the coloring agent obtained by the co-synthesis method.

Further, in Comparative Example 15 and Example 29, Example 16 and Example 30, Example 17 and Example 31, Example 18 and Example 32, Example 23 and Example 33, it was found in the yellow coloring composition. When the pigment derivative (1) is contained, both the brightness and the contrast value can be simultaneously improved.

<Production of green and blue coloring composition> (Production of Green Coloring Composition 1 (GP-1))

The mixture of the following components was stirred and mixed to make it uniform, and then dispersed in an Eiger polishing and dispersing machine ("Mini Model M-250 MK II" manufactured by Eiger Japan Co., Ltd.) for 5 hours using zirconia beads having a diameter of 0.5 mm. Further, it was filtered through a 5 μm sieve to prepare a green colored composition 1 (GP-1).

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

After the following mixture was stirred and mixed to be uniform, zirconia beads having a diameter of 0.5 mm were used, and dispersed by an Eiger mill disperser ("Mini Model M-250 MKII" manufactured by Eiger Japan Co., Ltd.) for 5 hours, and then filtered at 5 μm. The mesh was filtered to prepare a blue colored composition 1 (BP-1).

<Production of photosensitive coloring composition> [Example 34] (Production of photosensitive coloring composition 1 (GR-1))

The mixture of the following composition was uniformly stirred and mixed, and then filtered through a filter of 1 μm to prepare a photosensitive colored composition 1 (GR-1).

[Examples 35 to 43, Reference Examples 10 to 15] (Production of photosensitive coloring compositions 2 to 16 (GR-2 to 16))

In addition to using the yellow coloring composition, the green coloring composition or the blue coloring composition as shown in Table 3, and changing the yellow coloration at the chromaticity of x=0.290 and y=0.600 under the C light source at the time of coating film evaluation Photosensitive property was carried out in the same manner as in the photosensitive coloring composition 1 (GR-1) except that the ratio of the composition to the green coloring composition or the blue coloring composition was changed (the ratio was changed so that the total amount of the coloring composition was 45 parts). Coloring compositions 2 to 16 (GR-2 to 16).

<Evaluation of Coating Film of Photosensitive Coloring Composition>

Then, the brightness, film thickness, and comparative value of the coating film produced by the photosensitive coloring compositions 1 to 16 (GR-1 to 16) obtained were evaluated by the following methods.

(evaluation of brightness)

The photosensitive coloring composition was applied on a glass substrate of 100 mm × 100 mm and 1.1 mm thick by a spin coater, followed by drying at 70 ° C for 20 minutes, and then using an ultrahigh pressure mercury lamp at 300 mJ/cm ² . Ultraviolet exposure was carried out, and development was carried out with an alkali imaging solution at 23 °C. In the case of the alkali developing solution, 1.5% by weight of sodium carbonate, 0.5% by weight of sodium hydrogencarbonate, 8.0% by weight of an anionic surfactant ("Pelex NBL" manufactured by Kao Corporation, Japan), and 90% by weight of water are used. The constituents. Thereafter, the film was further heated by heating at 230 ° C for 30 minutes. Further, the brightness (Y) of the obtained coating film was measured by a microspectrophotometer ("OSP-SP100" manufactured by Olympus, Japan), and judged based on the following criteria. Further, the produced coating film was subjected to heat treatment at 230 ° C to obtain the chromaticity (C light source) shown in Table 3.

○: 59.5 or more

△: 58.0 or more and less than 59.5

×: not up to 58.0

(assessment of tinting strength)

The film thickness at the chromaticity of x(C)=0.290 and y(C)=0.600 was measured by the same coating film as the evaluation of the brightness, and was determined according to the following criteria. The smaller the film thickness when the chromaticity of x(C)=0.290 and y(C)=0.600 is displayed, the larger the coloring power is, which is preferable.

○: less than 2.5 [μm]

△: 2.5 or more and less than 3.0 [μm]

×: 3.0 or more [μm]

(evaluation of comparison value)

The measurement method of the comparative value of the coating film can be measured in the same manner as the measurement of the comparative values of the yellow colored compositions of Examples 15 to 33 and Reference Examples 4 to 9. Among them, the same coating film as the evaluation of the brightness is used, and the comparative value is calculated, and then judged according to the following criteria.

○: 3500 or more

△: 3000 or more and less than 3,500

×: not up to 3000

The results of evaluation of the photosensitive coloring compositions prepared in the examples and the reference examples are shown in Table 3.

As is clear from the results of Table 3, in the case of forming a color filter, an example of a photosensitive coloring composition containing a quinophthalone compound represented by the formula (1) was used, and a reference example was compared. The result was brightness, contrast value, And the coloring power can be satisfied at the same time, especially the brightness is more excellent.

<Production of color filter>

First, the production of the red photosensitive coloring composition 1 and the blue photosensitive coloring composition 1 used in the production of the color filter was performed. Further, in the green aspect, the photosensitive coloring composition 6 (GR-6) was used.

(production of red coloring composition 1 (RP-1))

The mixture of the composition shown below was stirred and mixed to make it uniform, and then zirconia beads having a diameter of 0.1 mm were used, dispersed in a pico mill for 8 hours, and then filtered through a 5 μm sieve. Into red Coloring composition 1 (RP-1).

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

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

(Modulation of Blue Coloring Composition 2 (BP-2))

The mixture of the composition shown below was stirred and mixed to make it uniform, and then zirconia beads having a diameter of 0.1 mm were used, dispersed in a pico mill for 8 hours, and then filtered through a 5 μm sieve. Blue coloring composition 2 (BP-2).

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

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

First, the black matrix on the glass substrate is processed into an image, and then the red photosensitive coloring composition 1 (RR-1) is coated on the substrate by a spin coater to form a colored film having a film thickness of x=0.640 and y=0.330. . The film was irradiated with ultraviolet rays at 300 mJ/cm ² using an ultrahigh pressure mercury lamp through a mask. Next, it was spray-imaged with an alkali developing solution composed of a 0.2% by weight aqueous solution of sodium carbonate to remove the unexposed portion, and then washed with ion-exchanged water, and the substrate was heated at 230 ° C for 20 minutes to form a red filter. Color clip. In the same manner, the green photosensitive coloring composition 6 (GR-6) was formed into a film thickness of x=0.290 and y=0.600, and formed by blue photosensitive coloring composition 1 (BR-1). The coating was applied to a film thickness of x=0.150 and y=0.060 to form a green color filter segment and a blue color filter segment to obtain a color filter.

When the photosensitive coloring composition 6 (GR-6) was used, it was found that a color filter having high luminance and high contrast value and excellent coloring power can be produced.

"Embodiment II"

"PGMAC" means propylene glycol monomethyl ether acetate.

(weight average molecular weight (Mw) of resin)

The weight average molecular weight (Mw) of the resin is determined by using HLC-8220GPC (manufactured by Tosoh Corporation, Japan), TSK-GEL SUPER HZM-N for two columns, and the solvent is converted to polystyrene by THF. Molecular weight.

First, a method of producing a binder resin, a dye derivative, a colorant, a yellow coloring composition, and a blue coloring composition will be described by way of examples and reference examples.

<Method for Producing Binder Resin Solution> (modulation of acrylic resin solution 1)

196 parts of cyclohexanone was placed in a reaction vessel equipped with a thermometer, a condenser, a nitrogen introduction tube, a dropping tube, and a stirring device in a separable 4-necked flask, and the temperature was raised to 80 ° C, and the reaction vessel was replaced. After nitrogen gas, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, and 20.7 parts of p-isopropylidene phenol were epoxy. A mixture of ethane-modified acrylate ("Aronix M110" manufactured by Japan East Asia Synthetic Co., Ltd.) and 1.1 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After the completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a solution of an acrylic resin. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried at 180 ° C for 20 minutes to determine the nonvolatile matter, and the amount of the nonvolatile matter was 20% by mass in the previously synthesized resin solution. It was prepared into an acrylic resin solution 1. Its weight average molecular weight (Mw) was 26,000.

(modulation of acrylic resin solution 2)

207 parts of cyclohexanone was placed in a reaction vessel equipped with a thermometer, a condenser, a nitrogen introduction tube, a dropping tube, and a stirring device in a separable 4-necked flask, and the temperature was raised to 80 ° C, and the reaction vessel was replaced. After nitrogen gas, 20 parts of methacrylic acid, 20 parts of p-isopropylidene phenol oxirane modified acrylate ("Aronix M110" manufactured by Japan East Asia Synthesis Co., Ltd.), and 45 parts of methyl group were dropped by a dropping tube. A mixture of methyl acrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 1.33 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After the completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a copolymer resin solution. Next, the total amount of the copolymer solution was further stopped, nitrogen gas was stopped, and the mixture was stirred while being injected with dry air for 1 hour. After cooling to room temperature, 6.5 parts of isocyanate-2-methylpropenyloxyethyl ester (Japan Showa) was added. A mixture of Karenz MOI), 0.08 parts of dibutyltin laurate, and 26 parts of cyclohexanone was added dropwise at 70 ° C for 3 hours. After the completion of the dropwise addition, the reaction was further 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 dried by heating at 180 ° C for 20 minutes to determine a nonvolatile matter, and cyclohexanone was added to a non-volatile content of 20% by mass in the previously synthesized resin solution. Acrylic resin solution 2. Its weight average molecular weight (Mw) was 18,000.

<Manufacture of Pigment Derivative (1)>

The dye derivative (1) was obtained by the method of the synthesis described in Japanese Patent No. 4585781.

<Method for Producing Colorant> (Manufacture of yellow colorant 1 (PY-1))

The compound (1) is obtained by a synthesis method as described in JP-A-2008-81566.

First, 100 parts of the compound (1), 70 parts of 2,3-naphthalenedicarboxylic anhydride, and 143 parts of benzoic acid were added to 300 parts of methyl benzoate, and the mixture was further heated to 180 ° C to carry out a reaction for 4 hours. Then, the formation of the quinophthalone yellow compound (a) represented by the following formula (50) and the disappearance of the compound (1) of the starting material were determined by TOF-MS. Thereafter, 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 further separated by filtration, washed with methanol, and dried to obtain 120 parts of the quinoline compound (a). The result of mass analysis by TOF-MS was identified as the quinophthalone compound (a).

Next, 100 parts of the above quinophthalone compound (a), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a 1-gallon kneader made of stainless steel (manufactured by Inoue, Japan) at 60 ° C. The mixture was mixed for 6 hours and subjected to salt milling. Next, the mixture is put into 3 liters of warm water, heated to about 70 ° C while stirring for 1 hour to make it into a slurry, repeatedly filtered, washed with water to remove sodium chloride and diethylene glycol, and then 80 Drying overnight at ° C gave 98 parts of yellow colorant 1 (PY-1). Its average primary particle size is 31.3 nm.

(Manufacture of yellow colorant 2 (PY-2))

First, 20 parts of the yellow coloring agent 1 (PY-1), the quinoline yellow compound (a), 80 parts of the CI pigment yellow 138 ("Paliotol Yellow K0960-HD" manufactured by BASF), 1200 A portion of sodium chloride and 120 parts of diethylene glycol were placed in a 1-gallon kneader (manufactured by Inoue, Ltd.) made of stainless steel, and mixed at 60 ° C for 6 hours to carry out a salt milling treatment. Next, the mixture is put into 3 liters of warm water, heated to about 70 ° C while stirring for 1 hour to make it into a slurry, repeatedly filtered, washed with water to remove sodium chloride and diethylene glycol, and then 80 Drying overnight at ° C gave 98 parts of yellow colorant 2 (PY-2). Its average primary particle size is 31.3 nm.

(Manufacture of yellow colorant 3 (PY-3))

The compound (2) is obtained by the same method as the synthesis of the compound (1), using the quinoline yellow compound (c) as a raw material, and the synthesis method described in JP-A-2008-81566.

First, 100 parts of the compound (2), 108 parts of tetrachlorophthalic anhydride, and 143 parts of benzoic acid were added to 300 parts of methyl benzoate, and the mixture was heated to 180 ° C to carry out a reaction for 4 hours. Then, the formation of the quinophthalone compound (b) and the disappearance of the compound (2) of the starting material were determined by TOF-MS. Thereafter, 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 further separated by filtration, washed with methanol, and dried to obtain 120 parts of a quinoline compound (b) as shown in the following formula (51). As a result of mass analysis by TOF-MS, it can be identified as a quinophthalone compound (b).

Thereafter, 40 parts of the obtained quinoline yellow compound (b), 60 parts of CI Pigment Yellow No. 138 ("Paliotol Yellow K0960-HD" manufactured by BASF Corporation), 1200 parts of sodium chloride, and 120 parts were further added. Diethylene glycol plus It was placed in a 1-gallon kneader made of stainless steel (manufactured by Inoue, Ltd., Japan), and mixed at 60 ° C for 8 hours. Then, the mixture is put into warm water, heated to about 70 ° C while stirring for 1 hour to make it into a slurry form, repeatedly filtered, washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C for one night. 97 parts of yellow colorant 3 (PY-3) were obtained. Its average primary particle size is 36.8 nm.

(Manufacture of yellow colorant 4 (PY-4))

First, 40 parts of 8-aminomethylquinoline, 150 parts of 2,3-naphthalenedicarboxylic anhydride, and 154 parts of benzoic acid were added to 200 parts of methyl benzoate, and the mixture was heated to 180 ° C and stirred for 4 hours. Thereafter, 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 further separated by filtration, washed with methanol, and dried to obtain 116 parts of the quinoline compound (c) represented by the following formula (52). The result of mass analysis by TOF-MS was identified as the quinoline yellow compound (c).

Thereafter, 20 parts of the obtained quinoline yellow compound (c) and 80 parts of CI Pigment Yellow No. 138 ("Paliotol Yellow K0960-HD" manufactured by BASF Corporation), 1200 parts of sodium chloride, and 120 parts were further added. Diethylene glycol was placed in a 1-gallon kneader made of stainless steel (manufactured by Inoue, Ltd.), and mixed at 60 ° C for 8 hours. Secondly, the mixture is put into warm water. The mixture was heated to about 70 ° C while stirring for 1 hour to make it into a slurry. After repeated filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried overnight at 80 ° C to obtain 97 parts of yellow colorant 4 ( PY-4). Its average primary particle diameter was 34.1 nm.

(Manufacture of yellow colorant (PY-5))

First, 100 parts of CI Pigment Yellow No. 138 ("Paliotol Yellow K0960-HD" manufactured by BASF), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were added to a 1-gallon kneading machine made of stainless steel (Japan Inoue Co., Ltd.) Manufactured and mixed at 70 ° C for 6 hours. Next, 3000 parts of the mixture is put into warm water, heated to about 70 ° C while stirring for 1 hour to make it into a slurry, repeated filtration, washing with water to remove sodium chloride and diethylene glycol, and then 80 After drying overnight at ° C, 98 parts of a yellow coloring agent (PY-5) was obtained. Its average primary particle size is 35.5 nm.

(Manufacture of blue colorant (PB-1))

First, 225 parts of sebacic acid and 78 parts of anhydrous aluminum chloride were added to 1250 parts of n-pentanol in a reaction vessel, followed by stirring. Thereafter, 266 parts of DBU (1,8-Diazabicyclo[5.4.0]undec-7-ene: 1,8-diazabicyclo[5.4.0]-7-undecene) was added thereto and heated. It was refluxed at 136 ° C for 5 hours. Further, the reaction solution was cooled to 30 ° C under stirring, and added to a mixed solvent of 5,000 parts of methanol and 10,000 parts of water under stirring to obtain a blue slurry. The slurry was further filtered, washed with a mixed solvent of 2000 parts of methanol and 4000 parts of water, and dried to obtain 135 parts of chloroaluminum indigo. Thereafter, 100 parts of chloroaluminum in the reaction vessel was gradually added to 1200 parts of concentrated sulfuric acid at room temperature. Stir at 40 ° C After an hour, the sulfuric acid solution was then injected into 24,000 parts of 3 ° C cold water. The blue precipitate was filtered, washed with water, and dried to obtain 102 parts of an anthocyanin aluminum pigment represented by the following formula (53).

Then, 100 parts of the anthraquinone aluminum pigment of the formula (53), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were added to a 1-gallon kneader made of stainless steel (manufactured by Inoue, Japan) Medium and mixed at 70 ° C for 6 hours. Then, 3000 parts of the mixture is put into warm water, heated to about 70 ° C while stirring for 1 hour to make it into a slurry, repeated filtration, washing with water to remove sodium chloride and diethylene glycol, and then at 80 ° C After drying overnight, a blue colorant (PB-1) was obtained. Its average primary particle diameter was 30.4 nm.

(Manufacture of blue colorant (PB-2))

To 1000 parts of methanol in a reaction vessel, 100 parts of an anthocyanin aluminum pigment of the formula (53) and 49.5 parts of diphenyl phosphate were added, and the mixture was heated to 40 ° C to carry out a reaction for 8 hours. After the reaction product was cooled to room temperature, the product was filtered, washed with methanol, and dried to obtain 114 parts of an anthocyanin aluminum pigment represented by the following formula (54).

The obtained anthraquinone aluminum pigment of the formula (54) was subjected to a salt milling treatment similar to that of the blue coloring agent (PB-1) to obtain a blue coloring agent (PB-2). Its average primary particle size was 31.2 nm.

(Manufacture of blue colorant (PB-3))

First, 100 parts of the anthraquinone aluminum pigment of the formula (53) and 43.2 parts of diphenylphosphonic acid were added to 1000 parts of methanol in a reaction vessel, and the mixture was heated to 40 ° C to carry out a reaction for 8 hours. After the reaction mixture was cooled to room temperature, the product was filtered, washed with methanol, and dried to obtain 112 parts of an anthocyanin aluminum pigment represented by the following formula (55).

The obtained anthraquinone aluminum pigment of the formula (55) was further subjected to a salt milling treatment similar to the blue coloring agent (PB-1) to obtain a blue coloring agent (PB-3). Its average primary particle diameter was 29.5 nm.

(Manufacture of blue colorant (PB-4))

First, an anthraquinone aluminum pigment represented by the following formula (56) is obtained according to the synthesis method described in JP-A-2010-79247.

The obtained anthraquinone aluminum pigment of the formula (56) was subjected to a salt milling treatment similar to that of the blue coloring agent (PB-1) to obtain a blue coloring agent (PB-4). Its average primary particle diameter was 33.0 nm.

(Manufacture of blue colorant (PB-5))

First, 200 parts of pyridine, 800 parts of xylene, and 54.6 parts of benzenesulfonic acid were added to 100 parts of the anthraquinone aluminum pigment of the formula (53), and heating under reflux was continued for 8 hours. After filtering, washing with methanol, then adding After drying, 110 parts of an anthraquinone aluminum pigment represented by the following formula (57) was obtained.

Thereafter, salt milling treatment was carried out in the same manner as in the case of the blue coloring agent (PB-1) to prepare a blue coloring agent (PB-5). The resulting coloring agent had a volume average primary particle diameter of 37 nm.

<Method for Producing Colored Composition> (production of yellow coloring composition (DY-1))

First, a mixture of the following composition was stirred and mixed to make it uniform, and then a zirconia bead having a diameter of 0.5 mm was used, and an Eiger mill of a Media wet disperser ("Mini Model M-250 MKII" manufactured by Eiger Japan Co., Ltd.) was used. After dispersing for 4 hours, it was filtered through a 5 μm sieve to prepare a yellow colored composition (DY-1).

(Production of yellow coloring composition (DY-2))

In the production of the yellow colored composition (DY-1), except that the yellow coloring agent (PY-1) was changed to the yellow coloring agent (PY-2), the yellow coloring composition (DY-) was produced in the same manner. 2).

(production of yellow coloring composition (DY-3))

In the production of the yellow colored composition (DY-1), except that the yellow coloring agent (PY-1) was changed to the yellow coloring agent (PY-3), the same operation was carried out to prepare a yellow colored composition (DY- 3).

(Production of yellow coloring composition (DY-4))

In the production of the yellow colored composition (DY-1), except that the yellow coloring agent (PY-1) was changed to the yellow coloring agent (PY-4), the same operation was carried out to prepare a yellow colored composition (DY- 4).

(production of yellow coloring composition (DY-5))

In the production of the yellow colored composition (DY-1), except that the yellow coloring agent (PY-1) was changed to the yellow coloring agent (PY-5), the same operation was carried out to prepare a yellow colored composition (DY- 5).

(production of blue coloring composition (DB-1))

After the mixture of the following composition was stirred and mixed to be uniform, zirconia beads having a diameter of 0.5 mm were used, and dispersed by an Eiger mill ("Mini Model M-250 MK II" manufactured by Eiger Japan Co., Ltd.) of a Media wet disperser. After 4 hours, it was filtered through a 5 μm sieve to prepare a blue colored composition (DB-1).

(production of blue coloring composition (DB-2))

In the production of the blue coloring composition (DB-1), except that the blue coloring agent (PB-1) was changed to the blue coloring agent (PB-2), the same operation was carried out to prepare a blue coloring composition. (DB-2).

(production of blue coloring composition (DB-3))

In the production of the blue coloring composition (DB-1), except that the blue coloring agent (PB-1) was changed to the blue coloring agent (PB-3), the same operation was carried out to prepare a blue coloring composition. (DB-3).

(production of blue coloring composition (DB-4))

In the production of the blue coloring composition (DB-1), except that the blue coloring agent (PB-1) was changed to the blue coloring agent (PB-4), the same operation was carried out to prepare a blue coloring composition. (DB-4).

(production of blue coloring composition (DB-5))

In the production of the blue coloring composition (DB-1), except that the blue coloring agent (PB-1) was changed to the blue coloring agent (PB-5), the same operation was carried out to prepare a blue coloring composition. (DB-5).

[Example 1] (Green coloring composition (DG-1))

The yellow colored composition (DY-1) and the blue colored composition (DB-1) were mixed and mixed with the following composition to prepare a green colored composition (DG-1).

Next, the obtained green coloring composition (DG-1) was coated on a 100 mm × 100 mm, 1.1 mm thick glass substrate by a spin coater, and dried at 70 ° C for 20 minutes, and then at 230 ° C. After heating for 1 hour, it was allowed to cool, and then a coated substrate was produced. The chromaticity of the obtained coating film was measured by a microspectrophotometer ("OSP-SP100" manufactured by Olympus, Japan), and the chromaticity of the substrate was determined to be x = 0.290 and y = 0.600 at the C light source.

[Examples 2 to 17, Reference Examples 1 to 5] (Green coloring composition (DG-2 to 22))

First, the yellow coloring composition and the blue coloring composition shown in Table 1 were changed, and the same operation as the green coloring composition (DG-1) was carried out. In the coated substrate, by using a C light source, x=0.290, The mixing ratio of y = 0.600 was stirred and mixed to prepare a green coloring composition (DG-2 to 22). Among them, the total amount of the green coloring composition was 100.0 parts.

<Evaluation of green coloring composition>

In the green coloring composition (DG-1 to 22) obtained, the test relating to the viscosity and coloring power of the dispersion was carried out in the following manner. The results are shown in Table 2.

(assessment of viscosity)

The viscosity of the colored composition is adjusted at 25 ° C on the day of use. The E-type viscometer ("ELD-type viscometer" manufactured by Toki Sangyo Co., Ltd.) was measured for its viscosity at a number of revolutions of 20 rpm. The results are judged based on the following criteria.

○: Less than 10.0 [mPa. s]

△: 10.0 or more and less than 13.0 [mPa. s]

×: 13.0 or more [mPa. s]

(assessment of tinting strength)

The tinting strength was evaluated by measuring the film thickness of the coating film. The film thickness of the obtained coating film was measured by a surface shape measuring instrument "Dektak 8 (manufactured by Veeco Co., Ltd.)". The results are judged based on the following criteria. The smaller the film thickness of the chromaticity which gives the purpose, the greater the coloring power, and the better.

◎: not up to 1.2 [μm]

○: 1.2 or more and less than 1.6 [μm]

△: 1.6 or more and less than 2.0 [μm]

×: 2.0 or more [μm]

As is clear from the results of Table 2, the coloring composition containing the quinophthalone yellow compound having a specific structure and the anthraquinone aluminum pigment had good results in terms of viscosity and coloring power as compared with the reference examples.

<Production of photosensitive coloring composition> [Embodiment 18] (Green photosensitive coloring composition (RG-1))

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

[Examples 18 to 34, Reference Examples 6 to 10] Production of (RG-2 to 20)

In the same manner as in the green photosensitive coloring composition (RG-1), a green photosensitive coloring composition (RG-2 to 22) was produced in the composition shown in Table 3.

<Evaluation of green photosensitive coloring composition>

In terms of the obtained green photosensitive coloring composition (RG-1 to 22), the tests relating to brightness, contrast value, and coloring power were carried out by the following methods. The results are shown in Table 4.

(evaluation of brightness)

The green photosensitive coloring composition (RG-1 to 22) was applied on a glass substrate of 100 mm × 100 mm and 1.1 mm thick by a spin coater, dried at 70 ° C for 20 minutes, and then an ultrahigh pressure mercury lamp. Ultraviolet exposure was carried out at a cumulative amount of light of 150 mJ/cm ² , and then development was carried out at 23 ° C with an alkali developing solution to obtain a coated substrate. Thereafter, the film was heated at 230 ° C for 1 hour, and after standing and cooling, a coated substrate was produced. The chromaticity of the obtained coating film was measured by a microspectrophotometer ("OSP-SP100" manufactured by Olympus Co., Ltd., Japan), and the chromaticity of the substrate was measured at a light source of x=0.290 and y=0.600. :Y(c). Further, in the case of the alkali developing solution, 1.5% by weight of sodium carbonate, 0.5% by weight of sodium hydrogencarbonate, 8.0% by weight of an anionic surfactant ("Pelex NBL" manufactured by Kao Corporation, Japan), and 90% by weight are used. The water is composed of. The criteria for its determination are as follows.

○: 59.5 or more

△: 58.0 or more and less than 58.5

×: not up to 58.0

(evaluation of comparison value)

The light emitted from the backlight unit for the liquid crystal display device is polarized by the polarizing plate, and passes through the coating film of the colored composition coated on the glass substrate to reach the other polarizing plate. At this time, when the polarizing plate is parallel to the polarizing surface of the polarizing plate, the light passes through the polarizing plate, but when the polarizing surface is perpendicular, the light is blocked by the polarizing plate. However, when the light which is polarized by the polarizing plate passes through the coating film of the coloring composition, light scattering occurs due to the colorant particles, and a part of the polarizing surface occurs. The amount of light transmitted when the offset is parallel to the polarizing plate is reduced, or only a part of the light is transmitted when it is perpendicular to the polarizing plate. The luminance on the polarizing plate of the transmitted light is measured, and the luminance of the polarizing plate in parallel is compared with the luminance in the vertical direction, and the contrast value is calculated.

(comparative value) = (luminance in parallel) / (luminance in vertical)

Therefore, when light scattering occurs due to the coloring agent in the coating film, the luminance in parallel is lowered, and the luminance in the vertical direction is increased, so that the contrast value is lowered.

Further, the luminance meter is a color luminance meter ("BM-5A" manufactured by Topcon Japan Co., Ltd.), and a polarizing plate ("NPF-G1220DUN" manufactured by Nitto Denko Corporation) is used as the polarizing plate. At the time of the measurement, it was measured by a black mask which was opened by a 1 cm square hole in the measurement part. Among them, the same coating film as that used for the evaluation of the brightness was used, and it was judged according to the following criteria.

○: 4000 or more

△: 3500 or more and less than 4000

×: not up to 3500

(assessment of tinting strength)

The coloring power was measured by the same coating film as the evaluation of the brightness, and the film thickness of the coating film was measured. The film thickness of the obtained coating film was measured by a surface shape measuring instrument "Dektak 8 (manufactured by Veeco Co., Ltd.)". The results are judged based on the following criteria. The smaller the film thickness of the chromaticity of the object is, the smaller the coloring power is, which is preferable.

◎: Less than 2.0 [μm]

○: 2.0 or more and less than 2.5 [μm]

△: 2.5 or more and less than 3.0 [μm]

×: 3.0 or more [μm]

<Production of color filter>

First, the preparation of the red photosensitive coloring composition and the blue photosensitive coloring composition used in the production of the color filter was carried out. Further, in the case of the green photosensitive coloring composition, (GR-6) is used.

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

After the mixture of the following composition was uniformly stirred and mixed, zirconia beads having a diameter of 0.5 mm were used, and dispersed by an Eiger mill disperser ("Mini Model M-250 MK II" manufactured by Eiger Japan Co., Ltd.) for 5 hours, and then 5.0 μm. The sieve was filtered to prepare a red colored composition 1 (DR-1).

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

(Production of blue photosensitive coloring composition (RB-1))

After the mixture of the following composition was uniformly stirred and mixed, zirconia beads having a diameter of 0.5 mm were used, and dispersed by an Eiger mill disperser ("Mini Model M-250 MK II" manufactured by Eiger Japan Co., Ltd.) for 5 hours, and then 5.0 μm. The sieve was filtered to prepare a blue colored composition (DB-6).

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

(production of color filter)

The black matrix on the glass substrate was first processed into an image, and the red photosensitive coloring composition (RR-1) was applied onto the substrate by a spin coater to form a colored film. The film was irradiated with ultraviolet rays at 150 mJ/cm ² using an ultrahigh pressure mercury lamp through a mask. Next, it was spray-imaged with an alkali developing solution composed of a 0.2% by weight aqueous sodium carbonate solution to remove the unexposed portion, and then washed with ion-exchanged water, and the substrate was heated at 220 ° C for 20 minutes to form a C. Under the light source (hereinafter, also used in green and blue) red color filter segments of x=0.640 and y=0.330. In the same manner, the green photosensitive coloring composition (RG-6) was formed to be in the range of x=0.290 and y=0.600, and the blue photosensitive coloring composition (RB-1) was formed to be in the range of x=0.150, y. =0.060, a green color filter segment and a blue color filter segment are formed to obtain a color filter.

When the photosensitive coloring composition (RG-6) is used, a color filter having high brightness and high contrast value and excellent coloring power can be produced.

"Embodiment III"

In the following, the weight average molecular weight (Mw) is converted by TSK gel column (manufactured by Tosoh Corporation of Japan) and GPC (manufactured by Tosoh Corporation of Japan, HLC-8320GPC) of the device RI detector. The molecular weight of polystyrene.

First, the yellow coloring agent and the dye derivative used in the coloring composition of the present embodiment will be described.

<Production of yellow coloring agent> (Manufacture of yellow colorant 1 (Y-1))

First, 100 parts of quinoline yellow pigment CI Pigment Yellow No. 138 ("Paliotol Yellow K0960-HD" manufactured by BASF), 1200 parts of sodium chloride, and 120 parts of diethylene glycol are added to a gallon of stainless steel. The kneader (manufactured by Inoue, Ltd., Japan) was mixed at 60 ° C for 6 hours. Next, the mixture is put into 5 liters of warm water, heated to 70 ° C and stirred for 1 hour to make it into a slurry, repeatedly filtered, washed with water to remove sodium chloride and diethylene glycol, and then 80 After drying overnight at ° C, 98 parts of yellow colorant 1 (Y-1) was obtained. Its average primary particle diameter was 30.1 nm.

(Manufacture of yellow colorant 2 (Y-2))

The compound (1) is obtained according to the synthesis method described in JP-A-2008-81566.

First, 100 parts of the compound (1), 70 parts of 2,3-naphthalenedicarboxylic anhydride, and 143 parts of benzoic acid were added to 300 parts of methyl benzoate, and the mixture was further heated to 180 ° C to carry out a reaction for 4 hours. Then, the formation of the quinophthalone compound (a) and the disappearance of the compound (1) of the starting material were determined by TOF-MS. after that, After allowing to cool to room temperature, the reaction mixture was poured into 3130 parts of acetone and stirred at room temperature for 1 hour. The product was further separated by filtration, washed with methanol, and dried to obtain 120 parts of quinoline compound (a). The result of mass analysis by TOF-MS was identified as the quinophthalone compound (a).

Next, 100 parts of the above quinophthalone compound (a), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a 1-gallon kneader (manufactured by Inoue, Ltd.) made of stainless steel, and 60 Mix for 6 hours at °C and carry out salt milling. Next, the mixture was put into 3 liters of warm water, heated to 70 ° C while stirring for 1 hour to make a slurry, repeated filtration, washing with water to remove sodium chloride and diethylene glycol, and then at 80 ° C After drying overnight, 98 parts of yellow colorant 2 (Y-2) were obtained. Its average primary particle size is 31.3 nm.

(Manufacture of yellow colorant 3 (Y-3))

First, 70 parts of quinoline yellow compound (a), 30 parts of CI Pigment Yellow No. 138 ("Paliotol Yellow K0960-HD" manufactured by BASF Corporation), 1200 parts of sodium chloride, and 120 parts of diethylene glycol are added. A 1 gallon kneader made of stainless steel (manufactured by Inoue, Ltd., Japan) was mixed at 60 ° C for 8 hours. Next, the mixture is put into warm water, heated to about 70 ° C while stirring for 1 hour to make it into a slurry, repeatedly filtered, washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. One night, 97 parts of yellow colorant 3 (Y-3) were obtained. Its average primary particle diameter was 30.4 nm.

(Manufacture of yellow colorant 4 (Y-4))

In addition to 70 parts of quinoline yellow compound (a) and 30 parts of C.I. Pigment Yellow No. 138 ("Paliotol Yellow K0960-HD" manufactured by BASF), Manufactured with 50 parts of quinophthalone yellow compound (a) and 50 parts of CI Pigment Yellow No. 138 ("Paliotol Yellow K0960-HD" manufactured by BASF Corporation), and yellow colored composition 2 (Y-2) The same operation gave yellow colorant 4 (Y-4). Its average primary particle diameter was 29.6 nm.

(Manufacture of yellow colorant 5 (Y-5))

In addition to 70 parts of quinoline yellow compound (a) and 30 parts of CI Pigment Yellow No. 138 ("Paliotol Yellow K0960-HD" manufactured by BASF Corporation), each was changed to 20 parts of quinoline yellow compound (a) and 80 parts. The yellow coloring agent 5 (Y-5) was obtained in the same manner as in the production of the yellow coloring agent 2 (Y-2) except for CI Pigment Yellow No. 138 ("Paliotol Yellow K0960-HD" manufactured by BASF Corporation). Its average primary particle diameter was 31.8 nm.

(Manufacture of yellow colorant 6 (Y-6))

First, in 200 parts of methyl benzoate, 40 parts of 8-aminomethylquinoline, 150 parts of 2,3-naphthalenedicarboxylic anhydride, and 154 parts of benzoic acid were added, and the mixture was heated to 180 ° C for 4 hours. Thereafter, 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 further subjected to filtration separation, methanol washing, and drying to obtain 116 parts of quinoline compound (c). The result of mass analysis by TOF-MS was identified as the quinoline yellow compound (c).

Next, 100 parts of the obtained quinoline yellow compound (c), 1200 parts of sodium chloride, and 120 parts of diethylene glycol are added to a 1-gallon kneader made of stainless steel (manufactured by Inoue, Japan), and Mix for 8 hours at 60 °C. Next, the mixture is put into warm water, heated to about 70 ° C while stirring for 1 hour to make it into a slurry, repeatedly filtered, washed with water to remove After sodium chloride and diethylene glycol, it was dried overnight at 80 ° C to obtain 97 parts of a yellow colorant 6 (Y-6). Its average primary particle diameter was 34.1 nm.

(Manufacture of yellow colorant 7 (Y-7))

The compound (2) is obtained by the same method as the synthesis of the compound (1), using the quinoline yellow compound (c) as a raw material, and the synthesis method described in JP-A-2008-81566.

First, 100 parts of the compound (2), 108 parts of tetrachlorophthalic anhydride, and 143 parts of benzoic acid were added to 300 parts of methyl benzoate, and the mixture was further heated to 180 ° C to carry out a reaction for 4 hours. Then, the formation of the quinophthalone compound (b) and the disappearance of the compound (2) of the starting material were determined by TOF-MS. Thereafter, 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 further subjected to filtration separation, methanol washing, and drying to obtain 120 parts of quinoline yellow compound (b). As a result of mass analysis by TOF-MS, it can be identified as a quinophthalone compound (b).

Thereafter, 100 parts of the obtained quinophthalone compound (b), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a 1-gallon kneader (manufactured by Inoue, Ltd.) made of stainless steel, and Mix for 8 hours at 60 °C. Next, the mixture is put into warm water, heated to about 70 ° C while stirring for 1 hour to make it into a slurry, repeatedly filtered, washed with water to remove chlorination. After sodium and diethylene glycol, it was dried overnight at 80 ° C to obtain 98 parts of yellow coloring agent 7 (Y-7). Its average primary particle size was 31.1 nm.

(Manufacture of yellow colorant 8 (Y-8))

A quinoline yellow compound was obtained in the same manner as in the production of yellow colorant 1 (Y-1) except that 70 parts of 2,3-naphthalene dicarboxylic anhydride was changed to 70 parts of 1,2-naphthalene dicarboxylic anhydride. (d) Yellow colorant 8 (Y-8). Its average primary particle diameter was 31.6 nm.

(Manufacture of yellow colorant 9 (Y-9))

First, 100 parts of the compound (2), 176 parts of tetrabromophthalic anhydride, and 143 parts of benzoic acid were added to 300 parts of methyl benzoate, and the mixture was further heated to 180 ° C to carry out a reaction for 6 hours. Then, the formation of the quinophthalone compound (g) and the disappearance of the compound (2) of the starting material were determined by TOF-MS. Thereafter, 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 further subjected to filtration separation, methanol washing, and dried to obtain 138 parts of quinoline compound (h). As a result of mass analysis by TOF-MS, it was identified as a quinophthalone compound (h).

Thereafter, 100 parts of the obtained quinophthalone compound (h), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a 1-gallon kneader (manufactured by Inoue, Ltd.) made of stainless steel, and Mix at 80 ° C for 8 hours. Next, the mixture is put into warm water, heated to about 70 ° C while stirring for 1 hour to make it into a slurry, repeatedly filtered, washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. One night, 97 parts of yellow colorant 9 (Y-9) were obtained. Its average primary particle diameter was 28.3 nm.

(Manufacture of yellow colorant 10 (Y-10))

First, 52 parts of the quinophthalone compound (a) was dissolved in 428 parts of 98% sulfuric acid and 472 parts of 25% fuming sulfuric acid, and further stirred at 85 ° C for 2 hours to carry out a sulfonation reaction. Next, the reaction solution was further dropped into 6000 parts of ice water, and the quinophthalone compound which was precipitated therefrom was separated by filtration and washed with water to obtain a paste. The resulting paste was then redispersed in 8000 parts of water and stirred at room temperature for 1 hour. After separating by filtration and washing with water, it was dried overnight at 80 ° C to obtain 54 parts of quinoline yellow compound (k). As a result of mass analysis by TOF-MS, it was identified as a quinophthalone compound (k).

Thereafter, 50 parts of the obtained quinoline yellow compound (k), 50 parts of CI Pigment Yellow No. 138 ("Paliotol Yellow K0960-HD" manufactured by BASF Corporation), 1200 parts of sodium chloride, and 120 parts of Ethylene glycol was placed in a 1-gallon kneader (manufactured by Inoue, Ltd.) made of stainless steel, and mixed at 60 ° C for 8 hours. Next, the mixture is put into warm water, heated to about 70 ° C while stirring for 1 hour to make it into a slurry, repeatedly filtered, washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. One night, 95 parts of yellow colorant 10 (Y-10) were obtained. Its average primary particle size is 36.8 nm.

(Manufacture of yellow colorant 11 (Y-11))

First, 44 parts of the quinophthalone compound (b) was dissolved in 540 parts of 95% sulfuric acid, and then 38 parts of N-methylol phthalimide was added thereto, and stirred at 85 ° C for 7 hours. . After cooling, the reaction solution was added dropwise to 3,600 parts of ice water, and the quinophthalone compound which was precipitated was separated by filtration and washed with water to obtain a paste. The resulting paste was redispersed in 5000 parts of water and stirred at room temperature for 1 hour. After separation by filtration and washing with water, at 80 ° C After drying overnight, 53 parts of quinoline yellow compound (r) were obtained. As a result of mass analysis by TOF-MS, it was identified as a quinoline yellow compound (r).

Thereafter, 50 parts of the obtained quinoline yellow compound (r), 50 parts of CI Pigment Yellow No. 138 ("Paliotol Yellow K0960-HD" manufactured by BASF Corporation), 1200 parts of sodium chloride, and 120 parts of Ethylene glycol was placed in a 1-gallon kneader (manufactured by Inoue, Ltd.) made of stainless steel, and mixed at 60 ° C for 8 hours. Next, the mixture is put into warm water, heated to about 70 ° C while stirring for 1 hour to make it into a slurry, repeatedly filtered, washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. One night, 98 parts of yellow colorant 11 (Y-11) were obtained. Its average primary particle diameter was 35.4 nm.

(Manufacture of yellow colorant 12 (Y-12))

500 parts of isoporphyrin yellow pigment CI Pigment Yellow No. 139 ("IRGAPHOR YELLOW-2R-CF" manufactured by Ciba Japan Co., Ltd.), 500 parts of sodium chloride, and 250 parts of diethylene glycol were added to stainless steel. The mixture was mixed in a 1 gallon kneader (manufactured by Inoue, Japan) at 120 ° C for 8 hours. Next, the mixture is put into 5 liters of warm water, heated to about 70 ° C while stirring for 1 hour to make it into a slurry, repeated filtration, washing with water to remove sodium chloride and diethylene glycol, and then 80 Drying overnight at ° C gave 490 parts of yellow colorant 12 (Y-12). Its average primary particle diameter was 34.2 nm.

(Manufacture of yellow colorant 13 (Y-13))

First, 200 parts of nickel complex yellow pigment C.I. Pigment Yellow No. 150 ("E-4GN" manufactured by Lanxess), 1400 parts of sodium chloride, and 360 The diethylene glycol was placed in a 1-gallon kneader made of stainless steel (manufactured by Inoue, Ltd.), and mixed at 80 ° C for 6 hours. Next, the mixture was put into 8 liters of warm water, heated to 80 ° C and stirred for 2 hours to make it into a slurry, repeated filtration, washing with water to remove sodium chloride and diethylene glycol, and then 85 After drying overnight at ° C, 190 parts of yellow colorant 13 (Y-13) were obtained. Its average primary particle size was 31.9 nm.

<Pigment Derivatives (1), (2)>

The dye derivatives (1) and (2) are obtained in accordance with the synthesis method described in Japanese Patent No. 4585781.

Next, the pigment dispersant of this embodiment will be described.

<Production of Pigment Dispersant> (Manufacture of ethylene polymer (A-1))

First, 100 parts of methyl methacrylate, 200 parts of butyl acrylate, and 200 parts of diethylene glycol monomethyl ether methacrylate are placed in a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer. (BRIEM PME-100 manufactured by Nippon Oil & Fats Co., Ltd.), 1-thiopropanol in 28 parts, and 226 parts of propylene glycol monomethyl ether acetate, and replaced with nitrogen. Thereafter, the inside of the reaction vessel was heated to 90 ° C, and further reacted for 8 hours after adding 0.5 part of AIBN. After the 95% reaction was determined by the nonvolatile measurement, it was cooled to room temperature to obtain a nonvolatile content of 70% of the ethylene polymer (A-1) having a single terminal hydroxyl group having a weight average molecular weight of about 3,500 and having 2 free hydroxyl groups. Solution.

(Manufacture of ethylene polymers (A-2) to (A-15), comparative ethylene polymers (A'-1) to (A'-3))

In the same manner as the above-mentioned ethylene polymer (A-1), the ethylene polymer (A-2) having two free hydroxyl groups in a single terminal portion was obtained by using the same as the raw material and the amount of addition described in Table 1. A-15), comparing the non-volatile fraction of the ethylene polymers (A'-1) to (A'-3) to a 70% by weight solution.

The abbreviations in Table 1 are as follows.

(Manufacture of pigment dispersant (B-1))

100 parts of a non-volatile 70% solution of ethylene polymer (A-1) and 15.3 parts of isophorone diisocyanate are placed in a reaction vessel 1 equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer. 26.8 parts of propylene glycol monomethyl ether acetate and 0.027 parts of dibutyltin dilaurate as a catalyst were replaced by nitrogen. The inside of the reaction vessel was then heated to 100 ° C. After allowing to react for 4 hours, it was cooled to 40 ° C to obtain a prepolymer solution having an isocyanate group. Thereafter, in a reaction vessel 2 equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 6.08 parts of imine dipropylamine and 156.3 parts of propylene glycol monomethyl ether acetate were charged and heated to 60 °C. Further, 30 parts of the aforementioned prepolymer solution was added dropwise thereto over 30 minutes, and after the reaction was continued for 30 minutes, it was allowed to cool to room temperature to terminate the reaction. Thereafter, propylene glycol monomethyl ether acetate was added thereto to obtain a solution having a nonvolatile content of 30% of the pigment dispersant (B-1). It has a weight average molecular weight of about 10,000 and a theoretical amine value of 47 mg KOH/g.

(Production of pigment dispersants (B-1) to (B-18), comparative pigment dispersants (B'-1) to (B'-3))

(B-2) to (B-18), (B'-1) to (B) were synthesized in the same manner as the above-mentioned pigment dispersant (B-1), except that the raw materials and the amounts of addition described in Table 3 were used. The non-volatile portion of each of the various pigment dispersants of B'-3) is a 30% solution.

The abbreviation in Table 3 is as follows.

IPDI: Isophorone diisocyanate

HDI: hexamethylene diisocyanate

DBTDL: Dibutyltin dilaurate

IBPA: imine dipropylamine [alias: N,N-bis(3-aminopropyl)amine]

MIBPA: methylimine dipropylamine [alias: N,N-bis(3-aminopropyl)methylamine]

(Comparative Pigment Dispersant B'-4)

Made by Ajinomoto Jingji Co., Ltd.: AJISPER-PB-711 (non-volatile fraction 40%)

(Comparative Pigment Dispersant B'-5)

The polymer part of the cadre is dimethylamine methylated propylene glycol methacrylate-methacrylated styrene methacrylate copolymer, and the branched polymer part is a base composed of polymethyl methacrylate. A non-volatile propylene glycol monomethyl ether acetate solution having a cationic comb-shaped graft copolymer having a base equivalent weight of 48 mg KOH/g (Japanese Unexamined Patent Publication No. Hei 9-176511: the pigment described in Example 6) Dispersant).

<Production of Adhesive Resin> (Manufacture of adhesive resin (C-1))

First, 98.4 parts of propylene glycol monomethyl ether acetate was added to the reaction vessel, and then nitrogen gas was injected into the vessel while heating to 110 ° C, followed by 12.3 parts of methacrylic acid and 20 parts of butyl acrylate at the same temperature. 29.2 parts of benzyl methacrylate, 24.2 parts of p-isopropylidene phenol oxirane modified acrylate ("Aronix M-110" manufactured by Japan East Asia Synthesis Co., Ltd.), A mixture of 14.3 parts of 4-hydroxybutyl acrylate and 1.65 parts of AIBN was dropped thereinto for polymerization within 2 hours. After the completion of the dropwise addition, the reaction was further continued at 110 ° C for 3 hours, and then allowed to cool to room temperature to complete the reaction. Further, propylene glycol monomethyl ether acetate was added thereto to obtain a solution having a nonvolatile content of 20% of the binder resin (C-1). The binder resin has a weight average molecular weight of about 30,000 and a theoretical Tg of 2.1 °C.

(Manufacture of adhesive resins (C-2) to (C-4))

The propylene glycol monomethyl ether acetate was added in the same manner as the above-mentioned binder resin (C-1), except that the raw materials and the amounts described in Table 4 were used, and the binder resin (C-2) was obtained. The nonvolatile matter to (C-4) is divided into 20% solution.

The abbreviation in Table 4 is as follows.

MMA: Methyl methacrylate

nBA: butyl acrylate

BzMA: benzyl methacrylate

M-110: Conversion of iso-p-propyl phenol oxirane manufactured by Japan East Asia Synthesis Co., Ltd. Acrylate

4HBA: 4-hydroxybutyl acrylate

HEMA: 2-hydroxyethyl methacrylate

PME-400: methoxypolyethylene glycol methacrylate manufactured by Nippon Oil & Fats Co., Ltd.

AIBN: 2,2'-azobis(isobutyronitrile)

<Production of yellow coloring composition> [Example 1] (Production of yellow coloring composition 1 (YP-1))

After the mixture of the following components was stirred and mixed to be uniform, zirconia beads having a diameter of 0.5 mm were used, and dispersed by an Eiger polishing disperser ("Mini Model M-250 MK II" manufactured by Eiger Japan Co., Ltd.) for 5 hours. The mixture was filtered through a 5 μm sieve to prepare a yellow colored composition 1 (YP-1).

[Examples 2 to 33, Reference Examples 1 to 10] [Production of yellow coloring compositions 2 to 43 (YP-2 to 43)]

The yellow colored compositions 2 to 43 (YP-2 to 43) were produced in the same manner as in the yellow colored composition 1 (YP-1) except that the materials described in Table 5 were changed.

With respect to the obtained yellow colored composition (YP-1 to 43), the viscosity characteristics, brightness, and contrast value were measured by the following methods. The evaluation results are shown in Table 5.

(viscosity characteristics)

The viscosity of the yellow coloring composition (YP-1 to 43) on the next day of the preparation (hereinafter referred to as the initial viscosity), and the E-type viscosity meter ("ELD type viscosity meter" manufactured by Nippon Toki Sangyo Co., Ltd.) at 25 ° C The conditions of the number of revolutions of 20 rpm were measured. At the same time, the viscosity promoted over time at 40 ° C for one week (hereinafter referred to as time-dependent viscosity) was also measured, and the rate of change in viscosity over time was calculated by the following formula, and the stability over time was evaluated in the following four stages.

[Change rate of viscosity over time (%)] = [Time-dependent viscosity] / [Initial viscosity] × 100

◎: The rate of change over time is less than 105%

○: Change rate over time to 105% or more and less than 130%

△: Change rate over time to 130% or more and less than 150%

×: Change rate over time to 150% or more

(brightness)

The yellow colored composition (YP-1 to 43) was applied on a glass substrate of 100 mm × 100 mm and 1.1 mm thick by a spin coater, and then heated at 230 ° C for 20 minutes to obtain a coating film. At this time, the film thickness of the coating film was applied to the coating condition of x=0.440 (rotation number and time of the spin coater) in the C light source after heat treatment at 230° C., and was applied as appropriate. The obtained coating film was measured for its brightness (Y) by a microspectrophotometer ("OSP-SP100" manufactured by Olympus, Japan), and was judged according to the following criteria.

○: 89.0 or more

△: 87.5 or more and less than 89.0

×: not up to 87.5

(comparative value)

The light emitted from the backlight unit for the liquid crystal display device is polarized by the polarizing plate, and passes through the coating film of the colored composition coated on the glass substrate to reach the other polarizing plate. At this time, when the polarizing plate is parallel to the polarizing surface of the polarizing plate, the light passes through the polarizing plate, but when the polarizing surface is perpendicular to the polarizing plate, the light is blocked by the polarizing plate. However, when the light which is polarized by the polarizing plate passes through the coating film of the coloring composition, light scattering occurs due to the colorant particles, and a part of the polarizing surface is shifted, and the amount of light transmitted when it is parallel to the polarizing plate is reduced, or is polarized. Only a portion of the light passes through the plate when it is vertical. The luminance of the transmitted light on the polarizing plate is measured, and the luminance of the polarizing plate in parallel and the ratio of the luminance in the vertical direction are calculated as the contrast value.

(comparative value) = (luminance in parallel) / (luminance in vertical)

Therefore, when light scattering occurs due to the coloring agent in the coating film, the luminance in parallel is lowered, and the luminance in the vertical direction is increased, so that the contrast value can be lowered.

Further, the luminance meter is a color luminance meter ("BM-5A" manufactured by Topcon Japan Co., Ltd.), and a polarizing plate ("NPF-G1220DUN" manufactured by Nitto Denko Corporation) is used as the polarizing plate. In the measurement, the same coating film as that used for the evaluation of the brightness was used, and the measurement portion was measured by a black mask having a hole of 1 cm square, and then determined according to the following criteria.

○: 3500 or more

△: 3000 or more and less than 3,500

×: not up to 3000

From the results of the evaluation of Table 5, it is understood that the quinophthalone yellow pigment of the present embodiment and the ethylene-unsaturated monomer having at least one of an ethylene oxide chain or a propylene oxide chain are included in the copolymerization of ethylene polymerization. The colored compositions of Examples 1 to 33 composed of the pigment dispersing agents exhibited a low initial viscosity and a low rate of change in viscosity over time, and thus exhibited good stability. At the same time, the results have high brightness and high contrast value, and are shown as excellent coloring compositions for color filters. In contrast, a reference example in which a pigment dispersant composed of an ethylene polymer containing no ethylene oxide chain or propylene oxide chain is used is used. In the color compositions of 1 to 3 and 6 to 8, the initial viscosity of Reference Example 1 was low and the rate of change of viscosity over time was high, while the brightness was low and the contrast value was low. In addition, in the cases of Reference Examples 2, 3, and 6 to 8, the initial viscosity and the change rate of the viscosity over time were high, and the brightness was low and the contrast value was low. At the same time, the same applies to Reference Examples 4 and 5 in which different pigment dispersants are used. Reference Example 9 using a pigment dispersant composed of a non-quinoline yellow pigment and an ethylene polymer having at least one of an ethylene oxide chain or a propylene oxide chain and an ethylene polymer contained in a copolymerization composition The coloring composition of 10 was a satisfactory value in terms of the contrast value, but the result was inferior to the coloring composition of the example in terms of brightness.

<Production of photosensitive coloring composition>

Next, the green coloring composition used in the photosensitive coloring composition of the present embodiment will be described. Explain.

<Production of green coloring composition> (production of green coloring composition (GP-1))

The mixture of the following components was stirred and mixed to make it uniform, and then dispersed in an Eiger polishing and dispersing machine ("Mini Model M-250 MK II" manufactured by Eiger Japan Co., Ltd.) for 5 hours using zirconia beads having a diameter of 0.5 mm. Further, it was filtered through a 5 μm sieve to prepare a green colored composition (GP-1).

[Example 34] (Production of photosensitive coloring composition 1 (GR-1))

The mixture of the following composition was uniformly stirred and mixed, and then filtered through a 1 μm filter to prepare a photosensitive coloring composition (GR-1). The ratio of the yellow colored composition to the green colored composition is the ratio of the chromaticity of x=0.290 and y=0.600 under the C light source.

[Examples 35 to 66, Reference Examples 11 to 20] (Production of photosensitive coloring compositions 2 to 43 (GR-2 to 43))

In addition to changing the combination of the coloring compositions shown in Table 6 and changing the ratio of the yellow coloring composition to the green coloring composition, the photosensitive coloring composition 1 (GR-1) was used to prepare a photosensitive property. Coloring compositions 2 to 43 (GR-2 to 43). In addition, the ratio of the yellow coloring composition and the green coloring composition was selected in the chromaticity of x=0.290 and y=0.600 in the case of producing a coated substrate by a C light source. Further, the total content of the yellow coloring composition and the green coloring composition was 45.0 parts.

In terms of each of the photosensitive coloring compositions obtained, the brightness and the comparative value were measured by the following methods. (Brightness) is a photosensitive coloring composition (GR-1 to 43), coated on a glass substrate of 100 mm × 100 mm and 1.1 mm thick by a spin coater, dried at 70 ° C for 20 minutes, and then subjected to ultra high pressure. The mercury lamp was subjected to ultraviolet exposure with an accumulated amount of light of 150 mJ/cm ² , and then developed at 23 ° C with an alkali developing solution to obtain a coated substrate. Thereafter, the film was heated at 220 ° C for 30 minutes, and placed and cooled to prepare a coated substrate. At this time, the film thickness of the coating film was heat-treated at 230 ° C, and then applied under appropriate application conditions (rotation number and time of the spin coater) in a C light source of y = 0.600. The obtained coating film was measured for its brightness (Y) by a microspectrophotometer ("OSP-SP100" manufactured by Olympus, Japan), and was judged according to the following criteria.

○: 59.5 or more

△: 58.0 or more and less than 59.5

×: not up to 58.0

(comparative value)

For the measurement method of the contrast value of the coating film, the same coating film as the evaluation of the brightness is used, and the same method as the comparison of the yellow coloring composition described above is used, and the comparative value is calculated and judged according to the following criteria. .

○: 3500 or more

△: 3000 or more and less than 3,500

×: not up to 3000

As a result of the evaluation of Table 6, it is understood that ethylene containing the quinophthalone yellow pigment of the present embodiment and at least one of an ethylene oxide chain or a propylene oxide chain is contained in the copolymerization composition. The photosensitive coloring compositions of Examples 34 to 66 of the yellow coloring agent of the pigment dispersing agent composed of the polymer were excellent in both the brightness and the comparative value, and showed excellent coloring compositions for color filters. In contrast, a pigment dispersant composed of an ethylene polymer containing no ethylene oxide chain or propylene oxide chain is used. The photosensitive coloring compositions of Reference Examples 11 to 20 were inferior in either of their brightness and comparative values, or either of them was inferior to the photosensitive coloring composition of the examples.

<Production of color filter>

Next, the red photosensitive coloring composition and the blue photosensitive coloring composition used in the color filter of the present embodiment will be described. Further, in the case of the green photosensitive coloring composition, the photosensitive coloring composition 1 (GR-1) of the present embodiment is used.

<Red photosensitive coloring composition> (production of red coloring composition (RP-1))

After the mixture having the composition of the following composition was stirred and mixed to be uniform, the zirconia beads having a diameter of 0.5 mm were used, and dispersed by an Eiger attritor ("Mini Model M-250 MK II" manufactured by Eiger Japan Co., Ltd.) for 5 hours. Further, it was filtered through a 5 μm sieve to prepare a red colored composition 1 (RP-1).

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

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

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

After the mixture of the following composition was stirred and mixed to make it uniform, dispersion was carried out for 5 hours using an Eiger mill ("Mini Model M-250 MK II" manufactured by Eiger Japan Co., Ltd.) using a zirconia bead having a diameter of 0.1 mm. Further, it was filtered through a 5 μm sieve to prepare a blue colored composition (BP-1).

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

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

The black matrix on the glass substrate was first processed into an image, and the red photosensitive coloring composition (RR-1) was applied onto the substrate by a spin coater to form a colored film having a film thickness of x=0.640 and y=0.330. The film was irradiated with ultraviolet rays at 300 mJ/cm ² using an ultrahigh pressure mercury lamp through a mask. Next, it was spray-imaged with an alkali developing solution composed of a 0.2% sodium carbonate aqueous solution to remove the unexposed portion, and then washed with ion-exchanged water, and the substrate was heated at 230 ° C for 20 minutes to form a red color. Color filter fragment. In the same manner, the green photosensitive coloring composition 1 (GR-1) was formed into a film thickness of x=0.290 and y=0.600, and the blue photosensitive coloring composition (BR-1) was combined. The coating was applied to a film thickness of x=0.150 and y=0.060 to form a green color filter segment and a blue color filter segment, thereby obtaining a color filter.

With the photosensitive coloring composition 1 (GR-1), a color filter having high luminance and a high contrast value can be produced.

"Embodiment IV"

The method for measuring the weight average molecular weight (Mw) of the resin is as follows. (Measurement of Weight Average Molecular Weight (Mw) of Resin

The weight average molecular weight (Mw) of the resin was measured by TSK gel column (manufactured by Tosoh Corporation of Japan) and GPC (manufactured by Tosoh Corporation of Japan, HLC-8120GPC) of the apparatus RI detector. The weight average molecular weight (Mw) of the converted polystyrene.

Next, a method of producing a binder resin solution, a dye derivative, a colorant, a green coloring composition, and a blue coloring composition used in the examples and the reference examples will be described.

<Method for Producing Binder Resin Solution> (modulation of acrylic resin solution 1)

196 parts of cyclohexanone was placed in a reaction vessel equipped with a thermometer, a condenser, a nitrogen introduction tube, a dropping tube, and a stirring device in a separable 4-necked flask, and the temperature was raised to 80 ° C, and the reaction vessel was replaced. After nitrogen gas, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, and 20.7 parts of p-isopropylidene phenol were epoxy. A mixture of ethane-modified acrylate ("Aronix M110" manufactured by Japan East Asia Synthetic Co., Ltd.) and 1.1 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After the completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a solution of an acrylic resin. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried at 180 ° C for 20 minutes to determine the nonvolatile matter, and the amount of the nonvolatile matter was 20% by mass in the previously synthesized resin solution. It was prepared into an acrylic resin solution 1. Its weight average molecular weight (Mw) was 26,000.

(modulation of acrylic resin solution 2)

207 parts of cyclohexanone was placed in a reaction vessel equipped with a thermometer, a condenser, a nitrogen introduction tube, a dropping tube, and a stirring device in a separable 4-necked flask, and the temperature was raised to 80 ° C, and the reaction vessel was replaced. After nitrogen gas, 20 parts of methacrylic acid, 20 parts of p-isopropylidene phenol oxirane modified acrylate ("Aronix M110" manufactured by Japan East Asia Synthesis Co., Ltd.), and 45 parts of methyl group were dropped by a dropping tube. A mixture of methyl acrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 1.33 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After the completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a copolymer resin solution. Next, the total amount of the copolymer solution was further stirred, and after nitrogen gas was stopped and the dry air was injected for 1 hour while stirring, after cooling to room temperature, A mixture of 6.5 parts of isocyanate-2-methylpropenyloxyethyl ester (Karenz MOI manufactured by Showa Denko Co., Ltd.), 0.08 parts of dibutyltin laurate, and 26 parts of cyclohexanone at 70 ° C was used. Instilled in hours. After the completion of the dropwise addition, the reaction was further 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 the non-volatile matter was measured by heating at 180 ° C for 20 minutes, and cyclohexanone was added in such a manner that the non-volatile content was 20% by mass in the previously synthesized resin solution. Formed into acrylic resin solution 2. Its weight average molecular weight (Mw) was 18,000.

<Method for Producing Pigment Derivative> (Manufacture of Pigment Derivative 1)

First, a dye derivative (1) is obtained according to the synthesis method described in Japanese Patent No. 4585781.

<Method for Producing Colorant> (Manufacture of quinoline yellow compound (1))

First, a quinophthalone compound (1) is obtained according to the synthesis method described in JP-A-2008-81566. As a result of mass analysis by TOF-MS, it was identified as a quinophthalone compound (1).

(Manufacture of quinoline yellow compound (2))

First, in 200 parts of methyl benzoate, 40 parts of 8-aminomethylquinoline, 150 parts of 2,3-naphthalenedicarboxylic anhydride, and 154 parts of benzoic acid were added, and the mixture was heated to 180 ° C for 4 hours. Thereafter, 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 further subjected to filtration separation, methanol washing, and drying to obtain 116 parts of a specific quinophthalone pigment represented by the formula (A-3). As a result of mass analysis by TOF-MS, it can be identified as a quinoline yellow pigment of the formula (A-3).

Then, the quinoline yellow pigment of the formula (A-3) is used as a raw material, and the synthesis method described in JP-A-2008-81566 is used in the same manner as in the synthesis of the quinophthalone compound (1). Quinoline yellow compound (2). As a result of mass analysis by TOF-MS, it was identified as a quinophthalone compound (2).

(Manufacture of quinoline yellow compound (3))

First, 20 parts of 8-hydroxy-2-methylquinoline, 25 parts of naphthalene dicarboxylic anhydride, and 300 parts of benzoic acid were mixed, and the reaction was further stirred at 200 ° C for 7 hours. After standing to cool, 1000 parts of methanol was further added and stirred for 1 hour. Thereafter, the precipitated solids were collected by suction filtration. The solid was again added to 2000 parts of methanol, and after stirring for 1 hour, the solid was collected by suction filtration. Thereafter, it was dried overnight in a vacuum dryer (40 ° C) to obtain 37 parts of quinoline yellow compound (3). As a result of mass analysis by TOF-MS, it was identified as a quinophthalone compound (3).

(Manufacture of yellow colorant (YA-1))

First, in 300 parts of methyl benzoate, 100 parts of quinoline yellow compound (1), 70 parts of 2,3-naphthalene dicarboxylic anhydride, and 143 parts of benzoic acid are added, and then heated to 180 ° C to carry out the reaction. 4 hours. Then, by TOF-MS, the formation of the specific quinophthalone pigment represented by the formula (A-1) and the disappearance of the quinophthalone compound (1) of the starting material are determined, and then the reaction is allowed to cool to room temperature, and then the reaction is carried out. The mixture was poured into 3130 parts of acetone and stirred at room temperature for 1 hour. The product was further subjected to filtration separation, methanol washing, and drying to obtain 120 parts of a specific quinophthalone pigment represented by the formula (A-1). As a result of mass analysis by TOF-MS, it can be identified as a quinoline yellow pigment of the formula (A-1).

Thereafter, 100 parts of the quinoline yellow pigment of the formula (A-1), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a 1-gallon kneader (manufactured by Inoue, Ltd.) made of stainless steel, and Mix for 6 hours at 60 °C. Next, the mixture is put into 3 liters of warm water, heated to about 70 ° C while stirring for 1 hour to make it into a slurry, repeatedly filtered, washed with water to remove sodium chloride and diethylene glycol, and then 80 After drying overnight at ° C, 98 parts of a yellow coloring agent (YA-1) was obtained. Its average primary particle size is 31.3 nm.

(Manufacture of yellow colorant (YA-2))

First, 50 parts of the quinoline yellow pigment of the formula (A-1), 50 parts of the CI Pigment Yellow No. 138 ("Paliotol Yellow K0960-HD" manufactured by BASF Corporation), 1200 parts of sodium chloride, and 120 parts Ethylene glycol was placed in a 1-gallon kneader (manufactured by Inoue, Ltd.) made of stainless steel, and mixed at 60 ° C for 8 hours. Next, the mixture is put into warm water, heated to about 70 ° C while stirring for 1 hour to make it into a slurry, repeatedly filtered, washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. One night, 97 parts of a yellow colorant (YA-2) was obtained. Its average primary particle diameter was 30.2 nm.

(Manufacture of yellow colorant (YA-3))

First, 100 parts of the benzoyl yellow compound (2), 108 parts of tetrachlorophthalic anhydride, and 143 parts of benzoic acid were added to 300 parts of methyl benzoate, and the mixture was heated to 180 ° C for 4 hours. Thereafter, 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 further subjected to filtration separation, methanol washing, and drying to obtain 118 parts of the specific quinophthalone pigment represented by the formula (A-2). TOF-MS As a result of the mass analysis, it can be identified as the quinophthalone yellow pigment of the formula (A-2).

Thereafter, 100 parts of the quinoline yellow pigment represented by the formula (A-2), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a 1-gallon kneader made of stainless steel (manufactured by Inoue, Ltd.). And mix at 60 ° C for 6 hours. Next, the mixture was put into 3 liters of warm water, heated to 70 ° C while stirring for 1 hour to make a slurry, repeated filtration, washing with water to remove sodium chloride and diethylene glycol, and then at 80 ° C After drying overnight, 98 parts of a yellow colorant (YA-3) was obtained. Its average primary particle size was 31.1 nm.

(Manufacture of yellow colorant (YA-4))

50 parts of quinoline yellow pigment of formula (A-2), 50 parts of CI Pigment Yellow No. 138 ("Paliotol Yellow K0960-HD" manufactured by BASF), 1200 parts of sodium chloride, and 120 parts The ethylene glycol was added to a 1-gallon kneader made of stainless steel (manufactured by Inoue, Ltd.), and mixed at 60 ° C for 8 hours. Next, the mixture is put into warm water, heated to about 70 ° C while stirring for 1 hour to make it into a slurry, repeatedly filtered, washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. One night, 97 parts of a yellow colorant (YA-4) was obtained. Its average primary particle diameter was 30.2 nm.

(Manufacture of yellow colorant (YA-5))

20 parts of the quinoline yellow pigment of the formula (A-2), 80 parts of the CI Pigment Yellow No. 138 ("Paliotol Yellow K0960-HD" manufactured by BASF Corporation), 1200 parts of sodium chloride, and 120 parts The ethylene glycol was added to a 1-gallon kneader made of stainless steel (manufactured by Inoue, Ltd.), and mixed at 60 ° C for 8 hours. Next, the mixture is put into warm water, heated to about 70 ° C while stirring for 1 hour to make it into a slurry, repeatedly filtered, washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. One night, 96 parts of yellow colorant (YA-5) were obtained. Its average primary particle diameter was 29.7 nm.

(Manufacture of yellow colorant (YA-6))

100 parts of the quinoline yellow pigment of the formula (A-3), 1200 parts of sodium chloride, and 120 parts of diethylene glycol are first added to a 1-gallon kneader made by a stainless steel (manufactured by Inoue, Japan). And mixed at 60 ° C for 8 hours. Next, the mixture is put into warm water, heated to about 70 ° C while stirring for 1 hour to make it into a slurry, repeatedly filtered, washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. One night, 97 parts of a yellow colorant (YA-6) was obtained. Its average primary particle diameter was 34.1 nm.

(Manufacture of yellow colorant (YA-7))

First, in 300 parts of methyl benzoate, add 100 parts of quinoline yellow compound (2), 176 parts of tetrabromophthalic anhydride, and 143 parts of benzoic acid, plus The reaction was carried out for 6 hours while heating to 180 °C. Thereafter, 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 further subjected to filtration separation, methanol washing, and drying to obtain 138 parts of the specific quinophthalone yellow pigment of the formula (A-5). As a result of mass analysis by TOF-MS, it can be identified as a quinoline yellow pigment of the formula (A-5).

Thereafter, 100 parts of the quinoline yellow pigment of the formula (A-5), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a 1-gallon kneader made of stainless steel (manufactured by Inoue, Ltd.). And mix at 80 ° C for 8 hours. Next, the mixture was put into 3 liters of warm water, heated to 70 ° C while stirring for 1 hour to make a slurry, repeated filtration, washing with water to remove sodium chloride and diethylene glycol, and then at 80 ° C After drying overnight, 97 parts of a yellow colorant (YA-7) was obtained. Its average primary particle diameter was 28.3 nm.

(Manufacture of yellow colorant (YA-8))

50 parts of quinoline yellow pigment of formula (A-5), 50 parts of CI Pigment Yellow No. 138 ("Paliotol Yellow K0960-HD" manufactured by BASF), 1200 parts of sodium chloride, and 120 parts The ethylene glycol was added to a 1-gallon kneader made of stainless steel (manufactured by Inoue, Ltd.), and mixed at 60 ° C for 8 hours. Next, the mixture is put into warm water, heated to about 70 ° C while stirring for 1 hour to make it into a slurry, repeated filtration, washing with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C One day and night, 98 parts of a yellow colorant (YA-8) was obtained. Its average primary particle diameter was 28.1 nm.

(Manufacture of yellow colorant (YB-1))

First, 29 parts of 6-hexyl-2-methylquinoline and 25 parts of naphthalene dicarboxylic anhydride, 300 parts of benzoic acid were mixed, and stirred at 200 ° C for 7 hours. After standing to cool, 1000 parts of methanol was further added and stirred for 1 hour. Thereafter, the precipitated solids were collected by suction filtration. The solid was again added to 2000 parts of methanol, and after stirring for 1 hour, the solid was collected by suction filtration. Thereafter, it was dried overnight in a vacuum dryer (40 ° C) to obtain 42 parts of the specific quinophthalone yellow dye (yellow coloring agent (YB-1)) represented by the formula (B-1). As a result of mass analysis by TOF-MS, it can be identified as a quinoline yellow dye of (B-1).

(Manufacture of yellow colorant (YB-2))

First, 34 parts of 8-(2-ethylhexyloxy)-2-methylquinoline and 25 parts of naphthalene dicarboxylic anhydride, 300 parts of benzoic acid were mixed, and stirred at 200 ° C for 7 hours. After standing to cool, 1000 parts of methanol was further added and stirred for 1 hour. Thereafter, the precipitated solids were collected by suction filtration. The solid was again added to 2000 parts of methanol, and after stirring for 1 hour, the solid was collected by suction filtration. Thereafter, it was dried overnight in a vacuum dryer (40 ° C) to obtain 50 parts of the specific quinophthalone yellow dye represented by the formula (B-5) (yellow Colorant (YB-2)). The result of mass analysis by TOF-MS can be identified as the quinophthalone yellow dye of the formula (B-5).

(Manufacture of yellow colorant (YB-3))

First, 44 parts of 8-(2-ethylhexyloxy)-5-phenyl-2-methylquinoline and 25 parts of naphthalene dicarboxylic anhydride, 300 parts of benzoic acid were mixed, and stirred at 200 ° C. hour. After standing to cool, 1000 parts of methanol was further added and stirred for 1 hour. Thereafter, the precipitated solids were collected by suction filtration. The solid was again added to 2000 parts of methanol, and after stirring for 1 hour, the solid was collected by suction filtration. Thereafter, it was dried overnight in a vacuum dryer (40 ° C) to obtain 57 parts of a specific quinophthalone yellow dye (yellow coloring agent (YB-3)) represented by the formula (B-6). The result of mass analysis by TOF-MS can be identified as the quinoline yellow dye of the formula (B-6).

(Manufacture of yellow colorant (YB-4))

First, 46 parts of 8-dodecyloxy-5-bromo-2-methylquinoline and 25 parts of naphthalene dicarboxylic anhydride, 300 parts of benzoic acid were mixed, and stirred at 200 ° C. hour. After standing to cool, 1000 parts of methanol was further added and stirred for 1 hour. Thereafter, the precipitated solids were collected by suction filtration. The solid was again added to 2000 parts of methanol, and after stirring for 1 hour, the solid was collected by suction filtration. Thereafter, it was dried overnight in a vacuum dryer (40 ° C) to obtain 46 parts of the specific quinophthalone yellow dye (yellow coloring agent (YB-4)) represented by the formula (B-8). The result of mass analysis by TOF-MS can be identified as the quinophthalone yellow dye of the formula (B-8).

(Manufacture of yellow colorant (YB-5))

First, 34 parts of 6-(2-ethylhexyloxy)-2-methylquinoline and 25 parts of naphthalene dicarboxylic anhydride, 300 parts of benzoic acid were mixed, and stirred at 200 ° C for 7 hours. After standing to cool, 1000 parts of methanol was further added and stirred for 1 hour. Thereafter, the precipitated solids were collected by suction filtration. The solid was again added to 2000 parts of methanol, and after stirring for 1 hour, the solid was collected by suction filtration. Thereafter, it was dried overnight in a vacuum dryer (40 ° C) to obtain 43 parts of a specific quinophthalone yellow dye (yellow coloring agent (YB-5)) represented by the formula (B-10). As a result of mass analysis by TOF-MS, it can be identified as a quinoline yellow dye of the formula (B-10).

(Manufacture of yellow colorant (YB-6))

First, 29 parts of 6-(2-ethoxyethoxy)-2-methylquinoline and 25 parts of naphthalene dicarboxylic anhydride, 300 parts of benzoic acid were mixed, and stirred at 200 ° C for 7 hours. After standing to cool, 1000 parts of methanol was further added and stirred for 1 hour. Thereafter, the precipitated solids were collected by suction filtration. The solid was again added to 2000 parts of methanol, and after stirring for 1 hour, the solid was collected by suction filtration. Thereafter, it was dried overnight in a vacuum dryer (40 ° C) to obtain 39 parts of the specific quinophthalone yellow dye (yellow coloring agent (YB-6)) represented by the formula (B-11). The result of mass analysis by TOF-MS can be identified as the quinoline yellow dye of the formula (B-11).

(Manufacture of yellow colorant (YB-7))

First, 34 parts of 6-(2-(1,3-) Alkan-2-yl)ethoxy)-2-methylquinoline and 25 parts of naphthalene dicarboxylic anhydride, 300 parts of benzoic acid were mixed and stirred at 200 ° C for 7 hours. After standing to cool, 1000 parts of methanol was further added and stirred for 1 hour. Thereafter, the precipitated solids were collected by suction filtration. The solid was further added to 2000 parts of methanol, and after stirring for 1 hour, it was collected by suction filtration. Thereafter, it was dried overnight in a vacuum dryer (40 ° C) to obtain 33 parts of a specific quinophthalone yellow dye (yellow coloring agent (YB-7)) represented by the formula (B-12). The result of mass analysis by TOF-MS can be identified as the quinoline yellow dye of the formula (B-12).

(Manufacture of yellow colorant (YB-3))

First, 34 parts of 4-(2-ethylhexyloxy)-2-methylquinoline and 25 parts of naphthalene dicarboxylic anhydride, 300 parts of benzoic acid were mixed, and stirred at 200 ° C for 7 hours. After standing to cool, 1000 parts of methanol was further added and stirred for 1 hour. Thereafter, the precipitated solids were collected by suction filtration. The solid was again added to 2000 parts of methanol, and after stirring for 1 hour, the solid was collected by suction filtration. Thereafter, it was dried overnight in a vacuum dryer (40 ° C) to obtain 42 parts of a specific quinophthalone yellow dye (yellow coloring agent (YB-8)) represented by the formula (B-13). As a result of mass analysis by TOF-MS, it can be identified as a quinoline yellow dye of the formula (B-13).

(Manufacture of yellow colorant (YB-9))

First, 20 parts of quinoline yellow compound (3) is mixed with 200 parts of N,N-dimethylacetamide, and then 3 parts of sodium hydroxide and 18 parts of 2-ethylhexyl-4-bromo are mixed. Butyric acid was then stirred at 90 ° C for 1 hour. After it was left to cool, 1000 parts of methanol and 1000 parts of water were further added and stirred for 1 hour. Thereafter, the precipitated solids were collected by suction filtration. The solid was again added to 1000 parts of methanol, and after stirring for 1 hour, the solid was collected by suction filtration. Thereafter, it was dried overnight in a vacuum dryer (40 ° C) to obtain 16 parts of a specific quinophthalone yellow dye (yellow coloring agent (YB-9)) represented by the formula (B-27). The result of mass analysis by TOF-MS can be identified as the quinoline yellow dye of the formula (B-27).

(Manufacture of yellow colorant (YB-10))

Mixing 20 parts of quinoline yellow compound (3) in 200 parts of N,N-dimethylacetamide, then mixing 3 parts of sodium hydroxide and 19 parts of 2-ethylhexyl-5-bromo Valeric acid was then stirred at 90 ° C for 1 hour. After it was left to cool, 1000 parts of methanol and 1000 parts of water were further added and stirred for 1 hour. Thereafter, the precipitated solids were collected by suction filtration. The solid was again added to 1000 parts of methanol, and after stirring for 1 hour, the solid was collected by suction filtration. Then dried overnight in a vacuum dryer (40 ° C). 20 parts of the specific quinophthalone yellow dye (yellow colorant (YB-10)) represented by the formula (B-28) was obtained. The result of mass analysis by TOF-MS can be identified as the quinoline yellow dye of the formula (B-28).

(Manufacture of yellow colorant (YB-11))

First, 20 parts of the commercially available CI Disperse Dye Yellow No. 160 was mixed with 200 parts of N,N-dimethylacetamide, and then 3 parts of sodium hydroxide and 18 parts of 2-ethylhexyl group were mixed. 4-Bromobutyric acid was then stirred at 90 ° C for 1 hour. After it was left to cool, 1000 parts of methanol and 1000 parts of water were further added and stirred for 1 hour. Thereafter, the precipitated solids were collected by suction filtration. The solid was again added to 1000 parts of methanol, and after stirring for 1 hour, the solid was collected by suction filtration. Thereafter, it was dried overnight in a vacuum dryer (40 ° C) to obtain 20 parts of a specific quinophthalone yellow dye (yellow coloring agent (YB-11)) represented by the formula (B-30). As a result of mass analysis by TOF-MS, it can be identified as a quinoline yellow dye of the formula (B-30).

(Manufacture of yellow colorant (YC-1))

First, 100 parts of CI Pigment Yellow No. 138 ("Paliotol Yellow K0960-HD" manufactured by BASF), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were added to a 1-gallon kneading machine made of stainless steel (Japan Inoue Co., Ltd.) Manufactured and mixed at 70 ° C for 6 hours. Next, the mixture is put into warm water, heated to 70 ° C while stirring for 1 hour to make a slurry, repeatedly filtered, washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C Day and night, 98 parts of yellow colorant (YC-1) were obtained. Its average primary particle size is 35.5 nm.

(Manufacture of green colorant (GC-1))

First, 100 parts of CI Pigment Green No. 58 ("FASTGEN GREEN A110" manufactured by DIC Corporation), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were added to a 1-gallon kneading machine made of stainless steel (manufactured by Inoue, Japan) Medium and mixed at 70 ° C for 6 hours. Next, the mixture is put into warm water, heated to 70 ° C while stirring for 1 hour to make a slurry, repeatedly filtered, washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C Day and night, 97 parts of green colorant (GC-1) were obtained. Its average primary particle diameter was 28.2 nm.

(Manufacture of blue colorant (BC-1))

First, 225 parts of sebaconitrile and 78 parts of anhydrous aluminum chloride were added to 1250 parts of n-pentanol in the reaction vessel, followed by stirring. Thereafter, 266 parts of DBU (1,8-Diazabicyclo [5.4.0] undec-7-ene) was added thereto and heated, and refluxed at 136 ° C for 5 hours. Then, the reaction solution cooled to 30 ° C under stirring, mixed solvent of 5000 parts of methanol and 10000 parts of water In the middle, it was poured under stirring to obtain a blue slurry. The slurry was further filtered, washed with a mixed solvent of 2000 parts of methanol and 4000 parts of water, and dried to obtain 135 parts of chloroaluminum indigo. Thereafter, 100 parts of chloroaluminum in the reaction vessel was gradually added to 1200 parts of concentrated sulfuric acid at room temperature. After further stirring at 40 ° C for 3 hours, the sulfuric acid solution was poured into 24,000 parts of 3 ° C cold water. The blue precipitate was filtered, washed with water and dried to obtain 102 parts of anthraquinone aluminum (1).

Thereafter, 100 parts of anthraquinone aluminum (1) and 49.5 parts of diphenyl phosphate were added to 1000 parts of methanol in the reaction vessel, and the mixture was further heated to 40 ° C for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol, and dried to obtain 114 parts of anthraquinone aluminum (2).

After that, salt grinding treatment is carried out. First, 100 parts of ruthenium aluminum (2), 1200 parts of sodium chloride, and 120 parts of diethylene glycol are added to stainless steel. A gallon kneader (manufactured by Inoue, Ltd., Japan) was mixed at 70 ° C for 6 hours. Then, the mixture is put into warm water, heated to about 70 ° C while stirring for 1 hour to make it into a slurry, repeatedly filtered, washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. Day and night, 98 parts of blue colorant (BC-1) were obtained. Its average primary particle size was 31.2 nm.

<Method for Producing Green and Blue Colored Composition> (Production of green coloring composition (DG-1))

After stirring and mixing the mixture of the following components, a zirconia bead having a diameter of 0.5 mm was used, and an Eiger attritor of a Media wet disperser ("Mini Model M-250 MK II" manufactured by Eiger Japan Co., Ltd.) was used. After dispersing for 5 hours, it was filtered through a 5 μm sieve to prepare a green colored composition 1 (DG-1).

(production of blue coloring composition (DB-1))

After the mixture of the following composition was stirred and mixed to be uniform, a zirconia bead having a diameter of 0.5 mm was used, and dispersed by a Media wet disperser ("Mini Model M-250 MK II" manufactured by Eiger Japan Co., Ltd.) for 5 hours, and then The mixture was filtered through a 5 μm sieve to prepare a blue colored composition (DB-1).

<Method for Producing Yellow Colored Composition> [Example 1] (production of yellow coloring composition (DY-1))

After the mixture of the following composition was stirred and mixed to be uniform, a zirconia bead having a diameter of 0.5 mm was used, and dispersed by a Media wet disperser ("Mini Model M-250 MK II" manufactured by Eiger Japan Co., Ltd.) for 5 hours, and then The mixture was filtered through a 5 μm sieve to prepare a yellow colored composition (DY-1).

[Examples 2 to 33, Reference Examples 1 to 5] (Yellow coloring composition (DY-2 to 38))

The yellow colored composition (DY-2 to 38) was obtained in the same manner as in the yellow colored composition (DY-1) of Example 1, except that the kind and the amount of the yellow coloring agent were changed as shown in Table 1. Further, the total content of the yellow colorants therein was 9.6 parts.

Yellow colorant (YC-2): commercially available C.I. Disperse Dye Yellow No. 54

Yellow colorant (YC-3): commercially available C.I. Disperse Dye Yellow 64

<Evaluation of yellow coloring composition>

The spectral transmittance, contrast value, coloring power, heat resistance, and light resistance of the yellow coating film produced using the obtained yellow colored composition (DY-1 to 38) were evaluated by the following methods. Table 2 shows the results of their evaluation.

(Assessment of spectral transmittance)

The composition was colored in yellow (DY-1 to 38), coated on a 100 mm × 100 mm, 1.1 mm thick glass substrate by a spin coater, followed by drying at 70 ° C for 20 minutes and then at 220 ° C for 20 minutes. It was left to cool to form a coated substrate. The prepared coated substrate was subjected to heat treatment at 220 ° C, and the transmittance at 450 nm was 5%, and 500 nm was measured by a micro spectrophotometer ("OSP-SP100" manufactured by Olympus, Japan). Split light transmittance of 550nm. The higher the spectral transmittance at 500 nm and 550 nm, the better the brightness. The spectral transmittance of the 500 nm and 550 nm was determined according to the following criteria.

○: 99% or more

△: 97 or more and less than 99%

×: less than 97%

(evaluation of comparison value)

The light emitted from the backlight unit for the liquid crystal display device is polarized by the polarizing plate, and passes through the coating film of the colored composition coated on the glass substrate to reach the other polarizing plate. At this time, when the polarizing plate is parallel to the polarizing surface of the polarizing plate, the light passes through the polarizing plate, but when the polarizing surface is perpendicular to the polarizing plate, the light is blocked by the polarizing plate. However, when the light which is polarized by the polarizing plate passes through the coating film of the coloring composition, light scattering occurs due to the colorant particles, and a part of the polarizing surface is shifted, and the amount of light transmitted when it is parallel to the polarizing plate is reduced, or is polarized. Only a portion of the light passes through the plate when it is vertical. The luminance of the transmitted light on the polarizing plate is measured, and the luminance of the polarizing plate in parallel and the ratio of the luminance in the vertical direction are calculated as the contrast value.

(comparative value) = (luminance in parallel) / (luminance in vertical)

Therefore, when light scattering occurs due to the coloring agent in the coating film, the luminance in parallel is lowered, and the luminance in the vertical direction is increased, so that the contrast value can be lowered. Further, among the luminance meters, a color luminance meter ("BM-5A" manufactured by Topcon Japan Co., Ltd.) was used, and a polarizing plate ("NPF-G1220DUN" manufactured by Nitto Denko Corporation) was used as the polarizing plate. At the time of the measurement, it was measured by a black mask which was opened by a 1 cm square hole in the measurement part.

At the same time, the coated substrate used in the evaluation of the comparative value was coated with a yellow coloring composition (DY-1 to 38) on a glass substrate of 100 mm × 100 mm and 1.1 mm thick by a spin coater, followed by coating. It was dried at 70 ° C for 20 minutes, then heated at 220 ° C for 20 minutes, and left to cool. The prepared coated substrate was subjected to heat treatment at 220 ° C, and then allowed to be combined with a chromaticity of x = 0.440 under a C light source. The comparison value is determined according to the following criteria.

○: 3000 or more

△: 2000 or more and less than 3000

×: not up to 2000

(assessment of tinting strength)

The film thickness at the chromaticity of x (C) = 0.440 was measured by the same coating film as the evaluation of the comparative value, and was determined according to the following criteria. The smaller the film thickness when the chromaticity of x (C) = 0.440 is given, the larger the coloring power is, which is preferable.

○: less than 2.0 [μm]

△: 2.0 or more and less than 3.0 [μm]

×: 3.0 or more [μm]

(Evaluation of heat resistance)

The yellow colored composition (DY-1 to 38) was coated on a 100 mm × 100 mm, 1.1 mm thick glass substrate by a spin coater, followed by drying at 70 ° C for 20 minutes, and then heating at 220 ° C for 20 minutes. In a minute, it was left to cool to prepare a coated substrate. The prepared coated substrate was subjected to heat treatment at 220 ° C, and then allowed to be combined with a chromaticity of x = 0.440 under a C light source. The chromaticity ([L*(1)], a*(1), b*(1)))) of the obtained coating film under a C light source is a microscopic spectrophotometer ("OSP-SP100" manufactured by Olympus, Japan). ")). Thereafter, the heat resistance test was performed by heating at 230 ° C for 1 hour, and the chromaticity ([L*(2)], a*(2), b*(2))) under the C light source was measured, and the following The calculation formula is used to determine the color difference ΔEab*, and is evaluated in the following three stages.

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

○: △Eab* is less than 5.0

△: △Eab* is above 5.0 and not up to 10.0

×: △Eab* is above 10.0

(Assessment of light resistance)

The coated substrate is prepared in the same manner as in the evaluation of heat resistance, and the chromaticity ([L*(1)), a*(1), b*(1))) under the C light source is microscopic spectrophotometry. The measurement ("OSP-SP100" manufactured by Olympus Corporation of Japan) was measured. Then, an ultraviolet-resistant color filter ("COLORED OPTICAL GLASS L38" manufactured by Hoya Co., Ltd., Japan) was attached to the substrate, and the ultraviolet light was irradiated with a xenon lamp of 470 W/m ² for 100 hours, and then the color under the C light source was measured. The degree ([L*(2), a*(2), b*(2)))), the color difference ΔEab* was obtained by the above calculation formula, and was evaluated on the same basis as the heat resistance.

As shown in Table 2, the coloring agent having the characteristics of the present embodiment contains the yellow coloring of the example of the quinophthalone yellow pigment represented by the general formula (1) and the quinophthalone yellow dye represented by the general formula (6). Composition, the result is spectral light transmittance, Both the contrast value and the coloring power are excellent, and there is no problem in terms of heat resistance and light resistance of the coating film.

On the other hand, with reference to the yellow colored compositions (DY-34 to 36) of Examples 1 to 3, the results were low in luminance. When the specific quinophthalone yellow dye was used alone, and the yellow colored composition (DY-37, 38) of Reference Examples 4 and 5 of C.I. Pigment Yellow No. 138 was used in combination, the brightness was good, but the comparative value was low. Further, the yellow colored composition (DY-34) of Reference Example 1 which was used alone as C.I. Pigment Yellow No. 138 of the conventional pigment had a problem that the coloring power was low in addition to the low brightness. The yellow colored composition (DY-35, 36) of Reference Examples 2 and 3 of CI disperse dye yellow No. 54 of non-quinoline yellow dye [B] and CI disperse dye yellow No. 64 was used, and the results were comparative values and heat resistance. Both sex and light resistance are poor.

<Method for Producing Green Photosensitive Colored Composition> [Example 34] (Green photosensitive coloring composition (RG-1))

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

[Examples 35 to 70, Reference Examples 6 to 15] (Production of green photosensitive coloring composition (RG-2 to 47))

In addition to using the yellow coloring composition as shown in Table 3, and the green coloring composition or the blue coloring composition, and changing the yellow coloring of the chromaticity of x=0.290 and y=0.600 under the C light source at the time of coating film evaluation The photosensitive material was produced in the same manner as the photosensitive coloring composition (RG-1) except for the ratio of the composition of the green coloring composition or the blue coloring composition (to the ratio of the total amount of the yellow coloring composition to 45 parts). Coloring composition ((RG-2 to 47).

<Evaluation of green photosensitive coloring composition>

The brightness, contrast value, coloring power, heat resistance, light resistance, and sensitivity of the green coating film produced by the obtained green photosensitive coloring composition (RG-1 to 47) were evaluated by the following methods. Table 4 shows the results of their evaluation.

(evaluation of brightness)

The green photosensitive coloring composition (RG-1 to 47) was applied on a glass substrate of 100 mm × 100 mm and 1.1 mm thick by a spin coater, followed by drying at 70 ° C for 20 minutes, and then ultrahigh pressure mercury. The lamp was subjected to ultraviolet light exposure at a total amount of light of 150 mJ/cm ² , and then developed at 23 ° C with an alkali developing solution to obtain a coated substrate. Thereafter, the mixture was heated at 220 ° C for 20 minutes, and after standing and cooled, the brightness Y (C) of the obtained coated substrate was measured by a microspectrophotometer ("OSP-SP100" manufactured by Olympus, Japan). The coated substrate was subjected to a heat treatment at 220 ° C, and then subjected to a chromaticity of x=0.290 and y=0.600 under a C light source. In the case of the alkali imaging solution, 1.5% by mass of sodium carbonate, 0.5% by mass of sodium hydrogencarbonate, 8.0% by mass of an anionic surfactant ("Pelex NBL" manufactured by Kao Corporation, Japan), and 90% by mass of water are used. By. Thereafter, the value of the brightness is determined based on the following criteria.

○: 60.5 or more

△: 58.5 or more and less than 60.5

×: not up to 58.5

(evaluation of comparison value)

The measurement method of the comparative value of the coating film was measured by the same method as the comparison of the yellow coloring composition. And use the same as the evaluation of brightness After the film is calculated, the comparison value is calculated, and then judged according to the following criteria.

○: 3500 or more

△: 3000 or more and less than 3,500

×: not up to 3000

(assessment of tinting strength)

The film thickness at the chromaticity of x(C)=0.290 and y(C)=0.600 was measured using the same coating film as the evaluation of the brightness, and was determined according to the following criteria. The smaller the film thickness of the chromaticity showing x(C)=0.290 and y(C)=0.600, the larger the coloring power is, the better.

○: and less than 2.5 [μm]

△: 2.5 or more and less than 3.0 [μm]

×: 3.0 or more [μm]

(Evaluation of heat resistance)

Using a green photosensitive coloring composition (RG-1 to 47), coating on a 100 mm × 100 mm, 1.1 mm thick glass substrate by a spin coater, followed by drying at 70 ° C for 20 minutes, and then using an ultrahigh pressure mercury lamp Ultraviolet exposure was carried out at a cumulative amount of light of 150 mJ/cm ² , followed by development with an alkali developing solution at 23 ° C. Thereafter, the mixture was heated at 220 ° C for 20 minutes, and after standing to cool, a coated substrate was obtained. The coated substrate prepared in this manner was subjected to a heat treatment at 220 ° C, and then subjected to a chromaticity of x=0.290 and y=0.600 under a C light source. The chromaticity ([L*(1), a*(1), b*(1)))) of the obtained coating film under the C light source is a microscopic spectrophotometer ("OSP-SP100" manufactured by Olympus, Japan" ) Determination. Thereafter, the heat resistance test was performed by heating at 230 ° C for 1 hour, and the chromaticity ([L*(2), a*(2), b*(2)))) under the C light source was measured, and the following Calculate the formula, find the color difference ΔEab*, and evaluate it in the following three stages.

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

○: △Eab* is less than 5.0

△: △Eab* is above 5.0 and not up to 10.0

×: △Eab* is above 10.0

(Assessment of light resistance)

First, a coated substrate is prepared in the same manner as in the evaluation of heat resistance, and the chromaticity under the C light source ([L*(1), a*(1), b*(1))]) is microscopic spectrophotometry. The measurement ("OSP-SP100" manufactured by Olympus Corporation of Japan) was measured. Then, an ultraviolet-resistant color filter ("COLORED OPTICAL GLASS L38" manufactured by Hoya Co., Ltd., Japan) was attached to the substrate, and the ultraviolet light was irradiated with a xenon lamp of 470 W/m ² for 100 hours, and then the color under the C light source was measured. The degree ([L*(2), a*(2), b*(2)))), the color difference ΔEab* was obtained by the above calculation formula, and was evaluated on the same basis as the heat resistance.

(assessment of sensitivity)

The green photosensitive coloring composition (RG-1 to 47) was first coated on a glass substrate of 10 cm × 10 cm by spin coating, and then heated at 70 ° C for 15 minutes in a dust-free oven to remove the solvent. A coating film of about 2 μm was obtained. Next, after cooling the substrate to room temperature, ultraviolet light exposure was performed with an ultrahigh pressure mercury lamp through a mask of 100 μm wide (pitch 200 μm) and 25 μm wide (pitch 50 μm) stripes, after which the substrate was again subjected to 23 After spraying with a sodium carbonate aqueous solution at ° C, it was washed with ion-exchanged water, air-dried, and heated at 220 ° C for 20 minutes in a dust-free oven. Further measuring the color filter segment formed by the above method The film thickness of the image of the 100 μm mask portion was determined based on the following criteria with a minimum exposure amount of 90% or more with respect to the film thickness after application. The smaller the minimum exposure amount, the higher the sensitivity of the photosensitive coloring composition.

○: and less than 50mJ/cm ²

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

×: 100 mJ/cm ² or more

As shown in Table 4, the coloring agent having the characteristics of the present embodiment contains a quinoline yellow pigment represented by the formula (1) and a quinoline yellow dye represented by the formula (6). As a result, the green photosensitive coloring composition of the example was excellent in brightness, contrast value, and coloring power, and there was no problem in heat resistance and light resistance of the coating film. In addition, the results were all good regardless of whether or not the dye was contained therein.

On the other hand, the yellow coloring agent is a green photosensitive coloring composition (RG-38, 43) of Reference Examples 6 and 11 of C.I. Pigment Yellow No. 138, which uses a conventional pigment alone, and as a result, the coloring power is low. The green photosensitive coloring composition (RG-41, 42, 46, 47) of 9, 10, 14, 15 which is a reference example of CI Pigment Yellow No. 138 in which the yellow coloring agent is used alone. ), the result is good brightness, but low contrast value, and sensitivity is also poor. The yellow coloring agent is a green photosensitive coloring composition (RG) of Reference Examples 7, 8, 12, and 13 of CI Disperse Dye Yellow No. 54 of non-quinoline yellow dye [B] and CI Disperse Dye Yellow No. 64. In the case of -39, 40, 44, 45), the results are inferior in all characteristics.

<Production of color filter>

First, the preparation of the red photosensitive coloring composition and the blue photosensitive coloring composition used in the production of the color filter was carried out.

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

After the mixture of the following composition was stirred and mixed to be uniform, zirconia beads having a diameter of 0.5 mm were used, and dispersed by an Eiger mill disperser ("Mini Model M-250 MK II" manufactured by Eiger Japan Co., Ltd.) for 5 hours, and then The 5.0 μm filter was filtered to prepare a red colored composition (DR-1).

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

(Production of blue photosensitive coloring composition (RB-1))

After the mixture of the following composition was stirred and mixed to be uniform, zirconia beads having a diameter of 0.5 mm were used, and dispersed by an Eiger mill disperser ("Mini Model M-250 MK II" manufactured by Eiger Japan Co., Ltd.) for 5 hours, and then 5.0. The sieve of μm was filtered to prepare a blue colored composition (DB-1).

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

(production of color filter)

The black matrix on the glass substrate was first processed into an image, and the red photosensitive coloring composition (RR-1) was applied onto the substrate by a spin coater to form a colored film. The film was further irradiated with ultraviolet rays at 150 mJ/cm ² using an ultrahigh pressure mercury lamp through a mask. Next, the alkali developing solution composed of a 0.2% by weight aqueous sodium carbonate solution was spray-developed to remove the unexposed portion, and then washed with ion-exchanged water, and the substrate was heated at 220 ° C for 20 minutes to form a red color filter. Fragment. Among them, the red color filter segment was subjected to heat treatment at 220 ° C, and it was combined with a chromaticity of x=0.640 and y=0.330 under a C light source (hereinafter, also used in green and blue). Then, in the same manner, the green color filter segment is combined with the chromaticity of x=0.290 and y=0.600 using the green photosensitive coloring composition (RG-19) to make the blue color filter segment use. The blue photosensitive coloring composition (RB-1) was combined with the chromaticity of x=0.150 and y=0.600, and each color filter segment was formed to obtain a color filter.

When the green photosensitive coloring composition (RG-19) is used, it is understood that the color filter can be made brighter and higher in contrast, and it is suitable for use without any problem in other physical properties.

"Embodiment V" <Method for producing quinoline yellow pigment>

2.9 parts of 6-hydroxy-2-methylquinoline and 2.5 parts of naphthalene dicarboxylic anhydride, 30 parts of benzoic acid were mixed, and stirred at 200 ° C for 7 hours. After standing to cool, 100 parts of methanol was further added and stirred for 1 hour. Thereafter, the precipitated solids were collected by suction filtration. The solid was again added to 200 parts of methanol, and after stirring for 1 hour, the solid was collected by suction filtration. Thereafter, it was dried overnight in a vacuum dryer (40 ° C) to obtain 4.2 parts of a product. Its yield was 82%. The compound was then identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan, autoflex II). As a result, m/z = 408 (molecular weight 407.5) was identified as the target.

2.3 parts of 6-isopropyl-2-methylquinoline and 2.5 parts of naphthalene dicarboxylic anhydride, 30 parts of benzoic acid were mixed, and stirred at 200 ° C for 7 hours. After standing to cool, 100 parts of methanol was further added and stirred for 1 hour. Thereafter, the precipitated solids were collected by suction filtration. Add the solid again The mixture was poured into 200 parts of methanol, and after stirring for 1 hour, the solid was collected by suction filtration. Thereafter, it was dried overnight in a vacuum dryer (40 ° C) to obtain 3.1 parts of a product. Its yield was 67%. The compound was then identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan, autoflex II). As a result, m/z = 366 (molecular weight 365.4) was confirmed as the target.

2.7 parts of 7-trifluoromethyl-2-methylquinoline and 2.5 parts of naphthalene dicarboxylic anhydride, 30 parts of benzoic acid were mixed, and stirred at 200 ° C for 7 hours. After standing to cool, 100 parts of methanol was further added and stirred for 1 hour. Thereafter, the precipitated solids were collected by suction filtration. The solid was again added to 200 parts of methanol, and after stirring for 1 hour, the solid was collected by suction filtration. Thereafter, it was dried overnight in a vacuum dryer (40 ° C) to obtain 2.9 parts of a product. Its yield was 58%. The compound was then identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan, autoflex II). As a result, m/z = 392 (molecular weight 391.3) was confirmed as a target.

2.7 parts of 8-n-butoxy-2-methylquinoline and 2.5 parts of naphthalene dicarboxylic anhydride, 30 parts of benzoic acid were mixed, and stirred at 200 ° C for 7 hours. After standing to cool, 100 parts of methanol was further added and stirred for 1 hour. Thereafter, the precipitated solids were collected by suction filtration. The solid was again added to 200 parts of methanol, and after stirring for 1 hour, the solid was collected by suction filtration. Thereafter, it was dried overnight in a vacuum dryer (40 ° C) to obtain 3.1 parts of a product. Its yield was 62%. The compound was then identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan, autoflex II). As a result, m/z = 396 (molecular weight 395.5) was confirmed as the target.

3.4 parts of 8-(2-ethylhexyloxy)-2-methylquinoline and 2.5 parts of naphthalene dicarboxylic anhydride, 30 parts of benzoic acid were mixed and stirred at 200 ° C for 7 hours. After standing to cool, 100 parts of methanol was further added and stirred for 1 hour. Thereafter, the precipitated solids were collected by suction filtration. The solid was again added to 200 parts of methanol, and after stirring for 1 hour, the solid was collected by suction filtration. Thereafter, it was dried overnight in a vacuum dryer (40 ° C) to obtain 5.0 parts of a product. Its yield was 88%. The compound was then identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan, autoflex II). The result is m/z = 452 (molecular weight 451.5) Set as the target.

4.4 parts of 8-(2-ethylhexyloxy)-5-phenyl-2-methylquinoline and 2.5 parts of naphthalene dicarboxylic anhydride, 30 parts of benzoic acid were mixed, and stirred at 200 ° C for 7 hours. . After standing to cool, 100 parts of methanol was further added and stirred for 1 hour. Thereafter, the precipitated solids were collected by suction filtration. The solid was again added to 200 parts of methanol, and after stirring for 1 hour, the solid was collected by suction filtration. Thereafter, it was dried overnight in a vacuum dryer (40 ° C) to obtain 5.7 parts of a product. Its yield is 85%. The compound was then identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan, autoflex II). As a result, m/z = 528 (molecular weight: 527.7) was identified as the target.

4.1 parts of 8-dodecyloxy-2-methylquinoline and 2.5 parts of naphthalene dicarboxylic anhydride, 30 parts of benzoic acid were mixed, and stirred at 200 ° C for 7 hours. After standing to cool, 100 parts of methanol was further added and stirred for 1 hour. Thereafter, the precipitated solids were collected by suction filtration. The solid was again added to 200 parts of methanol, and after stirring for 1 hour, the solid was collected by suction filtration. Thereafter, it was dried overnight in a vacuum dryer (40 ° C) to obtain 3.6 parts of a product. Its yield was 57%. The compound was then identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan, autoflex II). As a result, m/z = 508 (molecular weight: 507.6) was confirmed as the target.

4.4 parts of 8-(2-ethylhexyloxy)-5-bromo-2-methylquinoline and 2.5 parts of naphthalene dicarboxylic anhydride, 30 parts of benzoic acid were mixed, and stirred at 200 ° C for 7 hours. . After standing to cool, 100 parts of methanol was further added and stirred for 1 hour. Thereafter, the precipitated solids were collected by suction filtration. The solid was again added to 200 parts of methanol, and after stirring for 1 hour, the solid was collected by suction filtration. Thereafter, it was dried overnight in a vacuum dryer (40 ° C) to obtain 4.1 parts of a product. The yield was 61%. The compound was then identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan, autoflex II). As a result, m/z = 531 (molecular weight 530.5) was identified as the target.

2.9 parts of 6-trifluoromethoxy-2-methylquinoline and 2.5 parts of naphthalene dicarboxylic anhydride, 30 parts of benzoic acid were mixed, and stirred at 200 ° C for 7 hours. After standing to cool, 100 parts of methanol was further added and stirred for 1 hour. Thereafter, the precipitated solids were collected by suction filtration. The solid was again added to 200 parts of methanol, and after stirring for 1 hour, the solid was collected by suction filtration. Thereafter, it was dried overnight in a vacuum dryer (40 ° C) to obtain 4.3 parts of a product. Its yield was 83%. The compound was then identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan, autoflex II). As a result, m/z = 408 (molecular weight 407.3) was determined as the intended product.

3.4 parts of 6-(2-ethylhexyloxy)-2-methylquinoline and 2.5 parts of naphthalene dicarboxylic anhydride, 30 parts of benzoic acid were mixed, and stirred at 200 ° C for 7 hours. After standing to cool, 100 parts of methanol was further added and stirred for 1 hour. Thereafter, the precipitated solids were collected by suction filtration. The solid was again added to 200 parts of methanol, stirred for 1 hour, and then aspirated. The solids were collected by filtration. Thereafter, it was dried overnight in a vacuum dryer (40 ° C) to obtain 3.9 parts of a product. Its yield was 68%. The compound was then identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan, autoflex II). As a result, m/z = 452 (molecular weight: 451.5) was identified as the intended product.

2.9 parts of 6-(2-ethoxyethoxy)-2-methylquinoline and 2.5 parts of naphthalene dicarboxylic anhydride, 30 parts of benzoic acid were mixed, and stirred at 200 ° C for 7 hours. After standing to cool, 100 parts of methanol was further added and stirred for 1 hour. Thereafter, the precipitated solids were collected by suction filtration. The solid was again added to 200 parts of methanol, and after stirring for 1 hour, the solid was collected by suction filtration. Thereafter, it was dried overnight in a vacuum dryer (40 ° C) to obtain 3.3 parts of a product. Its yield was 64%. The compound was then identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan, autoflex II). As a result, m/z = 412 (molecular weight 411.5) was confirmed as the target.

Will be 3.4 parts of 6-(2-(1,3-) Alkyl-2-yl)ethoxy)-2-methylquinoline and 2.5 parts of naphthalene dicarboxylic anhydride, 30 parts of benzoic acid were mixed, and stirred at 200 ° C for 7 hours. After standing to cool, 100 parts of methanol was further added and stirred for 1 hour. Thereafter, the precipitated solids were collected by suction filtration. The solid was again added to 200 parts of methanol, and after stirring for 1 hour, the solid was collected by suction filtration. Thereafter, it was dried overnight in a vacuum dryer (40 ° C) to obtain 3.0 parts of a product. Its yield was 53%. The compound was then identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan, autoflex II). As a result, m/z = 454 (molecular weight: 453.5) was identified as the intended product.

3.4 parts of 4-(2-ethylhexyloxy)-2-methylquinoline and 2.5 parts of naphthalene dicarboxylic anhydride, 30 parts of benzoic acid were mixed, and stirred at 200 ° C for 7 hours. After standing to cool, 100 parts of methanol was further added and stirred for 1 hour. Thereafter, the precipitated solids were collected by suction filtration. The solid was again added to 200 parts of methanol, and after stirring for 1 hour, the solid was collected by suction filtration. Thereafter, it was dried overnight in a vacuum dryer (40 ° C) to obtain 4.2 parts of a product. Its yield was 74%. The compound was then identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan, autoflex II). The result is m/z = 452 (molecular weight 451.5) Set as the target.

3.8 parts of ethyl 5-(2-methylquinolin-8-yloxy)pentanoate and 2.5 parts of naphthalene dicarboxylic anhydride, 30 parts of benzoic acid were mixed, and stirred at 200 ° C for 7 hours. After standing to cool, 100 parts of methanol was further added and stirred for 1 hour. Thereafter, the precipitated solids were collected by suction filtration. The solid was again added to 200 parts of methanol, and after stirring for 1 hour, the solid was collected by suction filtration. Thereafter, it was dried overnight in a vacuum dryer (40 ° C) to obtain 4.5 parts of a product. Its yield was 74%. The compound was then identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan, autoflex II). As a result, m/z = 482 (molecular weight: 481.5) was identified as the target.

2.0 parts of 8-hydroxy-2-methylquinoline and 2.5 parts of naphthalene dicarboxylic anhydride, 30 parts of benzoic acid were mixed, and stirred at 200 ° C for 7 hours. After standing to cool, 100 parts of methanol was further added and stirred for 1 hour. after that, The precipitated solids were collected by suction filtration. The solid was again added to 200 parts of methanol, and after stirring for 1 hour, the solid was collected by suction filtration. Thereafter, it was dried overnight in a vacuum dryer (40 ° C) to obtain 3.7 parts of a product. Its yield was 86%. The compound was then identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan, autoflex II). As a result, m/z = 339 (molecular weight 339.3) was confirmed as a target.

2.0 parts of quinophthalone yellow 15 is mixed in 20 parts of N,N-dimethylacetamide, and then 0.3 parts of sodium hydroxide and 1.8 parts of 2-ethylhexyl-4-bromobutyric acid are mixed. Then, it was stirred at 90 ° C for 1 hour. After it was left to cool, 100 parts of methanol and 100 parts of water were further added and stirred for 1 hour. Thereafter, the precipitated solids were collected by suction filtration. The solid was again added to 100 parts of methanol, and after stirring for 1 hour, the solid was collected by suction filtration. Thereafter, it was dried overnight in a vacuum dryer (40 ° C) to obtain 1.6 parts of a product. Its yield was 51%. The compound was then identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan, autoflex II). As a result, m/z = 538 (molecular weight 537.7) was confirmed as the target.

First, 2.0 parts of quinophthalone yellow 15 is mixed in 20 parts of N,N-dimethylacetamide, and then 0.3 parts of sodium hydroxide and 1.9 parts of 2-ethylhexyl-5-bromopentane are mixed. The acid was then stirred at 90 ° C for 1 hour. After it was left to cool, 100 parts of methanol and 100 parts of water were further added and stirred for 1 hour. Thereafter, the precipitated solids were collected by suction filtration. The solid was again added to 100 parts of methanol, and after stirring for 1 hour, the solid was collected by suction filtration. Thereafter, it was dried overnight in a vacuum dryer (40 ° C) to obtain 2.0 parts of a product. Its yield was 62%. The compound was then identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan, autoflex II). As a result, m/z = 552 (molecular weight: 551.7) was identified as the intended product.

First, 2.0 parts of quinoline yellow pigment 15 in 20 parts of N, N-dimethyl Mix with acetamide, add 0.3 parts of sodium hydroxide, 2.4 parts of 2-(2-(2-ethylhexyloxy)ethoxy)ethyl 2-bromobutyrate, then at 100 ° C Stir for 2 hours. After standing to cool, the reaction liquid was added to 50 parts of water, and 100 parts of chloroform was added to extract an organic layer. Thereafter, magnesium sulfate was further added to the organic layer, dried, filtered, and concentrated under reduced pressure. The concentrate thus obtained was purified by silica gel column chromatography (chloroform / ethyl acetate = 10/1 (volume ratio)) to obtain 2.8 parts of a product. Its yield was 76%. The compound was then identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan, autoflex II). As a result, m/z = 626 (molecular weight 625.8) was identified as the target.

First, 2.0 parts of quinophthalone yellow 15 is mixed in 20 parts of N,N-dimethylacetamide, and then 0.3 parts of sodium hydroxide and 2.5 parts of 5-bromopentanoic acid-2-(2) are mixed. -(2-Ethylhexyloxy)ethoxy)ethyl ester, followed by stirring at 100 ° C for 2 hours. After standing to cool, the reaction liquid was added to 50 parts of water, and 100 parts of chloroform was added to extract an organic layer. Thereafter, magnesium sulfate was further added to the organic layer, dried, filtered, and concentrated under reduced pressure. The concentrate thus obtained was purified by silica gel column chromatography (chloroform / ethyl acetate = 10/1 (volume ratio)) to obtain 2.7 parts of a product. The yield was 72%. The compound was then identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan, autoflex II). The result is m/z = 640 (molecule The amount 639.8) can be determined as the target.

First, 2.0 parts of quinophthalone yellow 15 is mixed in 20 parts of N,N-dimethylacetamide, and then mixed with 0.3 parts of sodium hydroxide and 9.7 parts of bis(2-ethylhexyl) 7- Oxabicyclo[4.1.0]heptane-3,4-dicarboxylate was then stirred at 150 ° C for 10 hours. After standing to cool, the reaction liquid was added to 50 parts of water, and 100 parts of chloroform was added to extract an organic layer. Thereafter, magnesium sulfate was further added to the organic layer to dryness, filtration, and concentration under reduced pressure. The concentrate thus obtained was purified by a silica gel column chromatography (chloroform / ethyl acetate = 10/1 (volume ratio)) to obtain a product of 1.3 parts. Its yield is 30%. The compound was then identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan, autoflex II). As a result, m/z = 750 (molecular weight 749.9) can be determined as a target.

First, mix 2.0 parts of Disperse Yellow 160 in 20 parts of N,N-dimethylacetamide, then mix 0.3 parts of sodium hydroxide, 1.8 parts. 2-Ethylhexyl-4-bromobutyric acid was then stirred at 90 ° C for 1 hour. After it was left to cool, 100 parts of methanol and 100 parts of water were further added and stirred for 1 hour. Thereafter, the precipitated solids were collected by suction filtration. The solid was again added to 100 parts of methanol, and after stirring for 1 hour, the solid was collected by suction filtration. Thereafter, it was dried overnight in a vacuum dryer (40 ° C) to obtain 2.0 parts of a product. Its yield is 60%. The compound was then identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan, autoflex II). As a result, m/z = 538 (molecular weight 537.7) was confirmed as the target.

The synthesis is carried out according to the synthesis method of the pigment (IV) in JP-A-6-009891.

Among them, Disperse Yellow 54 is used.

Among them, Disperse Yellow 64 is used.

<Modulation of Acrylic Resin Solution>

70.0 parts of cyclohexanone was placed in a reaction vessel equipped with a thermometer, a condenser, a nitrogen introduction tube, a dropping tube, and a stirring device in a separable 4-necked flask, and the temperature was raised to 80 ° C, and the reaction vessel was replaced. After nitrogen gas, 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, and 7.4 parts of p-isopropylidene phenol were epoxy-coated by a dropping tube. A mixture of ethane-modified acrylate ("Aronix M110" manufactured by Japan East Asia Synthetic Co., Ltd.) and 0.4 parts of 2,2'-azobisisobutyronitrile was dropped over 2 hours. After the completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a solution of an acrylic resin having a weight average molecular weight of 26,000. After cooling to room temperature, about 2 g of the resin solution was sampled and dried at 180 ° C for 20 minutes to determine the non-volatile matter, and the methoxypropyl acetate was added in such a manner that the non-volatile fraction of the previously synthesized resin solution was 20% by weight. Into an acrylic resin solution.

Among them, the polymerization average molecular weight (Mw) of the acrylic resin is TSK gel column (manufactured by Tosoh Corporation of Japan), and GPC (manufactured by Tosoh Corporation of Japan, LC-8120GPC) of the apparatus RI detector is used to develop a solvent using THF. The weight average molecular weight (Mw) of the converted polystyrene at the time of measurement.

<Method for producing pigment> (production of blue pigment 1)

First, 200 parts of the indigo blue pigment CI Pigment Blue 15:6 ("LIONOL BLUE ES" manufactured by Toyo Ink Manufacturing Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of ethylene glycol are added. A 1 gallon kneader made of stainless steel (manufactured by Inoue, Ltd., Japan) was mixed at 80 ° C for 6 hours. Next, the mixture is put into 8 liters of warm water, heated to about 80 ° C and stirred for 2 hours to make it into a slurry, repeatedly filtered, washed with water to remove sodium chloride and diethylene glycol, and then It was dried overnight at 85 ° C to obtain 190 parts of Blue Pigment 1. The pigment obtained had an average primary particle diameter of 79 nm.

(Production of Purple Pigment 1)

First 200 copies Purple pigment CI Pigment Violet No. 23 ("LIONOL VIOLET RL" manufactured by Toyo Ink Manufacturing Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were added to a 1-gallon kneader made of stainless steel (Japan Inoue Co., Ltd.) Manufactured and mixed at 80 ° C for 6 hours. Next, the mixture is put into 8 liters of warm water, heated to about 80 ° C and stirred for 2 hours to make it into a slurry, repeatedly filtered, washed with water to remove sodium chloride and diethylene glycol, and then Drying at 85 ° C overnight, 190 parts of purple pigment 1 were obtained. The pigment obtained had an average primary particle diameter of 28 nm.

(production of blue pigment 2)

60.0 parts of phthalonitrile and 300 parts of 1-chlorinated naphthalene and 15.6 parts of aluminum chloride were placed in a glass 4-necked flask, and stirred under reflux for 6 hours. After that, the heating is stopped, and then it is left to cool to about 200 ° C, and then heat is performed. Filter and wash with 600 parts of hot toluene and 300 parts of acetone. The obtained wet mass was then dispersed in 250 parts of toluene and refluxed for 3 hours with stirring. Further, the mixture was filtered while hot, washed with 600 parts of hot toluene and 300 parts of acetone, and then dispersed in 1500 parts of ion-exchanged water, and heated and stirred at 60 to 70 ° C for 60 minutes. Thereafter, the mixture was filtered, washed with water, and dried under vacuum at 50 ° C to obtain an anthocyanin aluminum pigment (AlPc-Cl) having a blue solid of the desired structure. Further, 30 parts of the obtained pigment was gradually dissolved in 1200 parts of concentrated sulfuric acid while maintaining the temperature at about 5 ° C, and stirred at this temperature for 1 hour. Thereafter, the mixture was poured while stirring at a temperature of not more than 5 ° C in 6000 parts of ice water, and stirred for 1 hour after the end of the injection. After filtration and washing with water, it was redispersed in 6500 parts of ion-exchanged water and filtered again. After washing with water, the wet mass was redispersed in 2500 parts of 4% aqueous ammonia and stirred under reflux for 6 hours. After filtering this wet mass, it was washed with ion-exchanged water, and then vacuum-dried at 50 ° C to obtain an anthocyanin aluminum pigment (AlPc-OH) having a blue solid of a desired structure.

Then, 50 parts of the (AlPc-OH) pigment, 150 parts of sodium chloride, and 25 parts of diethylene glycol were added to a 1-gallon kneader made by stainless steel (manufactured by Inoue, Japan), and mixed at 120 ° C. Mix for 6 hours. Then, the mixture was put into 5 liters of warm water, heated to 80 ° C and stirred for 1 hour to make it into a slurry, repeatedly filtered, washed with water to remove sodium chloride and diethylene glycol, and then at 85 ° C. After drying overnight, a blue pigment 2 was obtained. The pigment obtained had an average primary particle diameter of 28 nm.

(Production of Green Pigment 1)

Direct use of indigo green pigment C.I. Pigment Green No. 58 (DIC) It is a commercial product of "FASTGEN GREEN A110". The green pigment 1 had an average primary particle diameter of 22 nm.

(Production of yellow pigment 1)

270 parts of quinoline yellow pigment CI Pigment Yellow No. 138 (trade name: Paliotol Yellow K0960-HD, manufactured by BASF Corporation), 1350 parts of sodium chloride, and 500 parts of ethylene glycol are added to one gallon of stainless steel. The kneader (manufactured by Inoue, Ltd., Japan) was mixed at 120 ° C for 6 hours. Then, the mixture was put into 8 liters of warm water, heated to 80 ° C and stirred for 2 hours to make it into a slurry, repeatedly filtered, washed with water to remove sodium chloride and diethylene glycol, and then at 85 ° C. After drying overnight, 250 parts of yellow pigment 3 were obtained. The pigment obtained had an average primary particle diameter of 36 nm.

(Production of yellow pigment 2)

200 parts of nickel complex yellow pigment CI Pigment Yellow No. 150 ("E-4GN" manufactured by Lanxess), 1400 parts of sodium chloride, and 360 parts of ethylene glycol are added to a 1-gallon kneader made of stainless steel. (manufactured by Inoue, Japan), and mixed at 120 ° C for 6 hours. Then, the mixture was put into 8 liters of warm water, heated to 80 ° C and stirred for 2 hours to make it into a slurry, repeatedly filtered, washed with water to remove sodium chloride and diethylene glycol, and then at 85 ° C. After drying overnight, 190 parts of yellow pigment 2 were obtained. The obtained pigment had a volume average primary particle diameter of 67 nm.

(Production of yellow pigment 3)

500 parts of isoporphyrin yellow pigment CI Pigment Yellow No. 139 ("IRGAPHOR YELLOW 2R-CF" manufactured by Ciba Japan Co., Ltd.), 500 parts of sodium chloride, and 250 parts of diethylene glycol were added to stainless steel. gallon The kneader (manufactured by Inoue, Ltd., Japan) was mixed at 120 ° C for 8 hours. Next, the mixture is put into 5 liters of warm water, heated to 80 ° C and stirred for 1 hour to make it into a slurry, repeated filtration, washing with water to remove sodium chloride and diethylene glycol, and then 85 Drying overnight at ° C gave 490 parts of yellow pigment 1. The pigment obtained had an average primary particle diameter of 92 nm.

(production of red pigment 1)

200 parts of bismuth red pigment CI Pigment Red No. 177 ("Cromophthal Red A2B" manufactured by Ciba Japan Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were added to a 1-gallon kneader made of stainless steel ( In Japan, manufactured by Inoue, Ltd., and mixed at 80 ° C for 6 hours. Then, the mixture was put into 8 liters of warm water, heated to 80 ° C and stirred for 2 hours to make it into a slurry, repeatedly filtered, washed with water to remove sodium chloride and diethylene glycol, and then at 85 ° C. After drying overnight, 190 parts of red pigment 1 were obtained. The pigment obtained had an average primary particle diameter of 54 nm.

(production of coloring composition Q-1)

After the following mixture was stirred and mixed to be uniform, zirconia beads having a diameter of 0.5 mm were used, and dispersed by an Eiger mill ("Mini Model M-250 MK II" manufactured by Eiger Japan Co., Ltd.) for 5 hours, and then 5.0. The sieve of μm was filtered to prepare a colored composition Q-1.

(Production of coloring compositions Q-2 to 24)

In the following, in the same manner as in the coloring composition Q-1 except that quinoline yellow pigment represented by 2 is taken as quinophthalone yellow pigment 1, the coloring compositions Q-2 to 24 were produced.

(production of coloring composition DP-1)

After the following mixture was stirred and mixed to be uniform, zirconia beads having a diameter of 0.5 mm were used, and dispersed by an Eiger mill ("Mini Model M-250 MK II" manufactured by Eiger Japan Co., Ltd.) for 5 hours, and then 5.0. The sieve of μm was filtered to prepare a colored composition (DP-1).

(Production of coloring compositions DP-2 to 8)

Hereinafter, the coloring compositions DP-2 to 8 were produced in the same manner as in the coloring composition DP-1 except that the blue pigment 1 was replaced with the pigment shown in Table 3.

[Examples 1 to 20, Reference Examples 1 to 7] <Test of foreign matter of coating film of coloring compositions Q-1 to 24 and DP-5 to 7>

The evaluation was carried out by preparing a test substrate and calculating the number of particles. The colored composition was applied to the transparent substrate so that the dried coating film became about 2.0 mm, and then heated in an oven at 230 ° C for 20 minutes to obtain a test substrate. The surface was observed by a metal microscope "BX60" manufactured by Olympus Corporation of Japan. Calculate the number of particles observable in any five areas that can be transmitted at a magnification of 500 times. Among the evaluation results described below, ◎ and ○ are good, and Δ is a foreign matter, but there is no problem in use, and × is uneven coating (plaque) due to foreign matter.

◎: Less than 5

○: 5 or more and less than 20

△: 20 or more and less than 100

×: 100 or more

Below, Table 4 shows the results.

<Specification of Spectroscopic Compositions Q-1 to 24, DP-5 to 7>

A coating film was formed on the transparent substrate so that the transmittance at a wavelength of 450 nm became 5%, and the values of the transmittance at 500 nm and 550 nm at this time were measured. The higher the transmittance at 500 nm and 550 nm, the better the brightness. In the following evaluation results, the transmittance of 500 nm and 550 nm when quinoline yellow pigment and yellow pigment are normalized is ○ is 99% or more, Δ is 97 or more and less than 99%, and × is 97% or less. . When it is 99% or more, its brightness becomes high, so it is preferable. Below, Table 4 shows the results. Further, the light separation of the coating films of Example 5 and Reference Examples 1 and 3 is as shown in Figs. 1 to 3.

In Examples 1 to 20, as a result, the foreign matter of the coating film was small, which was preferable. The results of Examples 1 to 20 were excellent in spectral characteristics and showed a spectral shape in which the brightness became high. The light transmittance at 550 nm of Reference Examples 2 to 6 is preferable, but the light transmittance at 500 nm is low, and a spectroscopic shape in which the brightness cannot be further improved is displayed.

Reference Examples 1 to 4 using a hydroxyl group-containing dye on a quinoline ring were compared with the light split shapes of Examples 1 to 20 using a hydroxyl group-free dye (for example, the coating film of Example 5, Reference Examples 1, 3 of Fig. 1) In the case of light splitting, the light transmittance at 500 nm is low, and it is understood that the dye having a hydroxyl group on the quinoline ring is a dye which cannot be improved in brightness.

<Method for Producing Blue Photoresist Material>

The mixture described below was uniformly stirred and mixed, and then filtered through a 1.0 μm filter to obtain a blue photoresist material B-1.

[Example 21] <Adjustment of Photoresist Material G-1>

The mixture described below was uniformly stirred and mixed, and then filtered through a 1.0 μm filter to obtain a green photoresist (G-1).

[Examples 22 to 66, Reference Examples 8 to 15] <Adjustment of photoresist materials G-2 to 46, R-1 to 4, Y-1 to 4>

In the following, except that the type and the amount of the coloring composition are changed as shown in Tables 5 and 6, the photoresist materials G-2 to 46 and R-1 are obtained in the same manner as in the photoresist material G-1. 4. Y-1 to 4.

<Evaluation of photoresist materials>

The test results of the color properties (Y: brightness), coating foreign matter, heat resistance, and light resistance of the coating films of the obtained photoresist materials G-1 to 46, R-1 to 4, and Y-1 to 4 were The method is as follows. The results of the test are shown in Table 7.

<Color characteristics (Y: brightness)>

On the glass substrate, the photoresist materials G-1 to 46 were coated under a C light source to form a film thickness of x=0.264 and y=0.600, and the substrate was further heated at 230 ° C for 20 minutes. For the photoresist materials R-1 to 4, a photoresist material was applied to form a film thickness of x = 0.340 and y = 0.640, and the substrate was further heated at 230 ° C for 20 minutes. For the photoresist materials Y-1 to 4, a photoresist material was applied to form a film thickness of x=0.440 and y=0.506, and the substrate was further heated at 230 ° C for 20 minutes. Thereafter, the luminance (Y) of the obtained substrate was measured by a microspectrophotometer ("OSP-SP200" manufactured by Olympus Corporation, Japan).

Below, Table 7 shows the results.

<Coating film foreign matter test>

First, a photoresist film was applied on a transparent substrate to form a dried coating film of about 2.5 μm, and after full ultraviolet exposure, it was further heated at 230 ° C for 20 minutes in an oven, and after standing and cooling, an evaluation substrate was obtained. The surface was observed by a metal microscope "BX60" manufactured by Olympus Corporation of Japan. Calculate the number of particles observable in any five areas that can be transmitted at a magnification of 500 times. Among the evaluation results described below, ◎ and ○ are good, and Δ is a level of foreign matter, but there is no problem of use, and × is uneven coating due to foreign matter.

◎: Less than 5

○: 5 or more and less than 20

△: 20 or more and less than 100

×: 100 or more

Hereinafter, the results are shown in Table 7.

<Coating film heat resistance test>

The photoresist is coated on the transparent substrate to form a dry coating film of about 2.5 μm, and then exposed to ultraviolet light by a photomask having a predetermined image, and then sprayed with an alkali developing solution to remove the unexposed portion thereof to form a predetermined Image. Thereafter, it was further heated in an oven at 230 ° C for 20 minutes, and after standing and cooled, the obtained coating film was subjected to a chromaticity 1 under a C light source (L*(1), a*(1), b*(1)). It was measured by a microspectrophotometer ("OSP-SP200" manufactured by Olympus Corporation, Japan). Thereafter, the heat resistance test was performed by heating at 230 ° C for 1 hour in an oven, and then measuring the chromaticity 2 (L*(2), a*(2), b*(2)) under the C light source. Then, the color difference ΔEab* was determined by the following calculation formula based on the measured color difference value, and the heat resistance of the coating film was evaluated in the following four stages. Among them, when the evaluation is Δ or more, it is a level which is practically no problem.

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

◎: △Eab* is less than 1.5

○: △Eab* is 1.5 or more and less than 3.0

△: △Eab* is above 3.0 and not up to 5.0

×: △Eab* is 5.0 or more

Hereinafter, the results are shown in Table 7.

<Coating film light resistance test>

The test substrate was produced in the same order as the film heat resistance test, and the chromaticity 1 (L*(1), a*(1), b*(1)) under the C light source was a microscopic spectrophotometer (Japan). Olympus manufactures "OSP-SP200"). After that, The substrate was placed in a light resistance tester ("SUNTESTCPS+" manufactured by TOYOSEIKI, Japan) and placed for 500 hours. After the substrate was taken out, the chromaticity 2 (L*(2), a*(2), b*(2)) under the C light source was measured, and the color difference was calculated in the same manner as the heat resistance test of the coating film. Eab*, the solvent resistance of the coating film was evaluated on the same basis as the coating film heat resistance test. Among them, when the evaluation is Δ or more, it is a level which is practically no problem.

Below, Table 7 shows the results.

<Coating film solvent resistance test>

The test substrate was produced in the same order as the film heat resistance test, and the chromaticity 1 (L*(1), a*(1), b*(1)) under the C light source was a microscopic spectrophotometer (Japan). Olympus manufactures "OSP-SP200"). Thereafter, the substrate was immersed in N-methylpyrrolidone for 30 minutes. After the substrate was taken out, the chromaticity 2 (L*(2), a*(2), b*(2)) under the C light source was measured, and the color difference ΔEab was calculated in the same manner as the heat resistance test of the coating film. * The solvent resistance of the coating film was evaluated on the same basis as the coating film heat resistance test. Among them, when the evaluation is Δ or more, it is a level which is practically no problem.

Hereinafter, the results are shown in Table 7.

The photoresist materials (G-1 to 20, G-22 to 41, R-1 to 3, Y-1 to 3) of Examples 21 to 66, the results of which showed in brightness (Y), coating film foreign matter, heat resistance Good in properties, light resistance and solvent resistance. On the other hand, the photoresist materials (G-44, G-45) of Reference Examples 11 and 12 were inferior in heat resistance and light resistance, and thus were difficult to be practically used. The photoresists (G-21, G-43 to 46, R-4, Y-4) of Reference Examples 8 to 15 were found to have a difference in luminance (Y) as compared with the examples.

[Example 58] <Color filter (CF-1)>

First, the black matrix on the glass substrate is processed into an image, and then the red photoresist material (R-1) is coated on the substrate by a spin coater to form a film thickness of x=0.640, y=0.340. The coloring film. The film was irradiated with ultraviolet rays at 300 mJ/cm ² using an ultrahigh pressure mercury lamp through a mask. Next, it was spray-imaged with an alkali developing solution composed of a 0.2% by weight aqueous solution of sodium carbonate to remove the unexposed portion, and then washed with ion-exchanged water, and the substrate was heated at 230 ° C for 20 minutes to form a red filter. Color clip. In the same manner, a film thickness of x=0.264 and y=0.600 was formed with a green photoresist (G-36), and a blue photoresist (B-1) was formed at x=0.150. The film thickness of y=0.060 was applied to form a green color filter segment and a blue color filter segment to obtain a color filter (CF-1).

<Production of Liquid Crystal Display Device>

On the obtained RGB color filter, a transparent ITO electrode layer was formed, and a polyimide phase alignment layer was formed thereon. A three-wavelength CCFL light source of a polarizing plate was combined on the other surface of the glass substrate to prepare a color display device. On the other hand, a TFT array and a pixel electrode were formed on one surface of the other (second) glass substrate, and a polarizing plate was formed on the other surface. Then, the two glass substrates prepared in this way are treated to face each other between the electrode layers. In this manner, the position is adjusted by keeping the two substrates at a fixed interval by the spacer beads, and then the periphery is sealed with a sealant to remain in the liquid crystal composition injection opening. After the liquid crystal composition is injected from the opening, the opening is sealed. The liquid crystal display device produced in this manner is combined with a three-wavelength CCFL light source of the backlight unit to form a color display device.

[Examples 68 to 71, Reference Examples 16, 17] (Color filter (CF-2 to 7))

Hereinafter, Examples 68 to 71 and Reference Examples 16 and 17 were produced in the same manner as in the production of the color filter (CF-1) by a combination of a photoresist material and a three-wavelength CCFL light source as shown in Table 8. Color filters (CF-2 to 7) and color display devices.

Then, in the obtained color display device, the light source is illuminated to display a color image, and the brightness of the color filter segment portion of each color is measured by a microscopic spectrophotometer ("OSP-SP200" manufactured by Olympus, Japan) (Y ). The results are shown in Table 8.

Comparing Examples 68, 69 and Reference Example 16, the color filter formed by the quinophthalone yellow pigment of the present embodiment is at least one color filter segment (green or color) compared with the color filter segment using the previous pigment. In the red color, the brightness of the color filter (CF-2, 3) of quinoline yellow pigment of the present embodiment can be improved. The result is that the brightness of the white display is increased, and the color filter is increased. performance.

Further, it was confirmed that the color filter (CF-1) formed of the quinophthalone yellow pigment of the present embodiment was green and red in Example 67, and the brightness thereof was increased, and as a result, the brightness of the white display was increased.

Further, when Comparative Example 71 and Reference Example 17 were compared, the color filter formed of the quinophthalone yellow pigment of the present embodiment was compared with at least one color filter segment as compared with the color filter segment containing the previously used pigment. The color filter (CF-6) formed of the quinoline yellow pigment of the present embodiment (yellow) can increase the brightness thereof, and as a result, it is possible to determine the brightness of the white display and improve the performance of the color filter.

When the green color, red, and yellow of the embodiment 70 are simultaneously contained in the color filter for a color filter of the present embodiment (CF-5), the brightness can be further increased, and as a result, the brightness of the white display can be determined.

From the above results, it is understood that the quinophthalone yellow pigment of the present embodiment and the coloring composition thereof can be used, and the color filter can be made brighter and can be used without any problem in other physical properties.

"Embodiment VI"

Further, the weight average molecular weight (Mw) of the resin is as follows.

(Polymer average molecular weight (Mw) of resin)

The polymerization average molecular weight (Mw) of the resin is a TSK gel column (manufactured by Tosoh Corporation, Japan), and is a GPC (manufactured by Tosoh Corporation of Japan, HLC-8120GPC) equipped with an RI detector. The weight average molecular weight (Mw) of the converted polystyrene.

Hereinafter, the adhesive resin used in the examples and the reference examples, A method of producing a coloring agent, a fine pigment, and an acrylic resin solution will be described.

<Method for Producing Binder Resin Solution> (modulation of acrylic resin solution 1)

196 parts of cyclohexanone was placed in a reaction vessel equipped with a thermometer, a condenser, a nitrogen introduction tube, a dropping tube, and a stirring device in a separable 4-necked flask, and the temperature was raised to 80 ° C, and the reaction vessel was replaced. After nitrogen gas, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, and 20.7 parts of p-isopropylidene phenol were epoxy. A mixture of ethane-modified acrylate ("Aronix M110" manufactured by Japan East Asia Synthetic Co., Ltd.) and 1.1 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After the completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a solution of an acrylic resin. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried at 180 ° C for 20 minutes to determine the nonvolatile matter, and the amount of the nonvolatile matter was 20% by mass in the previously synthesized resin solution. It was prepared into an acrylic resin solution 1. Its weight average molecular weight (Mw) was 26,000.

(modulation of acrylic resin solution 2)

207 parts of cyclohexanone was placed in a reaction vessel equipped with a thermometer, a condenser, a nitrogen introduction tube, a dropping tube, and a stirring device in a separable 4-necked flask, and the temperature was raised to 80 ° C, and the reaction vessel was replaced. After nitrogen gas, 20 parts of methacrylic acid, 20 parts of p-isopropylidene phenol oxirane modified acrylate ("Aronix M110" manufactured by Japan East Asia Synthesis Co., Ltd.), and 45 parts of methyl group were dropped by a dropping tube. Methyl acrylate, 8.5 parts of 2-hydroxyethyl methacrylate, A mixture of 1.33 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After the completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a copolymer resin solution. Next, the total amount of the copolymer solution was further 6.5 parts of isocyanate-2-methylpropenyloxyethyl ester after cooling to room temperature after stopping nitrogen gas and stirring with dry air for 1 hour. (Karenz MOI manufactured by Showa Denko Co., Ltd.), a mixture of 0.08 parts of dibutyltin laurate and 26 parts of cyclohexanone were added dropwise at 70 ° C for 3 hours. After the completion of the dropwise addition, the reaction was further 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 the non-volatile matter was measured by heating at 180 ° C for 20 minutes, and cyclohexanone was added in such a manner that the non-volatile content was 20% by mass in the previously synthesized resin solution. Formed into acrylic resin solution 2. Its weight average molecular weight (Mw) was 18,000.

<Method for Producing Colorant> (Manufacture of hydroxyaluminum phthalocyanine 1)

First, 225 parts of sebaconitrile and 78 parts of anhydrous aluminum chloride were added to 1250 parts of n-pentanol in the reaction vessel, followed by stirring. Thereafter, 266 parts of DBU (1,8-Diazabicyclo [5.4.0] undec-7-ene) was added thereto and heated, and refluxed at 136 ° C for 5 hours. The reaction solution cooled to 30 ° C under stirring was added to a mixed solvent of 5,000 parts of methanol and 10,000 parts of water with stirring to obtain a blue slurry. The slurry was further filtered, washed with a mixed solvent of 2000 parts of methanol and 4000 parts of water, and dried to obtain 135 parts of chloroaluminum indigo. Thereafter, 100 parts of chloroaluminum in the reaction vessel was gradually added to 1200 parts of concentrated sulfuric acid at room temperature. Stir at 40 ° C for 3 hours, then at 24,000 parts of 3 ° C cold The sulfuric acid solution was poured into water. The blue precipitate was filtered, washed with water, and dried to obtain 102 parts of hydroxyaluminum phthalocyanine 1 represented by the following formula (3).

(Manufacture of hydroxyaluminum 2)

In the production of hydroxyaluminium phthalocyanine 1, hydroxyaluminum phthalocyanine 2 represented by the following formula (4) was obtained by the same production method except that the phthalic acid was replaced with 250 parts of 4-methacrylonitrile.

(Manufacture of hydroxyaluminum phthalocyanine 3)

In the production of hydroxyaluminium phthalocyanine 1, a hydroxyaluminum phthalocyanine 3 represented by the following formula (5) was obtained by the same production method except that the phthalic acid substitution was changed to 285 parts of 4-chlorodecanedicarbonitrile. .

(Manufacture of blue colorant (BC-1))

First, 100 parts of hydroxyaluminum phthalocyanine 1, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were added to a stainless steel 1 gallon kneader (manufactured by Inoue, Japan), and mixed at 70 ° C. hour. Next, the mixture is put into 3000 parts of warm water, heated to 70 ° C while stirring for 1 hour to make a slurry, repeated filtration, washing with water to remove sodium chloride and diethylene glycol, and then at 80 ° C After drying overnight, a blue colorant (BC-1) was obtained. Its average primary particle diameter was 30.4 nm.

(Manufacture of blue colorant (B-1))

First, 100 parts of hydroxyaluminium phthalocyanine 1 and 49.5 parts of diphenyl phosphate were added to 1000 parts of methanol in the reaction vessel, and the mixture was further heated to 40 ° C for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol, and dried to obtain 114 parts of the specific anthraquinone pigment of the formula (1-1). After that, salt grinding treatment is carried out. 100 parts of the specific anthraquinone pigment represented by the formula (1-1), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were added to a 1-gallon kneader made of stainless steel (manufactured by Inoue, Ltd., Japan) ), and mixed at 70 ° C for 6 hours. Next, the mixture is put into 3000 parts of warm water, heated to 70 ° C while stirring for 1 hour to make it into a slurry, repeatedly filtered, washed with water to remove sodium chloride. After diethylene glycol and drying at 80 ° C for one day and night, 98 parts of a blue coloring agent (B-1) was obtained. Its average primary particle size was 31.2 nm.

(Manufacture of blue colorant (B-2))

First, 100 parts of hydroxyaluminum phthalocyanine and 43.2 parts of diphenylphosphonic acid were added to 1000 parts of methanol in a reaction vessel, and the mixture was further heated to 40 ° C for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol, and dried to obtain 112 parts of the specific anthraquinone pigment represented by the formula (1-2). The specific anthraquinone dye represented by the obtained formula (1-2) was subjected to a salt milling treatment similar to that of the blue coloring agent (B-1) to obtain a blue coloring agent (B-2). Its average primary particle diameter was 29.5 nm.

(Manufacture of blue colorant (B-3))

First, 100 parts of hydroxyaluminum phthalocyanine 2 and 28.0 parts of phenylphosphonic acid were added to 1000 parts of methanol in a reaction vessel, and the mixture was further heated to 40 ° C for 8 hours. After cooling to room temperature, the product was filtered, After washing with methanol and drying, 102 parts of the specific anthraquinone pigment represented by the formula (1-3) were obtained. The specific anthraquinone dye represented by the obtained formula (1-3) was subjected to a salt milling treatment similar to that of the blue coloring agent (B-1) to obtain a blue coloring agent (B-3). Its average primary particle diameter was 33.1 nm.

(Manufacture of blue colorant (B-4))

First, 100 parts of hydroxyaluminum phthalocyanine 3 and 41.5 parts of dibutyl phosphate were added to 1000 parts of methanol in a reaction vessel, and the mixture was further heated to 40 ° C for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol, and dried to obtain 109 parts of the specific anthraquinone pigment represented by the formula (1-4). The specific anthraquinone pigment represented by the obtained formula (1-4) is subjected to a salt milling treatment similar to that of the blue coloring agent (B-1) to prepare a blue coloring agent (B- 4). Its average primary particle size is 28.9 nm.

(Manufacture of green colorant (G-1))

First, 100 parts of C.I. Pigment Green No. 58 (manufactured by DIC Corporation) "FASTGEN GREEN A110"), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a 1-gallon kneader (manufactured by Inoue, Ltd.) made of stainless steel, and mixed at 70 ° C for 6 hours. Next, the mixture is put into 3000 parts of warm water, heated to 70 ° C and stirred for 1 hour to make it into a slurry, repeatedly filtered, washed with water to remove sodium chloride and diethylene glycol, and then 80 After drying overnight at ° C, 97 parts of a green coloring agent (G-1) was obtained. Its average primary particle diameter was 28.2 nm.

(Manufacture of quinoline yellow 1)

First, 20 parts of 8-hydroxy-2-methylquinoline and 25 parts of naphthalene dicarboxylic anhydride, 300 parts of benzoic acid were mixed, and stirred at 200 ° C for 7 hours. After standing to cool, 1000 parts of methanol was further added and stirred for 1 hour. Thereafter, the precipitated solids were collected by suction filtration. The solid was further added to 2000 parts of methanol, and after stirring for 1 hour, the solid was collected by suction filtration. Thereafter, it was dried overnight in a vacuum dryer (40 ° C) to obtain 37 parts of quinoline yellow 1 as shown in the following formula (6). The compound was then identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan, autoflex II). As a result, m/z = 339 (molecular weight 339.3) was confirmed as a target.

(Manufacture of yellow colorant (Y-1))

First, 29 parts of 6-hexyl-2-methylquinoline and 25 parts of naphthalene dicarboxylic anhydride, 300 parts of benzoic acid were mixed, and stirred at 200 ° C for 7 hours. Put it After standing to cool, 1000 parts of methanol was further added and stirred for 1 hour. Thereafter, the precipitated solids were collected by suction filtration. The solid was further added to 2000 parts of methanol, and after stirring for 1 hour, the solid was collected by suction filtration. Thereafter, it was dried overnight in a vacuum dryer (40 ° C) to obtain 42 parts of the specific quinophthalone yellow pigment (yellow coloring agent (Y-1)) represented by the formula (2-1). The compound was then identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan, autoflex II). As a result, m/z = 408 (molecular weight 407.5) was identified as the target.

(Manufacture of yellow colorant (Y-2))

First, 34 parts of 8-(2-ethylhexyloxy)-2-methylquinoline and 25 parts of naphthalene dicarboxylic anhydride, 300 parts of benzoic acid were mixed, and stirred at 200 ° C for 7 hours. After standing to cool, 1000 parts of methanol was further added and stirred for 1 hour. Thereafter, the precipitated solids were collected by suction filtration. The solid was further added to 2000 parts of methanol, and after stirring for 1 hour, the solid was collected by suction filtration. Thereafter, it was dried overnight in a vacuum dryer (40 ° C) to obtain 50 parts of the specific quinophthalone yellow pigment (yellow coloring agent (Y-2)) represented by the formula (2-5). The compound was then identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan, autoflex II). As a result, m/z = 452 (molecular weight: 451.5) was identified as the intended product.

(Manufacture of yellow colorant (Y-3))

First, 44 parts of 8-(2-ethylhexyloxy)-5-phenyl-2-methylquinoline and 25 parts of naphthalene dicarboxylic anhydride, 300 parts of benzoic acid were mixed, and then stirred at 200 ° C. hour. After standing to cool, 1000 parts of methanol was further added and stirred for 1 hour. Thereafter, the precipitated solids were collected by suction filtration. The solid was further added to 2000 parts of methanol, and after stirring for 1 hour, the solid was collected by suction filtration. Thereafter, it was dried overnight in a vacuum dryer (40 ° C) to obtain 57 parts of the specific quinophthalone yellow pigment (yellow coloring agent (Y-3)) represented by the formula (2-6). The compound was then identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan, autoflex II). As a result, m/z = 528 (molecular weight: 527.7) was identified as the target.

(Manufacture of yellow colorant (Y-4))

First, 46 parts of 8-dodecyloxy-5-bromo-2-methylquinoline and 25 parts of naphthalene dicarboxylic anhydride, 300 parts of benzoic acid were mixed, and stirred at 200 ° C for 7 hours. After cooling it, add 1000 parts of methanol and stir 1 hour. Thereafter, the precipitated solids were collected by suction filtration. The solid was further added to 2000 parts of methanol, and after stirring for 1 hour, the solid was collected by suction filtration. Thereafter, it was dried overnight in a vacuum dryer (40 ° C) to obtain 46 parts of the specific quinophthalone yellow pigment (yellow coloring agent (Y-4)) represented by the formula (2-8). The compound was then identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan, autoflex II). As a result, m/z = 531 (molecular weight 530.5) was identified as the target.

(Manufacture of yellow colorant (Y-5))

First, 34 parts of 6-(2-ethylhexyloxy)-2-methylquinoline and 25 parts of naphthalene dicarboxylic anhydride, 300 parts of benzoic acid were mixed, and stirred at 200 ° C for 7 hours. After standing to cool, 1000 parts of methanol was further added and stirred for 1 hour. Thereafter, the precipitated solids were collected by suction filtration. The solid was further added to 2000 parts of methanol, and after stirring for 1 hour, the solid was collected by suction filtration. Thereafter, it was dried overnight in a vacuum dryer (40 ° C) to obtain 43 parts of the specific quinophthalone yellow pigment (yellow coloring agent (Y-5)) represented by the formula (2-10). The compound was then identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan, autoflex II). As a result, m/z = 452 (molecular weight: 451.5) was identified as the intended product.

(Manufacture of yellow colorant (Y-6))

First, 29 parts of 6-(2-ethoxyethoxy)-2-methylquinoline and 25 parts of naphthalene dicarboxylic anhydride, 300 parts of benzoic acid were mixed, and stirred at 200 ° C for 7 hours. After standing to cool, 1000 parts of methanol was further added and stirred for 1 hour. Thereafter, the precipitated solids were collected by suction filtration. The solid was again added to 2000 parts of methanol, and after stirring for 1 hour, the solid was collected by suction filtration. Thereafter, it was dried overnight in a vacuum dryer (40 ° C) to obtain 39 parts of the specific quinophthalone yellow pigment (yellow coloring agent (Y-6)) represented by the formula (2-11). The compound was then identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan, autoflex II). As a result, m/z = 412 (molecular weight 411.5) was confirmed as the target.

(Manufacture of yellow colorant (Y-7))

First, 34 parts of 6-(2-(1,3-) Alkyl-2-yl)ethoxy)-2-methylquinoline and 25 parts of naphthalene dicarboxylic anhydride, 300 parts of benzoic acid were mixed, and stirred at 200 ° C for 7 hours. After standing to cool, 1000 parts of methanol was further added and stirred for 1 hour. Thereafter, the precipitated solids were collected by suction filtration. The solid was further added to 2000 parts of methanol, and after stirring for 1 hour, the solid was collected by suction filtration. Thereafter, it was dried overnight in a vacuum dryer (40 ° C) to obtain 33 parts of the specific quinophthalone yellow pigment (yellow coloring agent (Y-7)) represented by the formula (2-12). The compound was then identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan, autoflex II). As a result, m/z = 454 (molecular weight: 453.5) was identified as the intended product.

(Manufacture of yellow colorant (Y-8))

First, 34 parts of 4-(2-ethylhexyloxy)-2-methylquinoline and 25 parts of naphthalene dicarboxylic anhydride, 300 parts of benzoic acid were mixed, and stirred at 200 ° C for 7 hours. After standing to cool, 1000 parts of methanol was further added and stirred for 1 hour. Thereafter, the precipitated solids were collected by suction filtration. The solid was again added to 2000 parts of methanol, and after stirring for 1 hour, the solid was collected by suction filtration. Thereafter, it was dried overnight in a vacuum dryer (40 ° C) to obtain 42 parts of the specific quinophthalone yellow pigment (yellow coloring agent (Y-8)) represented by the formula (2-13). The compound was then identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan, autoflex II). As a result, m/z = 452 (molecular weight: 451.5) was identified as the intended product.

(Manufacture of yellow colorant (Y-9))

First, in 200 parts of N,N-dimethylacetamide, 20 parts of quinoline yellow pigment represented by formula (6), 3 parts of sodium hydroxide, and 18 parts of 2-ethylhexyl group are added. 4-Bromobutyric acid was further mixed, followed by stirring at 90 ° C for 1 hour. After it was left to cool, 1000 parts of methanol and 1000 parts of water were further added and stirred for 1 hour. Thereafter, the precipitated solids were collected by suction filtration. The solid was again added to 1000 parts of methanol, and after stirring for 1 hour, the solid was collected by suction filtration. Thereafter, it was dried overnight in a vacuum dryer (40 ° C) to obtain 16 parts of the specific quinophthalone yellow pigment (yellow coloring agent (Y-9)) represented by the formula (2-27). The compound was then identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan, autoflex II). As a result, m/z = 538 (molecular weight 537.7) was confirmed as the target.

(Manufacture of yellow colorant (Y-10))

First, in 200 parts of N,N-dimethylacetamide, 20 parts of quinoline yellow pigment represented by formula (6), 3 parts of sodium hydroxide, and 19 parts of 2-ethylhexyl group are added. 4-bromopentanoic acid was further mixed, followed by stirring at 90 ° C for 1 hour. After it was left to cool, 1000 parts of methanol and 1000 parts of water were further added and stirred for 1 hour. Thereafter, the precipitated solids were collected by suction filtration. The solid was again added to 1000 parts of methanol, and after stirring for 1 hour, the solid was collected by suction filtration. Thereafter, it was dried overnight in a vacuum dryer (40 ° C) to obtain 20 parts of the specific quinophthalone yellow pigment (yellow coloring agent (Y-10)) represented by the formula (2-28). The compound was then identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan, autoflex II). As a result, m/z = 552 (molecular weight: 551.7) was identified as the intended product.

(Manufacture of yellow colorant (Y-11))

First, 200 parts of N,N-dimethylacetamide, 20 parts of commercially available CI disperse dye yellow No. 160, 3 parts of sodium hydroxide, and 18 parts of 2-ethylhexyl-4-bromo Butyric acid is mixed again, then stirred at 90 ° C for 1 small Time. After it was left to cool, 1000 parts of methanol and 1000 parts of water were further added and stirred for 1 hour. Thereafter, the precipitated solids were collected by suction filtration. The solid was again added to 1000 parts of methanol, and after stirring for 1 hour, the solid was collected by suction filtration. Thereafter, it was dried overnight in a vacuum dryer (40 ° C) to obtain 20 parts of the specific quinophthalone yellow pigment (yellow coloring agent (Y-11)) represented by the formula (2-30). The compound was then identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan, autoflex II). As a result, m/z = 538 (molecular weight 537.7) was confirmed as the target.

(Manufacture of yellow colorant (YC-3))

First, 100 parts of CI Pigment Yellow No. 138 ("Paliotol Yellow K0960-HD" manufactured by BASF), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were added to a 1-gallon kneading machine made of stainless steel (Japan Inoue Co., Ltd.) Manufactured and mixed at 70 ° C for 6 hours. Next, the mixture is put into 3000 parts of warm water, heated to 70 ° C while stirring for 1 hour to make a slurry, repeated filtration, washing with water to remove sodium chloride and diethylene glycol, and then at 80 ° C After drying overnight, 98 parts of a yellow coloring agent (YC-3) was obtained. Its average primary particle size is 35.5 nm.

[Example 1] (Green coloring composition (DG-1))

After the mixture of the following composition was stirred and mixed to be uniform, zirconia beads having a diameter of 0.5 mm were used, and dispersed by an Eiger mill disperser ("Mini Model M-250 MKII" manufactured by Eiger Japan Co., Ltd.) for 5 hours, and then 5.0 μm. The sieve was filtered to prepare a green colored composition (GP-1). In the production of the coated substrate, the ratio of the blue colorant (B-1) to the yellow colorant (Y-1) was selected in accordance with the chromaticity of x=0.290 and y=0.600 under the C light source.

[Examples 2 to 24, Reference Examples 1 to 10] (Green coloring composition (DG-2 to 34))

The green coloration with Example 1 was changed except that the blue coloring agent (B-1) and the yellow coloring agent (Y-1) were changed to a combination of the coloring agents shown in Table 1, and the blending ratio of the coloring agent was changed. The composition (DG-1) was similarly operated to obtain a green colored composition (DG-2 to 34). The ratio of the blue colorant to the yellow colorant is selected in accordance with the chromaticity of x=0.290 and y=0.600 under the C light source at the time of preparation of the coated substrate. Further, the total content of the coloring agents was 11.0 parts.

<Production and evaluation of coating film>

The evaluation of the brightness (color characteristics), heat resistance, and light resistance of the green coating film produced by the obtained green coloring composition (DG-1 to 34) was carried out by the following method. The results of the evaluation are shown in Table 1.

(Brightness evaluation of film)

The green coloring composition (DG-1 to 34) was coated on a 100 mm × 100 mm, 1.1 mm thick glass substrate by a spin coater, followed by drying at 70 ° C for 20 minutes, followed by heating at 220 ° C. In a minute, it was left to cool to form a coated substrate. The brightness (Y) of the obtained coating film was measured by a microspectrophotometer ("OSP-SP100" manufactured by Olympus Corporation, Japan). The prepared coated substrate was subjected to a heat treatment at 220 ° C, and was subjected to a chromaticity of x=0.290 and y=0.600 under a C light source. Regarding the brightness (Y), if it is above 0.2 point, there is a significant difference.

(Evaluation of heat resistance of coating film)

The green coloring composition (DG-1 to 34) was coated on a 100 mm × 100 mm, 1.1 mm thick glass substrate by a spin coater, followed by drying at 70 ° C for 20 minutes, followed by heating at 220 ° C. In a minute, it was left to cool to form a coated substrate. The prepared coated film substrate was heat-treated at 220 ° C, and was uniformly combined with a chromaticity of x=0.290 and y=0.600 under a C light source. The chromaticity of the obtained coating film under a C light source ([L*(1), a*(1), b*(1)])) is a microscopic spectrophotometer ("OSP-SP100" manufactured by Olympus, Japan) ) Determination. Thereafter, the heat resistance test was performed by heating at 230 ° C for 1 hour, and then measuring the chromaticity under the C light source ([L*(2), a*(2), b*(2)))), and the following formula The color difference ΔEab* was determined and evaluated in the following three stages.

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

○: △Eab* is less than 5.0

△: △Eab* is above 5.0 and not up to 10.0

×: △Eab* is above 10.0

(Light resistance evaluation of coating film)

First, a coated substrate is prepared in the same manner as in the evaluation of heat resistance, and the chromaticity under the C light source ([L*(1), a*(1), b*(1))]) is microscopic spectrophotometry. The measurement ("OSP-SP100" manufactured by Olympus Corporation of Japan) was measured. Then, an ultraviolet-resistant color filter ("COLORED OPTICAL GLASS L38" manufactured by Hoya Co., Ltd., Japan) was attached to the substrate, and the ultraviolet light was irradiated with a xenon lamp of 470 W/m ² for 100 hours, and then the color under the C light source was measured. The degree ([L*(2), a*(2), b*(2)))), the color difference ΔEab* was obtained by the above calculation formula, and was evaluated on the same basis as the heat resistance.

Yellow colorant (YC-1): commercially available C.I. Disperse Dye Yellow No. 54

Yellow colorant (YC-2): commercially available C.I. Disperse Dye Yellow No. 64

As shown in Table 1, the coloring agent having the features of the embodiment has The green coloring composition containing the anthraquinone dye represented by the formula (8A) and the quinoline yellow pigment represented by the formula (6) is excellent in brightness, and the heat resistance and light resistance of the coating film are excellent. There is no problem in terms of sex.

On the other hand, the green colored compositions (DG-25 to 30, 33, and 34) of Reference Examples 1 to 6, 9, and 10 showed low luminance and also had problems in heat resistance and light resistance. Further, the green coloring compositions (DG-31, 32) of Reference Examples 7 and 8 showed no problem in terms of heat resistance and light resistance, but the brightness was low as compared with the examples.

<Method for Producing Green Photosensitive Colored Composition> [Example 25] (Green photosensitive coloring composition (RG-1))

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

[Examples 26 to 48, Reference Examples 11 to 20] (Green photosensitive coloring composition (RG-2 to 34))

A green photosensitive coloring composition (RG-2 to 34) was obtained in the same manner as in Example 25 except that the green coloring composition (DG-1) was changed to the green coloring composition shown in Table 2.

<Production and evaluation of coating film>

The evaluation of the brightness (color characteristics), heat resistance, light resistance, and voltage holding ratio of the green coating film produced by the obtained green photosensitive coloring composition (RG-1 to 34) was carried out in the following manner. The results of the evaluation are shown in Table 2.

(Brightness evaluation of film)

The green photosensitive coloring composition (RG-1 to 34) was coated on a 100 mm × 100 mm, 1.1 mm thick glass substrate by a spin coater, followed by drying at 70 ° C for 20 minutes, and ultrahigh pressure mercury. The lamp was subjected to ultraviolet light exposure at a total amount of light of 150 mJ/cm ² , and then developed at 23 ° C with an alkali developing solution to obtain a coated substrate. Thereafter, the film was heated at 220 ° C for 30 minutes, and allowed to stand for cooling, and then the brightness Y (C) of the coated substrate was measured by a microspectrophotometer ("OSP-SP100" manufactured by Olympus, Japan). Further, the produced coated substrate was subjected to heat treatment at 220 ° C to have a chromaticity of x=0.290 and y=0.600 under a C light source. In the case of the alkali imaging solution, 1.5% by mass of sodium carbonate, 0.5% by mass of sodium hydrogencarbonate, 8.0% by mass of an anionic surfactant ("Pelex NBL" manufactured by Kao Corporation, Japan), and 90% by mass of water are used. By. Among them, regarding the brightness Y (C), if it is above 0.2 point, there is a significant difference.

(Evaluation of heat resistance of coating film)

The green photosensitive coloring composition (RG-1 to 34) was dried on a glass substrate of 100 mm × 100 mm and 1.1 mm thick at 70 ° C for 20 minutes using a spin coater, and then an ultrahigh pressure mercury lamp was used. The cumulative amount of light was 150 mJ/cm ² for ultraviolet exposure, and then development was carried out with an alkali developing solution at 23 ° C, followed by heating at 220 ° C for 30 minutes, and after standing and cooling, a coated substrate was obtained. The prepared coated substrate was subjected to heat treatment at 220 ° C, and was then allowed to have a chromaticity of x = 0.290 and y = 0.600 under a C light source. The chromaticity ([L*(1), a*(1), b*(1)))) of the obtained coating film under the C light source is a microscopic spectrophotometer ("OSP-SP100" manufactured by Olympus, Japan" ) Determination. Thereafter, the heat resistance test was performed by heating at 230 ° C for 1 hour, and the chromaticity ([L*(2), a*(2), b*(2)))) under the C light source was measured, and the following Calculate the formula, find the color difference ΔEab*, and evaluate it in the following three stages.

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

○: △Eab* is less than 5.0

△: △Eab* is above 5.0 and not up to 10.0

×: △Eab* is above 10.0

(Light resistance evaluation of coating film)

First, a coated substrate is prepared in the same manner as in the evaluation of heat resistance, and the chromaticity under the C light source ([L*(1), a*(1), b*(1))]) is microscopic spectrophotometry. The measurement ("OSP-SP100" manufactured by Olympus Corporation of Japan) was measured. Then, an ultraviolet-resistant color filter ("COLORED OPTICAL GLASS L38" manufactured by Hoya Co., Ltd., Japan) was attached to the substrate, and the ultraviolet light was irradiated with a xenon lamp of 470 W/m ² for 100 hours, and then the color under the C light source was measured. The degree ([L*(2), a*(2), b*(2)))), the color difference ΔEab* was obtained by the above calculation formula, and was evaluated on the same basis as the heat resistance.

(assessment of voltage retention rate)

The green photosensitive coloring composition (RG-1 to 34) was applied to a glass substrate of 100 mm × 100 mm and 1.1 mm thick by a spin coater so that the film thickness of the dried film was 2.0 μm. The light amount was 50 mJ/cm ² and exposed to ultraviolet light, and then developed at 23 ° C with an alkali developing solution to obtain a coated film substrate. After heating at 220 ° C for 30 minutes and allowing to stand for cooling, 0.05 parts of the coating film was scraped off from the obtained coated substrate, and then immersed in 1.5 parts of liquid crystal (manufactured by Merck, MLC-2041), and dried at 120 After etching at ° C for 1 hour and centrifuging at 4000 rpm for 15 minutes, the supernatant was taken to prepare a coating film-extracted liquid crystal sample solution.

On the other hand, a glass substrate containing an ITO transparent electrode having an effective electrode size of 10 mm × 10 mm was placed in a face-to-face manner so that the ITO transparent electrode faces were placed face-to-face, and the cell gap was made 9 μm. unit. Then, the liquid crystal sample liquid is injected into the cell gap by the photoresist in the small unit, and the voltage of 60 μsec is applied at a voltage of 5 V at 60 ° C, and the cell voltage [V1] after 16.67 m seconds after the voltage is released. It was measured by VHR-1S manufactured by Toyo Technica Co., Ltd., Japan. In this measurement, five repeated measurements were performed, and the measured cell voltages were averaged. Then, the voltage holding ratio (%) of the obtained cell voltage was determined by the following formula and evaluated in the following three stages.

Voltage retention rate (%) = ([V1] / 5 × 100)

○: 95% or more

△: 90% or more and less than 95%

×: less than 90%

As shown in Table 2, the coloring agent having the characteristics of the present embodiment contains an anthraquinone dye represented by the formula (8A) and a quinoline coloring compound represented by the formula (6). The green photosensitive coloring composition was excellent in brightness, and was excellent in heat resistance, light resistance, and voltage holding ratio.

On the other hand, in the green photosensitive coloring compositions (RG-25 to 30, 33, and 34) of Reference Examples 11 to 16, 19, and 20, the brightness was lowered, and heat resistance and light resistance were inferior. Further, Reference Examples 15 to 18 of C.I. Pigment Green No. 58 were used, and the results were inferior in voltage holding ratio as compared with the examples.

<Production of color filter>

First, the preparation of the red photosensitive coloring composition and the blue photosensitive coloring composition used for the production of the color filter was performed.

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

After the mixture of the following composition was stirred and mixed to be uniform, zirconia beads having a diameter of 0.5 mm were used, and dispersed by an Eiger mill disperser ("Mini Model M-250 MKII" manufactured by Eiger Japan Co., Ltd.) for 5 hours, and then 5.0 μm. The sieve was filtered to prepare a red colored composition (DR-1).

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

After the mixture of the following composition was stirred and mixed to be uniform, zirconia beads having a diameter of 0.5 mm were used, and dispersed by an Eiger mill disperser ("Mini Model M-250 MKII" manufactured by Eiger Japan Co., Ltd.) for 5 hours, and then 5.0 μm. The sieve was filtered to prepare a blue colored composition (DB-1).

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

(production of color filter)

The black matrix on the glass substrate was first processed into an image, and the red photosensitive coloring composition (RR-1) was applied onto the substrate by a spin coater to form a colored film. The film was further irradiated with ultraviolet rays at 150 mJ/cm ² using an ultrahigh pressure mercury lamp through a mask. Next, the alkali developing solution composed of a 0.2% by weight aqueous sodium carbonate solution was spray-imaged to remove the unexposed portion, and then washed with ion-exchanged water, and the substrate was heated at 220 ° C for 20 minutes to form a substrate. Red color filter fragment. The red color filter segment can be combined with the chromaticity of x=0.640 and y=0.330 under the C light source (hereinafter, green and blue are also used) after the heat treatment at 220 °C. At the same time, in the same way, the green color filter segment is formed into a chromaticity of x=0.290 and y=0.600 with a green photosensitive coloring composition (RG-6), so that the blue color filter segment is The blue photosensitive coloring composition (RB-1) was formed to have a chromaticity of x=0.150 and y=0.060, and each color filter segment was formed to obtain a color filter.

As a result, it is understood that the green photosensitive coloring composition (RG-6) can be used in a high-density color filter and can be used without any problem in other physical properties.

"Embodiment VII"

Hereinafter, "PGMAC" means propylene glycol monomethyl ether acetate. Further, the method for measuring the weight average molecular weight (Mw) of the resin and the comparative value is as follows.

<Resin weight average molecular weight (Mw)>

The weight average molecular weight (Mw) of the resin is determined by using HLC-8220GPC (manufactured by Tosoh Corporation, Japan), TSK-GEL SUPER HZM-N for two columns, and the solvent is converted by THF. Molecular weight.

<comparison value>

The light emitted from the backlight unit for the liquid crystal display is polarized by the polarizing plate, and then passes through the coating film of the colored composition coated on the glass substrate to reach the polarizing plate at the other end. At this time, when the polarizing plate is parallel to the polarizing surface of the polarizing plate, the light passes through the polarizing plate, but when the polarizing surface is perpendicular to the polarizing plate, the light is blocked by the polarizing plate. However, when the light which is polarized by the polarizing plate passes through the coating film of the coloring composition, light scattering occurs due to the colorant particles, and a part of the polarizing surface is shifted, and the amount of light transmitted when it is parallel to the polarizing plate is reduced, or is polarized. Only a portion of the light passes through the plate when it is vertical. The luminance of the transmitted light on the polarizing plate is measured, and the luminance of the polarizing plate in parallel and the ratio of the luminance in the vertical direction are calculated as the contrast value.

(comparative value) = (luminance in parallel) / (luminance in vertical)

Therefore, when light scattering occurs due to the coloring agent in the coating film, since the luminance in the vertical direction is increased, the contrast value can be lowered.

Further, the luminance meter is a color luminance meter ("BM-5A" manufactured by Topcon Japan Co., Ltd.), and a polarizing plate ("NPF-G1220DUN" manufactured by Nitto Denko Corporation) is used as the polarizing plate. At the time of the measurement, it was measured by a black mask which was opened by a 1 cm square hole in the measurement part.

First, quinoline yellow pigment [A1] and quinoline yellow pigment [A2] used in the examples and the reference examples, a binder resin solution, a resin type dispersant solution, a quinoline yellow pigment [B], and an indigo Method for producing aluminized aluminum pigment, method for miniaturizing pigment, method for producing green colored composition and red colored composition, green photosensitive coloring composition, and red photosensitive A method of producing a color composition will be described.

<Method for producing quinoline yellow pigment [A1] [Quinoline yellow pigment [A1-1]]

2.3 parts of 6-isopropyl-2-methylquinoline and 2.5 parts of naphthalene dicarboxylic anhydride, 30 parts of benzoic acid were mixed, and stirred at 200 ° C for 7 hours. After standing to cool, 100 parts of methanol was further added and stirred for 1 hour. Thereafter, the precipitated solids were collected by suction filtration. The solid was again added to 200 parts of methanol, and after stirring for 1 hour, the solid was collected by suction filtration. Thereafter, it was dried overnight in a vacuum dryer (40 ° C) to obtain 3.1 parts of a product. Its yield was 67%. The product was then subjected to identification by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan, autoflex II). As a result, m/z = 366 (molecular weight 365.4) was confirmed as the target.

[Quinoline yellow pigment [A1-2]]

In the same manner as quinoline yellow pigment (A1-1), by 8-(1,3-di) The pigment formed by the reaction of alk-2-yl)-methyl-2-methylquinoline with naphthalene dicarboxylic anhydride is brominated by N-bromosuccinimide to give quinoline yellow pigment (A1-2). Then, the product was identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan Co., Ltd., autoflex II) to determine the target product.

[Quinoline yellow pigment [A1-3 to 14]]

The quinoline yellow pigment [A1-3 to 14] is obtained by reacting the corresponding 2-methylquinoline with naphthalene dicarboxylic anhydride in the same manner as the quinophthalone yellow pigment (A1-1). The product was further identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan Co., Ltd., autoflex II) to determine the target product.

<Method for producing quinoline yellow pigment [A2] [Quinoline yellow pigment [A2-1]]

10.8 parts of 6-isopropyl-2-methylquinoline, 12.1 parts of benzenetricarboxylic anhydride, and 60 parts of benzoic acid were mixed and stirred at 200 ° C for 7 hours. The purified yellow solid was washed with dimethylformamide to give 14 g of yellow material. Then, 0.2 g of pyridine and o-dichlorobenzene were added to 5 g of the yellow matter, followed by 3.8 parts of sulfinium chloride, and after distillation under reduced pressure, 1.76 g of 3-amino group was further added. 2-propanol was reacted at 180 ° C for 7 hours, and then cooled, washed with hexane, dried, and then purified through a silica gel column to obtain a yellow powder. Quality analyzer (TOF-MS: manufactured by Bruker Daltonics Japan, autoflex II) The identification of the compound can be determined as the target.

[Quinoline Yellow [A2-2]]

In the same manner as quinoline yellow pigment (A2-1), 5-bromo-8-(1,3-di) The alkyl-2-yl)methyl-2-methylquinoline is reacted with phthalic anhydride to give a yellow powder. Further, the compound was identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan Co., Ltd., autoflex II), and it was confirmed as a target.

[Quinoline yellow pigment [A2-3 to 16]]

The quinoline yellow pigment [A2-3 to 16] is obtained by reacting the corresponding 2-methylquinoline with phthalic anhydride in the same manner as the quinophthalone yellow pigment (A2-1). Further, the compound was identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan Co., Ltd., autoflex II), and it was confirmed as a target.

The structures of the quinoline yellow pigment [A1] and the quinoline yellow pigment [A2] produced are shown in Table 1.

<Method for Producing Binder Resin Solution> (Acrylic resin solution 1)

196 parts of cyclohexanone was placed in a reaction vessel equipped with a thermometer, a condenser, a nitrogen introduction tube, a dropping tube, and a stirring device in a separable 4-necked flask, and the temperature was raised to 80 ° C, and the reaction vessel was replaced with After nitrogen, 37.2 parts of benzyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, and 20.7 parts of p-isopropylidene phenol phenol B were dropped from the tube. A mixture of an alkene-modified acrylate ("Aronix M110" manufactured by Japan East Asia Synthetic Co., Ltd.) and 1.1 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After the completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a solution of an acrylic resin. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180 ° C for 20 minutes to measure non-volatile matter, and PGMAC was added to prepare an acrylic resin in such a manner that the non-volatile content was 20% by weight in the previously synthesized resin solution. Solution 1 (resin solution 1). Its weight average molecular weight (Mw) was 26,000.

(Acrylic resin solution 2)

370 parts of cyclohexanone was placed in a separable 4-necked flask equipped with a thermometer, a condenser, a nitrogen introduction tube, a dropping tube, and a stirring device, and the temperature was raised to 80 ° C, and the inside of the flask was replaced with nitrogen. A mixture of 18.2 parts of glycidyl methacrylate, 53 parts of methyl methacrylate, and 2.0 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After the dropwise addition, after further reacting at 100 ° C for 3 hours, 1.0 part of azobisisobutyronitrile was dissolved in 50 parts of cyclohexanone, and the reaction was further continued at 100 ° C for 1 hour. Next, replacing the air in the container with a replacement of 0.5 parts of tris-dimethylaminophenol and 0.1 part of hydroquinone in 9.3 parts of acrylic acid (equivalent equivalent of epoxy propylene) into the above container at 120 ° C The reaction was continued for 6 hours until the solid acid value became 0.5, and the reaction was terminated to obtain a solution of an acrylic resin. Thereafter, 19.5 parts of tetrahydrofurfuric anhydride (equivalent of the resulting hydroxyl group) and 0.5 part of triethylamine were further added and reacted at 120 ° C for 3.5 hours to obtain a solution of an acrylic resin.

After cooling to room temperature, about 2 g of the resin solution was sampled and dried at 180 ° C for 20 minutes to determine the nonvolatile matter, and PGMAC was added to prepare an acrylic resin solution in such a manner that the nonvolatile content was 20% by weight in the previously synthesized resin solution. 2 (Resin solution 2). Its weight average molecular weight (Mw) is 19,000.

<Manufacture of Resin Type Dispersant Solution> (Resin type dispersant solution 1)

80 parts of n-butyl methacrylate and 120 parts of benzyl methacrylate were placed in a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, and replaced with nitrogen. After heating the reaction vessel To 80 ° C, a solution of 0.1 part of 2,2'-azobisisobutyronitrile dissolved in 12 parts of 3-mercapto-1,2-propanediol was further added thereto, and reacted for 10 hours. A 95% reaction was then determined by solids determination. Then add 30 parts of benzenetetracarboxylic anhydride, 242 parts of cyclohexanone, 0.40 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst, and at 120 ° C The reaction was carried out for 7 hours. It was confirmed by the measurement of the acid value that 98% or more of the acid anhydride had been half-esterified, and then the reaction was terminated to obtain a resin type dispersant 1. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried at 180 ° C for 20 minutes to determine the nonvolatile content, so that the non-volatile content in the previously synthesized resin solution was 20% by mass. The resin type dispersant solution 1 (dispersant 1) was prepared with pentanone. Its weight average molecular weight (Mw) was 9,500.

(Resin type dispersant solution 2)

A resin type dispersant ("BYK-LPN6919" manufactured by BYK Chemical Co., Ltd., Japan) was diluted with PGMAC to adjust to a resin type dispersant solution 2 (dispersant 2) having a nonvolatile content of 20% by weight.

<Method for producing quinoline yellow pigment [B]> (Manufacture of quinoline yellow pigment [B-1])

The compound (1) is obtained by the synthesis method described in JP-A-2008-81566.

Then, add 300 parts to 300 parts of methyl benzoate. The compound (1), 70 parts of 2, 3-naphthalenedicarboxylic anhydride, and 143 parts of benzoic acid were further heated to 180 ° C to carry out a reaction for 4 hours. Then, the formation of the quinophthalone yellow pigment (B-1) represented by the following formula (50) and the disappearance of the compound (1) of the starting material were determined by TOF-MS. Thereafter, 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 further separated by filtration, washed with methanol, and dried to obtain 120 parts of quinoline yellow pigment (B-1). The result of mass analysis by TOF-MS was confirmed to be a quinophthalone yellow pigment (B-1).

(Manufacture of quinoline yellow pigment [B-2])

First, the compound (2) is obtained by the same method as the synthesis of the compound (1) by using the quinoline yellow pigment (B-1) as a raw material in accordance with the synthesis method described in JP-A-2008-81566.

Thereafter, 100 parts of the compound (2), 108 parts of tetrachlorophthalic anhydride, and 143 parts of benzoic acid were further added to 300 parts of methyl benzoate, and the mixture was further heated to 180 ° C to carry out a reaction for 4 hours. Then determine the quinoline by TOF-MS The formation of the yellow pigment (B-2) and the disappearance of the compound (2) of the starting material. Thereafter, 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 further separated by filtration, washed with methanol, and dried to obtain 120 parts of a quinoline yellow pigment (B-2) of the formula (51). The result of mass analysis by TOF-MS was confirmed to be a quinophthalone yellow pigment (B-2).

<Method for producing anthraquinone aluminum pigment> (Anthraquinone aluminum pigment (C-1))

First, 225 parts of sebaconitrile and 78 parts of anhydrous aluminum chloride were added to 1250 parts of n-pentanol in the reaction vessel, followed by stirring. Thereafter, 266 parts of DBU (1,8-Diazabicyclo [5.4.0] undec-7-ene) was added thereto and heated, and refluxed at 136 ° C for 5 hours. Thereafter, the reaction solution was cooled to 30 ° C under stirring, and a mixed solvent of 5000 parts of methanol and 10,000 parts of water was added while stirring to obtain a blue slurry. The slurry was further filtered, washed with a mixed solvent of 2000 parts of methanol and 4000 parts of water, and dried to obtain 135 parts of chloroaluminum indigo. Thereafter, 100 parts of chloroaluminum indigo in the reaction vessel was gradually added to 1200 parts of concentrated sulfuric acid at room temperature. After further stirring at 40 ° C for 3 hours, the sulfuric acid solution was poured into 24,000 parts of 3 ° C cold water. The blue precipitate is filtered and water After washing and drying, 102 parts of an anthocyanin aluminum pigment (C-1) represented by the following formula (53) was obtained.

(Anthraquinone aluminum pigment (C-2))

First, 100 parts of the anthraquinone aluminum pigment (C-1) of the formula (53) and 49.5 parts of diphenyl phosphate are added to 1000 parts of methanol in the reaction vessel, and then heated to 40 ° C to make it Reaction for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol, and dried to obtain 114 parts of an anthocyanin aluminum pigment (C-2) of the formula (54).

(Anthraquinone aluminum pigment (C-3))

First, add 100 parts to 1000 parts of methanol in the reaction vessel. The anthraquinone aluminum pigment (C-1) represented by the formula (53) and 43.2 parts of diphenylphosphonic acid were further heated to 40 ° C to cause a reaction for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol, and dried to obtain 112 parts of an anthocyanin aluminum pigment (C-3) represented by the formula (55).

<Pelletization method of pigment> (yellow coloring agent (PY-1))

First, 100 parts of quinoline yellow pigment (B-1), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were added to a 1-gallon kneader made by stainless steel (manufactured by Inoue, Japan) at 60 ° C. The mixture was mixed for 6 hours and subjected to salt milling. Next, the mixture was put into 3 liters of warm water, heated to 70 ° C while stirring for 1 hour to make a slurry, repeated filtration, washing with water to remove sodium chloride and diethylene glycol, and then at 80 ° C After drying overnight, 98 parts of a yellow coloring agent (PY-1) was obtained. Its average primary particle size is 31.3 nm.

(yellow coloring agent (PY-2))

First, 40 parts of quinoline yellow pigment (B-2), 60 parts of C.I. Pigment Yellow No. 138 ("Paliotol Yellow K0960-HD" manufactured by BASF), 1200 parts of sodium chloride and 120 parts of diethylene glycol were placed in a 1-gallon kneader (manufactured by Inoue, Ltd.) made of stainless steel, and mixed at 60 ° C for 8 hours. Next, the mixture is put into warm water, heated to about 70 ° C while stirring for 1 hour to make it into a slurry, repeatedly filtered, washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. One night, 97 parts of a yellow colorant (PY-2) was obtained. Its average primary particle size is 36.8 nm.

(yellow coloring agent (PY-3))

First, 100 parts of CI Pigment Yellow No. 138 ("Paliotol Yellow K0960-HD" manufactured by BASF), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were added to a 1-gallon kneading machine made of stainless steel (Japan Inoue Co., Ltd.) Manufactured and mixed at 70 ° C for 6 hours. Next, the mixture is put into 3000 parts of warm water, heated to 70 ° C while stirring for 1 hour to make a slurry, repeated filtration, washing with water to remove sodium chloride and diethylene glycol, and then at 80 ° C After drying overnight, 98 parts of a yellow coloring agent (PY-3) was obtained. Its average primary particle size is 35.5 nm.

(yellow coloring agent (PY-4))

First, 500 parts of the metal complex yellow pigment CI Pigment Yellow 150 ("E4GN" manufactured by Lanxess), 2500 parts of sodium chloride, and 250 parts of diethylene glycol were added to a 1-gallon kneader made of stainless steel ( In Japan, manufactured by Inoue, Ltd., and mixed at 100 ° C for 6 hours. Next, the mixture was put into 5 liters of warm water, heated to 70 ° C while stirring for 1 hour to make a slurry, repeated filtration, washing with water to remove sodium chloride and diethylene glycol, and then at 80 ° C After drying overnight, a yellow colorant (PY-4) was obtained. The obtained pigment had a volume average primary particle diameter of 28.3 nm.

(yellow coloring agent (PY-5))

First, 500 parts of isoporphyrin yellow pigment CI Pigment Yellow No. 139 ("Paliotol Yellow-D1819" manufactured by BASF), 2500 parts of sodium chloride, and 250 parts of diethylene glycol are added to a gallon of stainless steel. The kneader (manufactured by Inoue, Ltd., Japan) was mixed at 100 ° C for 6 hours. Next, the mixture was put into 5 liters of warm water, heated to 70 ° C while stirring for 1 hour to make a slurry, repeated filtration, washing with water to remove sodium chloride and diethylene glycol, and then at 80 ° C After drying overnight, a yellow colorant (PY-5) was obtained. The obtained pigment had a volume average primary particle diameter of 29.3 nm.

(green colorant (PG-1))

First, 500 parts of green pigment CI Pigment Green No. 58 (ascorbine zinc, DIC company made "FASTGEN GREEN A110"), 1500 parts of sodium chloride, and 250 parts of diethylene glycol were added to a 1 gallon kneading made of stainless steel. The machine (manufactured by Inoue, Japan) was mixed at 120 ° C for 8 hours. Next, the mixture was put into 5 liters of warm water, heated to 70 ° C while stirring for 1 hour to make a slurry, repeated filtration, washing with water to remove sodium chloride and diethylene glycol, and then at 80 ° C After drying overnight, a green colorant (PG-1) was obtained. The obtained pigment had a volume average primary particle diameter of 25.2 nm.

(green colorant (PG-2))

First, 500 parts of green pigment CI Pigment Green No. 36 ("LIONOL GREEN 6YK" manufactured by Toyo Ink Manufacturing Co., Ltd.), 2,500 parts of sodium chloride, and 250 parts of diethylene glycol were added to a 1-gallon kneader made of stainless steel. (manufactured by Inoue, Japan), and mixed at 100 ° C for 2 hours. Secondly, The mixture was put into 5 liters of warm water, heated to 70 ° C while stirring for 1 hour to make it into a slurry, repeatedly filtered, washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. One night, 490 parts of green colorant (PG-2) were obtained. The obtained pigment had a volume average primary particle diameter of 26.6 nm.

(green colorant (PG-3))

First, 500 parts of green pigment (CI Pigment Green No. 7, made by Japan Toyo Ink Manufacturing Co., Ltd., "LIONOL GREEN Y-101"), 1,500 parts of sodium chloride, and 250 parts of diethylene glycol are added to stainless steel. The mixture was kneaded in a gallon kneader (manufactured by Inoue, Japan) and mixed at 120 ° C for 8 hours. Next, the mixture was put into 5 liters of warm water, heated to 70 ° C while stirring for 1 hour to make a slurry, repeated filtration, washing with water to remove sodium chloride and diethylene glycol, and then at 80 ° C After drying overnight, a green colorant (PG-3) was obtained. The obtained pigment had a volume average primary particle diameter of 33.1 nm.

(red colorant (PR-1))

First, 500 parts of red pigment (CI Pigment Red No. 177, CROMOPHTAL RED A2B manufactured by Ciba Special Chemical Co., Ltd.), 1500 parts of sodium chloride, and 250 parts of diethylene glycol were added to a 1-gallon kneader made of stainless steel ( In Japan, manufactured by Inoue, Ltd., and mixed at 120 ° C for 8 hours. Next, the mixture was put into 5 liters of warm water, heated to 70 ° C while stirring for 1 hour to make a slurry, repeated filtration, washing with water to remove sodium chloride and diethylene glycol, and then at 80 ° C After drying overnight, a red colorant (PR-1) was obtained. The volume average primary particle diameter of the obtained pigment is 28.3nm.

(blue colorant (PB-1))

First, 100 parts of anthraquinone aluminum pigment (C-1), 1200 parts of sodium chloride, and 120 parts of diethylene glycol are added to a stainless steel one-gallon kneader (manufactured by Inoue, Japan), and 70 Mix at °C for 6 hours. Next, the mixture is put into 3000 parts of warm water, heated to 70 ° C while stirring for 1 hour to make a slurry, repeated filtration, washing with water to remove sodium chloride and diethylene glycol, and then at 80 ° C After drying overnight, a blue colorant (PB-1) was obtained. Its average primary particle diameter was 30.4 nm.

(blue colorant (PB-2))

A blue coloring agent was obtained by a salt milling treatment similar to the blue coloring agent (PB-1) except that the anthraquinone aluminum pigment (C-1) was changed to the anthraquinone aluminum pigment (C-2). (PB-2). Its average primary particle size was 31.2 nm.

(blue colorant (PB-3))

A blue coloring agent was obtained by a salt milling treatment similar to the blue coloring agent (PB-1) except that the anthraquinone aluminum pigment (C-1) was changed to the anthraquinone aluminum pigment (C-3). (PB-3). Its average primary particle diameter was 29.5 nm.

(blue colorant (PB-4))

First, 500 parts of blue pigment (CI Pigment Blue 15:6, manufactured by BASF, "Heliogen Blue-L-6700F"), 2500 parts of sodium chloride, and 250 parts of diethylene glycol are added to stainless steel. The mixture was kneaded in a gallon kneader (manufactured by Inoue, Japan) and mixed at 100 ° C for 2 hours. Next, the mixture is put into 5 liters of warm water, heated to 70 ° C while stirring for 1 hour to make it into a slurry, repeatedly filtered, washed with water to remove sodium chloride and After diethylene glycol, it was further dried at 80 ° C for one night to obtain 490 parts of a blue coloring agent (PB-4). The obtained pigment had a volume average primary particle diameter of 26.6 nm.

(blue colorant (PB-5))

500 parts of α-type anthraquinone copper-based cyanide pigment (CI Pigment Blue 15:1, manufactured by Toyo Ink Manufacturing Co., Ltd., "LIONOL BLUE 7120-V"), 2500 parts of sodium chloride, and 250 parts The ethylene glycol was added to a 1-gallon kneader made of stainless steel (manufactured by Inoue, Ltd.), and mixed at 100 ° C for 2 hours. Next, the mixture was put into 5 liters of warm water, heated to 70 ° C while stirring for 1 hour to make a slurry, repeated filtration, washing with water to remove sodium chloride and diethylene glycol, and then at 80 ° C After drying overnight, 490 parts of a blue colorant (PB-5) were obtained. The obtained pigment had a volume average primary particle diameter of 35.2 nm.

The obtained coloring agent is shown in Table 2.

<Method for Producing Green Colored Composition (DG-1)>

After the mixture of the following composition was stirred and mixed to be uniform, zirconia beads having a diameter of 0.5 mm were used, and dispersed by an Eiger mill disperser ("Mini Model M-250 MK II" manufactured by Eiger Japan Co., Ltd.) for 5 hours, and then 5.0. The sieve of μm was filtered to prepare a green colored composition (DG-1).

<Method for Producing Red Colored Composition (DR-1)>

After the mixture of the following composition was stirred and mixed to be uniform, zirconia beads having a diameter of 0.5 mm were used, and dispersed by an Eiger mill disperser ("Mini Model M-250 MK II" manufactured by Eiger Japan Co., Ltd.) for 5 hours, and then 5.0. The sieve of μm was filtered to prepare a red colored composition (DR-1).

<Method for Producing Green Photosensitive Colored Composition (RG-1)>

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

<Method for Producing Red Photosensitive Colored Composition (RR-1)>

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

[Example 1] (Coloring composition (P-1))

The mixture of the following components was warmed at 50 ° C while being stirred for 0.5 hour to make it uniform. Thereafter, zirconia beads having a diameter of 0.5 mm were used, and dispersed by an Eiger polishing disperser ("Mini Model M-250 MK II" manufactured by Eiger Japan Co., Ltd.) for 0.5 hour, and then filtered through a 5 μm sieve to prepare a colored composition ( P-1).

[Examples 2 to 24, Reference Examples 1, 2] (Coloring composition (P-2 to 24 and P-46, 47))

The same procedure as in the coloring composition (P-1) except that the quinoline yellow pigment, the resin type dispersant solution, the acrylic resin solution, the type of the solvent, and the blending amount (parts by weight) were changed as shown in Table 3. The colored composition (P-2 to 24) and the colored composition (P-46, 47) were prepared. Also, in which coloring is used together In the case of the agent, the total amount of the coloring agent was 10 parts in all of the coloring compositions.

The abbreviation in Table 3 is as follows.

Organic solvents

. Anon: cyclohexanone

[Example 25] (Coloring composition (P-25))

The mixture of the following components was stirred and mixed at 50 ° C for uniformity, and then zirconia beads having a diameter of 0.5 mm were used, and an Eiger polishing disperser ("Mini Model M-250 MK II" manufactured by Eiger Japan Co., Ltd.) was used. After dispersing for 5 hours, it was filtered through a 5 μm sieve to prepare a colored composition 25 (P-25).

[Examples 26 to 45, Reference Examples 3 to 8] (Coloring composition (P-26 to 45 and P-48 to 53))

The same as the coloring composition (P-25) except that the quinoline yellow pigment, the pigment, the resin type dispersant solution, the acrylic resin solution, the type of the solvent, and the blending amount (parts by weight) were changed as shown in Table 4. The composition was prepared into a coloring composition (P-26 to 45) and a coloring composition (P-48 to 58). Again, its When the coloring agent is used in combination, the total amount of the coloring agent is 10.0 parts in all the coloring compositions.

The abbreviation in Table 4 is as follows.

Organic solvents

. Anon: cyclohexanone

[Assessment of coloring composition]

The evaluation of the contrast value and the coloring power in the colored composition (P-1 to 53) was carried out in the following manner.

The results are shown in Tables 5 and 6.

(evaluation of comparison value)

The colored compositions (P-1 to 53) obtained were applied on a glass substrate of 100 mm × 100 mm and 1.1 mm thick by a spin coater, followed by drying at 70 ° C for 20 minutes, and then placed and cooled to prepare a composition. Coating substrate. Thereafter, the initial contrast value (initial CR) of the obtained coated substrate was measured. In this case, the coating conditions of the spin coater were adjusted so that the film thickness measured by the surface shape measuring instrument "Dektak 8 (manufactured by Veeco)" was 1 μm, and a coating film was produced.

(assessment of tinting strength)

The obtained colored compositions (P-1 to 32, and P-34 to 53) and the green colored composition (DG-1) were mixed to prepare a green colored composition. Wherein the blending ratio of the coloring composition (P-1 to 32, and P-34 to 53) and the green coloring composition (DG-1), wherein in the preparation of any coated substrate, is combined with the C light source x= The chroma of 0.290 and y=0.600, and the ratio is selected. Next, the obtained mixed coloring composition was applied by a spin coater so as to have y = 0.600 under a C light source, and then dried at 70 ° C for 20 minutes to obtain a coated substrate. Further, the coloring power was evaluated based on the results of measurement of the obtained coated substrate film thickness. The film thickness of the obtained coating film was measured by a surface shape measuring instrument "Dektak 8 (manufactured by Veeco Co., Ltd.)". The results are judged based on the following criteria. The smaller the film thickness of the chromaticity that gives the purpose It means that the greater the coloring power, the better.

◎: Not up to 2.40 [μm]

○: 2.40 or more and less than 2.56 [μm]

×: 2.56 or more [μm]

At the same time, the obtained colored composition (P-33) and the red colored composition (DR-1) were mixed to prepare a red colored composition. Further, the blending ratio of the coloring composition (P-33) and the red coloring composition (DR-1) was selected in accordance with the chromaticity of x=0.640 and y=0.334 in the C light source when the coated substrate was produced. proportion. Next, the obtained mixed coloring composition was applied by a spin coater so as to be applied to x = 0.640 under a C light source, and then dried at 70 ° C for 20 minutes to obtain a coated substrate. Then, the coloring power was evaluated in accordance with the measurement result of the film thickness of the obtained coated substrate. The film thickness of the obtained coating film was measured by the surface shape measuring instrument "Dektak 8 (manufactured by Veeco)". The results are judged based on the following criteria. The smaller the film thickness of the chromaticity which gives the purpose, the greater the coloring power, and it is excellent.

◎: less than 1.52 [μm]

○: 1.52 or more and less than 1.60 [μm]

×: 1.60 or more [μm]

As shown in Tables 5 and 6, the coloring agent having the features of the present embodiment contains quinoline yellow pigment [A1] having a specific structure, and further specific The coloring composition of the quinoline yellow pigment [A2] having a structure has an extremely high contrast value and excellent coloring power.

Among them, as in Examples 25 to 45 (colored composition (P-25 to 45)), when the coloring agent further contained a pigment, the comparative value was more favorable.

Further, in Example 3 (coloring composition (P-3)), compared with Examples 6 and 7 (coloring composition (P-6, 7)), the coloring composition containing the resin-type dispersing agent (P-6) And 7) are better in terms of comparison values.

On the other hand, as in the coloring composition of the reference example, when quinoline yellow pigment [A2] is not contained therein, the result is a decrease in the contrast value as a result of the fluorescence. Further, when quinoline yellow pigment [A1] was not contained therein, the result was good because the fluorescence was not emitted, but the coloring power was extremely poor.

[Example 46] (Photosensitive coloring composition (R-1))

The mixture of the following composition was uniformly stirred and mixed, and then filtered through a filter of 1 μm to prepare a photosensitive coloring composition (R-1).

[Examples 47 to 90, Reference Examples 9 to 16] (Photosensitive coloring composition (R-2 to 53))

The coloring composition, the acrylic resin solution, the photopolymerizable monomer, the photopolymerization initiator, the sensitizer, the organic solvent, the type of the antioxidant, and the blending amount (parts by weight) were changed as shown in Tables 7 to 9. The photosensitive coloring composition (R-2 to 53) was produced in the same manner as in the photosensitive coloring composition (R-1).

The abbreviations in Tables 7 to 9 are as follows.

Photopolymerizable monomer. Photopolymerizable monomer A: hexaacrylic acid / pentaerythritol pentaacrylate mixture ("Aronix M402" manufactured by Japan East Asia Synthesis Co., Ltd.) photopolymerization initiator. Starting agent A: 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (Ciba Japanese company manufactures "IRGACURE-379")

. Starting agent B: 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-ethanone 1-(O-ethylindenyl) (Ciba Japanese company manufactures "IRGACURE-OXE02") sensitizer. Sensitizer A: 4,4'-diethylamine diphenyl ketone ("EAB-F" manufactured by Japan Hodogaya Chemical Industry Co., Ltd.)

Antioxidants. Antioxidant A: hindered phenolic antioxidant propionic acid pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl]ester

. Antioxidant B: sulfur-based antioxidant 3,3'-di-octadecyl thiodipropionate

. Antioxidant C: Phosphorus-based antioxidant tris[2,4-di-(tri)-butylphenyl]phosphine

. Antioxidant D: hindered amine-based antioxidant bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate

. Antioxidant E: Salicylate-based antioxidant salicylic acid p-octyl phenyl ester

Organic solvents

. Anon: cyclohexanone

[Evaluation of photosensitive coloring composition]

The evaluation of the contrast value, the coloring power, and the brightness of the photosensitive coloring composition (R-1 to 53) was carried out in the following manner. The results of the test are shown in Tables 10 to 12.

(evaluation of comparison value)

The colored composition (R-1 to 53) obtained was applied on a glass substrate of 100 mm × 200 mm and 1.1 mm thick by a spin coater, followed by drying at 70 ° C for 20 minutes, and left to cool to prepare a coating film. Substrate. Thereafter, the initial contrast value (initial CR) of the obtained coated substrate was measured. In this case, the coating conditions of the spin coater were adjusted so that the film thickness measured by the surface shape measuring instrument "Dektak 8 (manufactured by Veeco)" was 1 μm, and a coating film was produced.

(assessment of tinting strength)

The obtained photosensitive coloring composition (R-1 to 32, R-34 to 53) and the green photosensitive coloring composition (RG-1) were mixed to prepare a green photosensitive coloring composition. Wherein, the blending ratio of the green photosensitive coloring composition (R-1 to 53) and the green photosensitive coloring composition (RG-1) is the same as that of the C light source when the coated substrate is formed, x=0.290, y The chromaticity of =0.600, the ratio is selected. Next, the obtained mixed coloring composition was applied by a spin coater under a C light source at y = 0.600, and then dried at 70 ° C for 20 minutes to obtain a coated substrate. Further, the coloring power was evaluated based on the measurement results of the obtained coated substrate film thickness. The film thickness of the obtained coating film was measured by a surface shape measuring instrument "Dektak 8 (manufactured by Veeco Co., Ltd.)". The results are judged based on the following criteria. The smaller the film thickness of the chromaticity of the object is, the larger the coloring power is, and it is considered to be excellent.

◎: Not up to 3.91 [μm]

○: 3.91 or more and less than 4.17 [μm]

×: 4.17 or more [μm]

The photosensitive coloring composition (R-33) obtained is photosensitive with red The color composition (RR-1) was mixed to prepare a red colored composition. In addition, the ratio of the photosensitive coloring composition (R-33) and the red photosensitive coloring composition (RR-1) is the same as that of the red light-sensitive coloring composition (RR-1) when the coated substrate is used, and the C light source is combined with x=0.640 and y=0.334. Chroma selects its scale. Thereafter, the obtained mixed coloring composition was applied by a spin coater so as to be x=0.640 under a C light source, and then dried at 70 ° C for 20 minutes to obtain a coated substrate. Further, the coloring power was evaluated based on the measurement results of the film thickness of the obtained coated film substrate. The film thickness of the obtained coating film was measured by a surface shape measuring instrument "Dektak 8 (manufactured by Veeco Co., Ltd.)". The results are judged based on the following criteria. The smaller the film thickness of the chromaticity which gives the purpose, the greater the coloring power, and it is excellent.

◎: Not up to 2.47 [μm]

○: 2.47 or more and less than 2.61 [μm]

×: 2.61 or more [μm]

(Evaluation of film brightness)

The photosensitive coloring compositions (R-1 to 32, R-34 to 53) were coated on a 100 mm × 100 mm, 1.1 mm thick glass substrate by a spin coater, followed by drying at 70 ° C for 20 minutes, after which After heating at 220 ° C for 30 minutes, it was left to cool to form a coated substrate. The brightness Y (C) of the obtained coating film was measured by a microspectrophotometer ("OSP-SP100" manufactured by Olympus Corporation, Japan). The prepared coated substrate was subjected to heat treatment at 220 ° C, and was then allowed to have a chromaticity of x = 0.290 and y = 0.600 under a C light source.

In addition, the photosensitive coloring composition (R-33) is in addition to the chromaticity of the chromaticity of x=0.640 and y=0.334. Line brightness evaluation.

As shown in Tables 10 to 12, the coloring agent having the characteristics of the present embodiment contains photosensitive coloring of quinoline yellow pigment [A1] having a specific structure and quinoline yellow pigment [A2] of another specific structure. The composition has an extremely high contrast value and excellent coloring power.

Among them, as in Examples 70 to 90 (photosensitive coloring composition (R-25 to 45)), when the pigment was further contained therein, the comparative value was better.

Further, in Example 48 (photosensitive coloring composition (R-3)), compared with Examples 51 and 52 (photosensitive coloring composition (R-6, 7)), photosensitive coloring of the resin-containing dispersing agent The composition (R-6, 7) is more excellent from the viewpoint of the comparative value.

On the other hand, when the photosensitive coloring composition of the reference example does not contain quinoline yellow pigment [A2], the result is affected by the fluorescence to lower the contrast value. Further, when quinoline yellow pigment [A1] was not contained therein, the result was good because the fluorescence was not emitted, but the coloring power was extremely poor.

Meanwhile, in terms of brightness, the photosensitive coloring composition of the present embodiment, The luminance of the photosensitive coloring composition of the reference example was higher than that of the reference example, and the result was good. Further, in terms of pigments, the brightness of the photosensitive coloring composition (R-30, 31 to 33, 36 to 45) containing the zinc anise pigment or the anthraquinone aluminum pigment is extremely high, and the result is excellent. .

[Production of color filter]

First, the production of the blue photosensitive coloring composition used in the production of the color filter was carried out. Further, a photosensitive coloring composition (R-33) was used for the red color, and a photosensitive coloring composition (R-41) was used for the green color.

(Production of blue photosensitive coloring composition (RB-1))

After the mixture of the following composition was stirred and mixed to be uniform, zirconia beads having a diameter of 0.5 mm were used, and dispersed by an Eiger mill disperser ("Mini Model M-250 MK II" manufactured by Eiger Japan Co., Ltd.) for 5 hours, and then 5.0. The sieve of μm was filtered to prepare a blue colored composition (DB-6).

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

(production of color filter)

The black matrix on the glass substrate is processed into an image, and the red photosensitive coloring composition (R-33) is applied to the substrate by a spin coater to be used under a C light source (hereinafter, also used in green and blue). The film thickness of x=0.640 and y=0.334 was applied to form a colored film. The film was further irradiated with ultraviolet rays at 300 mJ/cm ² using an ultrahigh pressure mercury lamp through a mask. Next, it was spray-imaged with an alkali developing solution composed of a 0.2% by weight aqueous solution of sodium carbonate to remove the unexposed portion, and then washed with ion-exchanged water, and the substrate was heated at 230 ° C for 20 minutes to form a red filter. Color clip. In the same manner, in the case of the green photosensitive coloring composition (R-41), y=0.600, and in the case of the blue photosensitive coloring composition (RB-1), x=0.150, y=0.060, each Coating was performed to form a green color filter segment and a blue color filter segment to obtain a color filter.

When the red photosensitive coloring composition (R-33) or the green photosensitive coloring composition (R-41) is used, a color filter of high contrast value and high brightness can be produced.

"Embodiment VIII" <Method for producing quinoline yellow pigment>

6.8 parts of 8-hydroxymethylquinoline and 9 parts of 4-ethoxyphthalic anhydride, 30 parts of benzoic acid were mixed and stirred at 200 ° C for 5 hours. After standing to cool, 50 parts of methanol was further added and stirred for 1 hour. Thereafter, the precipitated solids were collected by suction filtration. The solid was again added to 400 parts of methanol, and after stirring for 1 hour, the solid was collected by suction filtration. Thereafter, it was dried overnight in a vacuum dryer (40 ° C) to obtain 6.1 parts of a product. Its yield was 42%. The compound was then identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan, autoflex II). As a result, m/z = 333.23 (molecular weight 333.10) was identified as the target.

9.7 parts of 8-hydroxymethylquinoline and 10 parts of 4-hydroxyphthalic anhydride, 30 parts of benzoic acid, and 40 parts of methyl benzoate were mixed, and stirred at 200 ° C for 5 hours. After standing to cool, 50 parts of methanol was further added and stirred for 1 hour. Thereafter, the precipitated solids were collected by suction filtration. The solid was again added to 400 parts of methanol, and after stirring for 1 hour, the solid was collected by suction filtration. Thereafter, it was dried overnight in a vacuum dryer (40 ° C) to obtain 3.4 parts of a product. Its yield was 18%. The compound was then identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan, autoflex II). As a result, m/z = 305.15 (molecular weight: 30.07) was identified as the target.

Example 1

3.0 parts of quinophthalone yellow pigment 1 was mixed in 30 parts of N,N-dimethylacetamide, followed by mixing 0.4 parts of sodium hydroxide and 2.1 parts of 1-bromo-2-ethylhexane. And stirred at 105 ° C for 1 hour. After standing to cool, 20 parts of chloroform and 100 parts of water were further added to extract an organic layer. The organic layer was dried by adding 5 parts of magnesium sulfate, followed by filtration and concentration under reduced pressure. The concentrate thus obtained was purified by silica gel column chromatography (chloroform / ethyl acetate = 5 / 1 (volume ratio)) to obtain a product of 3.2 parts. Its yield was 81%. The compound was then identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan, autoflex II). As a result, m/z = 445.33 (molecular weight: 445.23) was identified as the target.

Example 2

3.0 parts of 8-(2-ethylhexyloxy)-5-phenyl-2-methylquinoline and 1.7 parts of 4-ethoxyphthalic anhydride, 30 parts of benzoic acid, and at 200 ° C Stir for 5 hours. After standing to cool, 100 parts of methanol was further added and stirred for 1 hour. After that, the precipitated solid is filtered by suction. set. The solid was again added to 200 parts of methanol, and after stirring for 1 hour, the solid was collected by suction filtration. Thereafter, it was dried overnight in a vacuum dryer (40 ° C) to obtain 3.4 parts of a product. Its yield is 75%. The compound was then identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan, autoflex II). As a result, m/z = 521.35 (molecular weight 521.26) was confirmed as a target.

Example 3

3.0 parts of quinophthalone yellow pigment 1 was mixed in 30 parts of N,N-dimethylacetamide, followed by mixing 0.4 parts of sodium hydroxide and 1.7 parts of 1-bromo diethyl ether at 105 ° C. Stir for 1 hour. After standing to cool, 20 parts of chloroform and 100 parts of water were further added to extract an organic layer. The organic layer was dried by adding 5 parts of magnesium sulfate, followed by filtration and concentration under reduced pressure. The concentrate thus obtained was purified by a silica gel column chromatography (chloroform / ethyl acetate = 5 / 1 (volume ratio)) to obtain a product of 3.0 parts. Its yield was 83%. The compound was then identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan, autoflex II). As a result, m/z = 405.32 (molecular weight: 405.16) was identified as the target.

Example 4

3.0 parts of quinophthalone yellow pigment 2 was mixed in 30 parts of N,N-dimethylacetamide, followed by mixing 0.9 parts of sodium hydroxide and 4.2 parts of 1-bromo-2-ethylhexane. And stirred at 105 ° C for 1 hour. After standing to cool, 20 parts of chloroform and 100 parts of water were further added to extract an organic layer. The organic layer was dried by adding 5 parts of magnesium sulfate, followed by filtration and concentration under reduced pressure. The concentrate thus obtained was purified by silica gel column chromatography (chloroform / ethyl acetate = 7 / 1 (volume ratio)) to obtain a product of 4.1 parts. Its yield was 78%. The compound was then identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan, autoflex II). As a result, it was confirmed that m/z = 529.45 (molecular weight: 529.32).

Example 5

3.0 parts of 8-(2-ethylhexyloxy)-2-methylquinoline and 2.7 parts of 4-cyclohexyloxyphthalic anhydride, 30 parts of benzoic acid were mixed, and stirred at 200 ° C for 5 hours. After standing to cool, 100 parts of methanol was further added and stirred for 1 hour. Thereafter, the precipitated solids were collected by suction filtration. The solid was again added to 200 parts of methanol, and after stirring for 1 hour, The solids were collected by suction filtration. Thereafter, it was dried overnight in a vacuum dryer (40 ° C) to obtain 4.6 parts of a product. Its yield was 83%. The compound was then identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan, autoflex II). As a result, m/z = 499.29 (molecular weight: 499.27) was identified as the target.

Example 6

3.0 parts of 8-(2-ethylhexyloxy)-2-methylquinoline and 2.7 parts of 4-phenoxyphthalic anhydride and 30 parts of benzoic acid were mixed and stirred at 200 ° C for 5 hours. After standing to cool, 100 parts of methanol was further added and stirred for 1 hour. Thereafter, the precipitated solids were collected by suction filtration. The solid was again added to 200 parts of methanol, and after stirring for 1 hour, the solid was collected by suction filtration. Thereafter, it was dried overnight in a vacuum dryer (40 ° C) to obtain 4.4 parts of a product. Its yield was 81%. The compound was then identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan, autoflex II). As a result, m/z = 491.31 (molecular weight 493.23) was determined as the target.

Example 7

3.0 parts of quinophthalone yellow pigment 2 was mixed in 30 parts of N,N-dimethylacetamide, followed by mixing 0.9 parts of sodium hydroxide and 5.3 parts of 1-bromo-4-trifluorotoluene. It was stirred at 105 ° C for 1 hour. After standing to cool, 20 parts of chloroform and 100 parts of water were further added to extract an organic layer. The organic layer was dried by adding 5 parts of magnesium sulfate, followed by filtration and concentration under reduced pressure. The concentrate thus obtained was purified by a silica gel column chromatography (chloroform / ethyl acetate = 5 / 1 (volume ratio)) to obtain a product of 4.5 parts. Its yield was 78%. The compound was then identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan, autoflex II). As a result, m/z = 593.58 (molecular weight: 593.11) was identified as the target.

Example 8

3.0 parts of 8-(2-ethylhexyloxy)-2-methylquinoline and 2.6 parts of 4-(2-ethoxyethoxy)phthalic anhydride, 30 parts of benzoic acid, and mixed at 200 ° C Stir under 5 hours. After standing to cool, 100 parts of methanol was further added and stirred for 1 hour. After that, the precipitated solid is filtered by suction. set. The solid was again added to 200 parts of methanol, and after stirring for 1 hour, the solid was collected by suction filtration. Thereafter, it was dried overnight in a vacuum dryer (40 ° C) to obtain 4.3 parts of a product. Its yield was 79%. The compound was then identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan, autoflex II). As a result, m/z = 489.46 (molecular weight: 489.25) was identified as the intended product.

Example 9

3.0 parts of 8-(2-ethylhexyloxy)-2-methylquinoline and 3.1 parts of 4-(2-(1,3-) Alkan-2-yl)ethoxy)phthalic anhydride, 30 parts of benzoic acid were mixed and stirred at 200 ° C for 5 hours. After standing to cool, 100 parts of methanol was further added and stirred for 1 hour. Thereafter, the precipitated solids were collected by suction filtration. The solid was again added to 200 parts of methanol, and after stirring for 1 hour, the solid was collected by suction filtration. Thereafter, it was dried overnight in a vacuum dryer (40 ° C) to obtain 4.3 parts of a product. Its yield was 74%. The compound was then identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan, autoflex II). As a result, m/z = 531.56 (molecular weight 531.26) was identified as the target.

Example 10

3.0 parts of 5-(2-methylquinolin-8-yloxy)decanoic acid-2-ethylhexyl ester and 2.2 parts of 4-(1,3-di-oxy-1,3-dihydrogen) Methyl isobenzofuran-5-yloxy)butanoate, 30 parts of benzoic acid were mixed, and stirred at 200 ° C for 5 hours. After standing to cool, 100 parts of methanol was further added and stirred for 1 hour. Thereafter, the precipitated solids were collected by suction filtration. The solid was again added to 200 parts of methanol, and after stirring for 1 hour, the solid was collected by suction filtration. Thereafter, it was dried overnight in a vacuum dryer (40 ° C) to obtain 3.6 parts of a product. The yield was 72%. The compound was then identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan, autoflex II). As a result, m/z = 603.62 (molecular weight 603.28) was determined as the target.

Example 11

3.0 parts of quinophthalone yellow pigment 2 was mixed in 30 parts of N,N-dimethylacetamide, followed by mixing 0.9 parts of sodium hydroxide and 6.6 parts of 4-bromobutyric acid-2-ethylhexyl The ester was stirred at 105 ° C for 1 hour. After standing to cool, 20 parts of chloroform and 100 parts of water were further added to extract an organic layer. The organic layer was dried by adding 5 parts of magnesium sulfate, followed by filtration and concentration under reduced pressure. The concentrate thus obtained was purified by silica gel column chromatography (chloroform / ethyl acetate = 10/1 (volume ratio)) to obtain 4.9 parts. Its yield was 71%. The compound was then identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan, autoflex II). As a result, m/z = 701.67 (molecular weight: 701.39) was identified as the target.

Example 12

3.0 parts of quinophthalone yellow pigment 2 was mixed in 30 parts of N,N-dimethylacetamide, and then 0.9 parts of sodium hydroxide and 6.9 parts of 5-bromopentanoic acid-2-ethylhexyl were mixed. The ester was stirred at 105 ° C for 1 hour. After standing to cool, 20 parts of chloroform and 100 parts of water were further added to extract an organic layer. The organic layer was dried by adding 5 parts of magnesium sulfate, followed by filtration and concentration under reduced pressure. The concentrate thus obtained was purified by silica gel column chromatography (chloroform / ethyl acetate = 10/1 (volume ratio)) to obtain 5.0 parts of a product. Its yield is 70%. The compound was then identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan, autoflex II). As a result, m/z = 729.83 (molecular weight: 729.42) was identified as the target.

Example 13

3.0 parts of 5-(2-methylquinolin-8-yloxy)pentanoic acid 2-ethylhexyl ester and 3.0 parts of 4-(1,3-di-oxy-1,3-dihydrogen) Isobenzofuran-5-yloxy)butyric acid-2-ethylhexyl ester, 30 parts of benzoic acid were mixed, and stirred at 200 ° C for 5 hours. After standing to cool, 100 parts of methanol was further added and stirred for 1 hour. Thereafter, the precipitated solids were collected by suction filtration. The solid was again added to 200 parts of methanol, and after stirring for 1 hour, the solid was collected by suction filtration. Thereafter, it was dried overnight in a vacuum dryer (40 ° C) to obtain 3.5 parts of a product. Its yield is 65%. The compound was then identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan, autoflex II). As a result, m/z = 715.90 (molecular weight: 71.41) was identified as the target.

Example 14

First, 3.0 parts of quinophthalone yellow pigment 2 was mixed in 30 parts of N,N-dimethylacetamide, and then 0.9 parts of sodium hydroxide and 8.0 parts of 5-bromopentanoic acid-2-(2) were mixed. -ethylhexyloxy)ethyl ester and stirred at 105 ° C for 1 hour. After standing to cool, 20 parts of chloroform and 100 parts of water were further added to extract an organic layer. The organic layer was dried by adding 5 parts of magnesium sulfate, followed by filtration and concentration under reduced pressure. The concentrate thus obtained was purified by silica gel column chromatography (chloroform / ethyl acetate = 10/1 (volume ratio)) to obtain 5.9 parts of a product. Its yield was 73%. The compound was then identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan, autoflex II). As a result, it was confirmed that m/z = 817.88 (molecular weight 817.48).

Example 15

First, 3.0 parts of quinophthalone yellow pigment 2 was mixed in 30 parts of N,N-dimethylacetamide, and then 0.9 parts of sodium hydroxide and 9.3 parts of 5-bromopentanoic acid-2-(3) were mixed. -(2-Ethylhexyloxy)propoxy)ethyl ester and stirred at 105 ° C for 1 hour. After standing to cool, 20 parts of chloroform and 100 parts of water were further added to extract an organic layer. The organic layer was further added with 5 portions of magnesium sulfate, dried, filtered and evaporated. The concentrate thus obtained was purified by silica gel column chromatography (chloroform / ethyl acetate = 10/1 (volume ratio)) to yield 6.4 part of product. Its yield was 71%. The compound was then identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan, autoflex II). As a result, m/z = 919.91 (molecular weight: 919.54) was identified as the target.

Example 16

First, 3.0 parts of quinophthalone yellow pigment 1 is mixed in 30 parts of N,N-dimethylacetamide, and then 0.5 parts of sodium hydroxide and 4.5 parts of 7-oxabicyclo[4.1.0 are mixed. Heptan-3-carboxylic acid-2-ethylhexyl ester and stirred at 105 ° C for 1 hour. After standing to cool, 20 parts of chloroform and 100 parts of water were further added to extract an organic layer. The organic layer was dried by adding 5 parts of magnesium sulfate, followed by filtration and concentration under reduced pressure. The concentrate thus obtained was purified by silica gel column chromatography (chloroform / ethyl acetate = 10/1 (volume ratio)) to obtain 3.9 parts of a product. Its yield is 75%. The compound was then identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan, autoflex II). As a result, m/z = 587.51 (molecular weight 587.29) was determined as the target.

Example 17

3.0 parts of 4-hydroxy-3-(2-methylquinolin-8-yloxy)cyclohexanecarboxylic acid-2-ethylhexyl ester and 2.1 parts of 5-(2-phenoxyethoxy) The phthalic anhydride and 30 parts of benzoic acid were mixed and stirred at 200 ° C for 5 hours. Place it cold Thereafter, 100 parts of methanol was further added and stirred for 1 hour. Thereafter, the precipitated solids were collected by suction filtration. The solid was again added to 200 parts of methanol, and after stirring for 1 hour, the solid was collected by suction filtration. Thereafter, it was dried overnight in a vacuum dryer (40 ° C) to obtain 3.6 parts of a product. Its yield was 73%. The compound was then identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan, autoflex II). As a result, m/z = 679.76 (molecular weight 679.31) was identified as the target.

Example 18

3.0 parts of bis(2-ethylhexyl) 4-hydroxy-5-(2-methylquinolin-8-yloxy)cyclohexane-1,2-dicarboxylate and 1.5 parts of 5-(( 2-Phenoxyethoxy)phthalic anhydride, 30 parts of benzoic acid were mixed, and stirred at 200 ° C for 5 hours. After standing to cool, 100 parts of methanol was further added and stirred for 1 hour. Thereafter, the precipitated solids were collected by suction filtration. The solid was again added to 200 parts of methanol, and after stirring for 1 hour, the solid was collected by suction filtration. Thereafter, it was dried overnight in a vacuum dryer (40 ° C) to obtain 3.4 parts of a product. Its yield was 78%. Then with a mass analyzer (TOF-MS: manufactured by Bruker Daltonics Japan, autoflex II) Identification of the compound was carried out. As a result, m/z = 835.88 (molecular weight 834.43) was identified as the target.

Example 19

3.0 parts of bis(2-ethylhexyl) 4-hydroxy-5-(2-methylquinolin-8-yloxy)cyclohexane-1,2-dicarboxylate and 1.4 parts of 5-benzene Ethoxy phthalic anhydride, 30 parts of benzoic acid were mixed, and stirred at 200 ° C for 5 hours. After standing to cool, 100 parts of methanol was further added and stirred for 1 hour. Thereafter, the precipitated solids were collected by suction filtration. The solid was again added to 200 parts of methanol, and after stirring for 1 hour, the solid was collected by suction filtration. Thereafter, it was dried overnight in a vacuum dryer (40 ° C) to obtain 3.2 parts of a product. Its yield is 75%. The compound was then identified by a mass spectrometer (TOF-MS: manufactured by Bruker Daltonics Japan, autoflex II). As a result, m/z = 819.72 (molecular weight: 819.43) was identified as the target.

Reference example 1

The synthesis is carried out according to the synthesis method of the pigment (IV) in JP-A-6-009891.

Reference example 2

Among them, Disperse Yellow 54 is used.

<Modulation of Acrylic Resin Solution>

70.0 parts of cyclohexanone was placed in a reaction vessel equipped with a thermometer, a condenser, a nitrogen introduction tube, a dropping tube, and a stirring device in a separable 4-necked flask, and the temperature was raised to 80 ° C, and the reaction vessel was replaced. After nitrogen gas, 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, and 7.4 parts of p-isopropylidene phenol were epoxy-coated by a dropping tube. A mixture of ethane-modified acrylate ("Aronix M110" manufactured by Japan East Asia Synthetic Co., Ltd.) and 0.4 parts of 2,2'-azobisisobutyronitrile was dropped over 2 hours. After the end of the dropwise addition, the reaction was continued for another 3 hours to obtain a flat weight. A solution of an acrylic resin having a molecular weight of 26,000. After cooling to room temperature, about 2 g of the resin solution was sampled and dried at 180 ° C for 20 minutes to determine the nonvolatile matter, and the amount of the nonvolatile matter was 20% by mass in the previously synthesized resin solution. Into an acrylic resin solution.

The polymerization average molecular weight (Mw) of the acrylic resin is a TSK gel column (manufactured by Tosoh Corporation, Japan), and GPC (manufactured by Tosoh Corporation of Japan, HLC-8120GPC) of the apparatus RI detector, and the solvent is used to use THF. The weight average molecular weight (Mw) of the converted polystyrene at the time of measurement.

<Method for producing pigment> (production of blue pigment 1)

First, 200 parts of phthalocyanine blue pigment CI Pigment Blue 15:6 ("LIONOL BLUE ES" manufactured by Toyo Ink Manufacturing Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of ethylene glycol are added to stainless steel. A 1 gallon kneader (manufactured by Inoue, Ltd., Japan) was mixed and mixed at 80 ° C for 6 hours. Next, the mixture was put into 8 liters of warm water, heated to 80 ° C and stirred for 2 hours to make it into a slurry, repeated filtration, washing with water to remove sodium chloride and diethylene glycol, and then 85 After drying overnight at ° C, 190 parts of Blue Pigment 1 were obtained. The pigment obtained had an average primary particle diameter of 79 nm.

(Production of Purple Pigment 1)

First 200 copies Purple pigment CI Pigment Violet No. 23 ("LIONOGEN VIOLET RL" manufactured by Toyo Ink Manufacturing Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were added to a 1-gallon kneader made of stainless steel (Japan Inoue Co., Ltd.) Manufactured and mixed at 80 ° C for 6 hours. Next, the mixture was put into 8 liters of warm water, heated to 80 ° C and stirred for 2 hours to make it into a slurry, repeated filtration, washing with water to remove sodium chloride and diethylene glycol, and then 85 After drying overnight at ° C, 190 parts of purple pigment 1 were obtained. The pigment obtained had an average primary particle diameter of 28 nm.

(Production of Green Pigment 1)

A commercially available product of anthraquinone-based green pigment C.I. Pigment Green No. 58 ("FASTGEN GREEN A110" manufactured by DIC Corporation) was used as it is. The green pigment 1 had an average primary particle diameter of 22 nm.

(production of blue pigment 2)

First, 225 parts of sebaconitrile and 78 parts of anhydrous aluminum chloride were mixed and stirred in 1250 parts of n-pentanol in a reaction vessel. Thereafter, 266 parts of DBU (1,8-Diazabicyclo [5.4.0] undec-7-ene) was added thereto and heated, and refluxed at 136 ° C for 5 hours. Thereafter, the reaction solution was cooled to 30 ° C under stirring, and added to a mixed solvent of 5,000 parts of methanol and 10,000 parts of water under stirring to obtain a blue slurry. After the slurry was further filtered, it was washed with a mixed solvent of 2000 parts of methanol and 4000 parts of water, and dried to obtain 135 parts of chloroaluminum indigo (AlPc-Cl). Thereafter, 100 parts of chloroaluminum indigo was gradually added to the reaction vessel in 1200 parts of concentrated sulfuric acid at room temperature. After further stirring at 40 ° C for 3 hours, 24,000 parts of 3 ° C cold water was poured into the sulfuric acid solution. The blue precipitate was filtered, washed with water and dried to obtain 92 parts of hydroxyaluminum (AlPc-OH).

Then, 2000 parts of N,N-dimethylformamidine was added to the reaction vessel. Amine, 100 parts of AlPc-OH, 53.9 parts of diphenyl phosphate. After reacting at 85 ° C for 3 hours, the solution was further injected in 12,000 parts of water. The reaction product was further filtered, washed with 24,000 parts of water, and dried overnight at 60 ° C under reduced pressure to obtain 123 parts of aluminum phthalocyanine (AlPc-DPP). Then, 50 parts of the AlPc-DPP pigment, 150 parts of sodium chloride, and 25 parts of diethylene glycol were placed in a 1-gallon kneader made by stainless steel (manufactured by Inoue, Japan), and mixed at 120 ° C. hour. Next, the mixture is put into 5 liters of warm water, heated to 80 ° C and stirred for 1 hour to make it into a slurry, repeated filtration, washing with water to remove sodium chloride and diethylene glycol, and then 85 Drying overnight at ° C gave a blue pigment 2. The pigment obtained had an average primary particle diameter of 29 nm.

(Production of yellow pigment 1)

270 parts of quinoline yellow pigment CI Pigment Yellow No. 138 (trade name Paliotol Yellow K0961HD manufactured by BASF Corporation), 1350 parts of sodium chloride, and 500 parts of diethylene glycol were added to a 1-gallon kneader made of stainless steel ( In Japan, manufactured by Inoue, Ltd., and mixed at 120 ° C for 6 hours. Next, the mixture was put into 8 liters of warm water, heated to 80 ° C and stirred for 2 hours to make it into a slurry, repeated filtration, washing with water to remove sodium chloride and diethylene glycol, and then 85 Drying overnight at ° C gave 250 parts of yellow pigment 3. The pigment obtained had an average primary particle diameter of 36 nm.

(Production of yellow pigment 2)

200 parts of nickel complex yellow pigment C.I. Pigment Yellow No. 150 ("E-4GN" manufactured by Lanxess Co., Ltd.), 1400 parts of sodium chloride, and 360 Diethylene glycol was added to a 1-gallon kneader made of stainless steel (manufactured by Inoue, Ltd.), and mixed at 120 ° C for 6 hours. Next, the mixture was put into 8 liters of warm water, heated to 80 ° C and stirred for 2 hours to make it into a slurry, repeated filtration, washing with water to remove sodium chloride and diethylene glycol, and then 85 After drying overnight at ° C, 190 parts of yellow pigment 2 were obtained. The pigment obtained had an average primary particle diameter of 67 nm.

(Production of yellow pigment 3)

500 parts of isoporphyrin yellow pigment CI Pigment Yellow No. 139 ("IRGAPHOR YELLOW-2R-CF" manufactured by Ciba Japan Co., Ltd.), 500 parts of sodium chloride, and 250 parts of diethylene glycol were added to stainless steel. The mixture was mixed in a 1 gallon kneader (manufactured by Inoue, Japan) at 120 ° C for 8 hours. Next, the mixture is put into 5 liters of warm water, heated to 80 ° C and stirred for 1 hour to make it into a slurry, repeated filtration, washing with water to remove sodium chloride and diethylene glycol, and then 85 Drying overnight at ° C gave 490 parts of yellow pigment 1. The pigment obtained had an average primary particle diameter of 92 nm.

(production of red pigment 1)

200 parts of bismuth red pigment CI Pigment Red No. 177 ("Cromophtal Red A2B" manufactured by Ciba Japan Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were added to a 1-gallon kneader made of stainless steel ( In Japan, manufactured by Inoue, Ltd., and mixed at 80 ° C for 6 hours. Next, the mixture was put into 8 liters of warm water, heated to 80 ° C and stirred for 2 hours to make it into a slurry, repeated filtration, washing with water to remove sodium chloride and diethylene glycol, and then 85 Dry at °C for one night and get 190 Red pigment 1. The pigment obtained had an average primary particle diameter of 54 nm.

(production of coloring composition Q-1)

After the mixture was stirred and mixed to be uniform, zirconia beads having a diameter of 0.5 mm were used, and dispersed by an Eiger mill disperser ("Mini Model M-250 MK II" manufactured by Eiger Japan Co., Ltd.) for 5 hours, and then 5.0 μm. The filter was filtered to prepare a colored composition Q-1.

(Production of coloring composition Q-2 to 23)

In the following, except that quinophthalone yellow pigment 1 was substituted with quinophthalone yellow pigment shown in Table 1, the coloring compositions Q-2 to 23 were produced in the same manner as in the production of the coloring composition Q-1.

(production of coloring composition DP-1)

After the mixture was stirred and mixed to be uniform, zirconia beads having a diameter of 0.5 mm were used, and dispersed by an Eiger mill disperser ("Mini Model M-250 MK II" manufactured by Eiger Japan Co., Ltd.) for 5 hours, and then 5.0 μm. The filter was filtered to prepare a colored composition (DP-1).

(Production of coloring compositions DP-2 to 8)

In the following, except that the blue pigment 1 was replaced with the pigment shown in Table 2, the colored compositions DP-2 to 8 were produced in the same manner as in the production of the colored composition DP-1.

[Examples 20 to 38, Reference Examples 3 to 9] <Test of foreign matter of coating film of colored compositions Q-1 to 23 and DP-5 to 7>

This evaluation was performed by preparing a test substrate and calculating the number of particles. The colored composition was applied to the transparent substrate so that the dried coating film became about 2.0 μm, and then heated in an oven at 230 ° C for 20 minutes to obtain a test substrate. Evaluation in Japan The metal microscope "BX60" manufactured by Olympus was used for surface observation. The number of particles observable in any five visible areas transmitted is calculated at a magnification of 500 times. Among the evaluation results described below, ◎ and ○ are good, and Δ is a foreign matter, but there is no problem in use, and × is uneven coating (plaque) due to foreign matter.

◎: Less than 5

○: 5 or more and less than 20

△: 20 or more and less than 100

×: 100 or more

The results are shown below in Table 3.

<Spectrum test of coloring compositions Q-1 to 23, DP-5 to 7>

A coating film was formed on the transparent substrate so that the transmittance at a wavelength of 450 nm became 5%, and the values of the transmittance at 500 nm and 550 nm at this time were measured. The higher the transmittance at 500 nm and 550 nm, the better the brightness. In the following evaluation results, the transmittance of 500 nm and 550 nm in the normalization of quinoline yellow pigment and yellow pigment, ○ is 99% or more, Δ is 97 or more and less than 99%, and × is not reached. 97%. When it is 99% or more, its brightness becomes high, so it is preferable. The results are shown below in Table 3. Further, the light splitting of the coating films of Example 1 and Reference Examples 1 and 4 is as shown in Figs. 1 to 3.

In Examples 20 to 38, as a result, the coating film was small and good. Further, Examples 20 to 38 were excellent in the results of the spectral characteristics, and showed a spectral shape having a high luminance. The transmittances of Reference Examples 5 to 8 at 550 nm were comparatively good, but the transmittance at 500 nm was low, and it was shown that the light-emitting shape could not be improved in brightness.

Reference examples 3 to 7 in which a dye containing a hydroxyl group in a quinoline ring was used, and a spectroscopic shape of Examples 20 to 38 in which a dye having no hydroxyl group was used was used. In the form of (for example, the light distribution of the coating film of Example 20 in FIGS. 1 to 3 and the coating film of Reference Examples 3 and 6), the light transmittance at 500 nm is low, so that the coloring matter containing a hydroxyl group in the quinoline ring cannot improve the brightness. pigment.

<Method for Producing Blue Photoresist Material>

The mixture described below was uniformly stirred and mixed, and then filtered through a 1.0 μm filter to obtain a blue photoresist material B-1.

[Example 39] <Adjustment of Photoresist Material G-1>

The mixture was uniformly stirred and mixed, and then filtered through a 1.0 μm filter to obtain a green photoresist (G-1).

[Examples 40 to 82, Reference Examples 10 to 18] <Adjustment of photoresist materials G-2 to 45, R-1 to 4, and Y-1 to 4>

In the following, the photoresist materials G-2 to 45, R-1 to 4 were obtained in the same manner as in the photoresist material G-1 except that the type and amount of the coloring composition were changed to those shown in Tables 5 and 6. , Y-1 to 4.

<Evaluation of photoresist materials>

The color properties (Y: brightness), coating film foreign matter, heat resistance, and light resistance of the coating films of the obtained photoresist materials G-1 to 45, R-1 to 4, and Y-1 to 4 are each below The method described is carried out. The test results are shown in Table 6.

<Color characteristics (Y: brightness)>

Under the C light source on the glass substrate, the photoresist materials G-1 to 45 were coated with a film thickness of x=0.264 and y=0.600, and the substrate was heated at 230 ° C for 20 minutes. At the same time, the photoresist materials R-1 to 4 were coated with a film thickness of x=0.340 and y=0.640, and the substrate was heated at 230 ° C for 20 minutes. At the same time, the photoresist materials Y-1 to 4 were coated with a photoresist having a film thickness of x=0.440 and y=0.506, and the substrate was heated at 230 ° C for 20 minutes. Thereafter, the brightness (Y) of the obtained substrate was measured by a microspectrophotometer ("OSP-SP200" manufactured by Olympus Corporation, Japan).

The results are shown below in Table 6.

<Coating film foreign matter test>

The dried coating film was applied to a transparent substrate to a thickness of about 2.5 μm to apply a photoresist, and after full ultraviolet exposure, it was further heated at 230 ° C for 20 minutes in an oven, and after standing and cooled, an evaluation substrate was obtained. The surface was observed by a metal microscope "BX60" manufactured by Olympus Corporation of Japan. The number of particles observable in any five visible areas transmitted is calculated at a magnification of 500 times. Among the evaluation results described below, ◎ and ○ are good, and Δ is a foreign matter, but there is no problem in use, and × is uneven coating due to foreign matter.

◎: Less than 5

○: 5 or more and less than 20

△: 20 or more and less than 100

×: 100 or more

The results are shown below in Table 6.

<Coating film heat resistance test>

The photoresist is coated on the transparent substrate so as to form a dry coating film of about 2.5 μm, and then exposed to ultraviolet light by a photomask having a predetermined image, and then sprayed with an alkali developing solution to remove the unexposed portion thereof by a sprayer. A predetermined image is formed. Thereafter, it was further heated in an oven at 230 ° C for 20 minutes, and after standing and cooled, the obtained coating film was subjected to a chromaticity 1 under a C light source (L*(1), a*(1), b*(1)). It was measured by a microspectrophotometer ("OSP-SP200" manufactured by Olympus Corporation, Japan). Thereafter, the heat resistance test was carried out by heating at 230 ° C for 1 hour in an oven, and then measuring the chromaticity 2 (L*(2), a*(2), b*(2)) under the C light source. Then, using the measured color difference, the following formula is used, The color difference ΔEab* was determined, and the heat resistance of the coating film was evaluated in the following four stages. Among them, when the evaluation is Δ or more, it is a level which is practically no problem.

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

◎: △Eab* is less than 1.5

○: △Eab* is 1.5 or more and less than 3.0

△: △Eab* is above 3.0 and not up to 5.0

×: △Eab* is 5.0 or more

The results are shown below in Table 6.

<Coating film light resistance test>

The test substrate was produced in the same order as the film heat resistance test, and the chromaticity 1 (L*(1), a*(1), b*(1)) under the C light source was a microscopic spectrophotometer (Japan). Olympus manufactures "OSP-SP200"). Thereafter, the substrate was placed in a light resistance tester ("SUNTESTCPS+" manufactured by TOYOSEIKI, Japan) and placed for 500 hours. After the substrate was taken out, the chromaticity 2 (L*(2), a*(2), b*(2)) under the C light source was measured, and the color difference ΔEab was calculated in the same manner as the heat resistance test of the coating film. * The solvent resistance of the coating film was evaluated on the same basis as the coating film heat resistance test. Among them, when the evaluation is Δ or more, it is a level which is practically no problem.

The results are shown below in Table 6.

<Coating film solvent resistance test>

The test substrate was produced in the same order as the film heat resistance test, and the chromaticity 1 (L*(1), a*(1), b*(1)) under the C light source was a microscopic spectrophotometer (Japan). Olympus manufactures "OSP-SP200"). Thereafter, the substrate was immersed in N-methylpyrrolidone for 30 minutes. Take out the substrate Then, the chromaticity 2 (L*(2), a*(2), b*(2)) under the C light source is measured, and the color difference ΔEab* is calculated in the same manner as the heat resistance test of the coating film, and then The solvent resistance of the coating film was evaluated on the same basis as the coating film heat resistance test. Among them, when the evaluation is Δ or more, it is a level which is practically no problem.

The results are shown below in Table 6.

The results show the brightness (Y), coating foreign matter, heat resistance of the photoresist materials (G-1 to 19, G-25 to 43, R-1 to 3, Y-1 to 3) of Examples 39 to 82. It is good in light resistance and solvent resistance.

In contrast, the photoresist materials (G-20 to G-24, G-44, 45, R-4, Y-4) of Reference Examples 10 to 16, and Examples 39 to 82 (G-1 to 19) The result of comparison of G-25 to 43, R-1 to 3, and Y-1 to 3) has a low luminance (Y).

[Example 83] <Color filter (CF-1)>

The black matrix on the glass substrate is processed into an image, and the red photoresist material (R-1) is formed by a spin coater on the substrate to have a film thickness of x=0.640 and y=0.340 under the C light source. Coating to form a colored film. The film was irradiated with ultraviolet rays at 300 mJ/cm ² using an ultrahigh pressure mercury lamp through a mask. Next, the alkali developing solution composed of a 0.2% by weight aqueous sodium carbonate solution was spray-imaged to remove the unexposed portion, and then washed with ion-exchanged water, and the substrate was heated at 230 ° C for 20 minutes to form a substrate. Red color filter fragment. In the same manner, each of the green photoresist materials (G-15) was formed to have a film thickness of x=0.264 and y=0.600, and the blue photoresist material (B-1) was formed to be x=0.150. A film thickness of y = 0.060 was applied to form a green color filter segment and a blue color filter segment to obtain a color filter CF-1).

<Production of Liquid Crystal Display Device>

A transparent ITO electrode layer was formed on the obtained RGB color filter, and a polyimide phase alignment layer was formed thereon. A three-wavelength CCFL light source of a polarizing plate was combined on the other surface of the glass substrate to prepare a color display device. On the other hand, a TFT array and a pixel electrode are formed on one surface of the other (second) glass substrate, and a polarizing plate can be formed on the other surface. Then, the two glass substrates prepared in this way are arranged such that the electrode layers are disposed face to face, and the positions are adjusted by the spacer beads to keep the two substrates at a fixed interval, and then sealed with a sealant to remain in the liquid crystal composition. The object injection opening. After the liquid crystal composition is injected from the opening, the opening is sealed. The liquid crystal display device produced in this manner was combined with a three-wavelength CCFL light source of the backlight unit to form a color display device.

[Examples 83 to 87, Reference Examples 19, 20] (Color filter (CF-2 to 7))

Hereinafter, the filtration of Examples 83 to 87 and Reference Examples 19 and 20 was carried out in the same manner as in the production of the color filter (CF-1) by using a combination of a photoresist material as shown in Table 8 and a 3-wavelength CCFL light source. Color devices (CF-2 to 7) and color display devices.

Then, on the obtained color display device, the light source is illuminated to display a color image, and the brightness (Y) of each color filter segment portion is further microscopically A photometer ("OSP-SP200" manufactured by Olympus Corporation, Japan) was measured. The results are shown in Table 8.

When the examples 84 and 85 were compared with the reference example 19, the color filter formed of the quinophthalone yellow pigment of the present embodiment was compared with at least one color filter segment when compared with the color filter segment using the previous pigment ( In the green or red color, the color filter (CF-2, 3) formed of the quinophthalone yellow pigment of the present embodiment can be improved in brightness. The result is an increase in the brightness of the white display and an improvement in the performance of the color filter.

The green and red of Example 83 simultaneously contain the quinoline yellow of the present embodiment. The color filter (CF-1) formed by the element can be determined to further increase the brightness thereof, and as a result, the brightness of the white display can be increased.

Further, when Comparative Example 87 and Reference Example 20 were compared, the color filter formed of the quinophthalone yellow pigment of the present embodiment was compared with the color filter segment containing the pigment used previously, at least in one color filter segment ( In the yellow color, the color filter (CF-6) formed by the quinoline yellow pigment of the present embodiment can be used to increase the brightness thereof, and as a result, it is possible to determine the brightness of the white display and improve the performance of the color filter.

When the green, red, and yellow colors of the embodiment 86 are simultaneously contained in the color filter for a color filter of the present embodiment (CF-5), it is confirmed that the brightness is further increased, and as a result, the brightness of the white display can be increased.

As a result of the above, it is understood that the quinophthalone yellow pigment of the present embodiment and the coloring composition thereof can be used to increase the brightness of the color filter, and it is suitable for use without any problem in other physical properties.

Fig. 1 is a view showing the spectrum of the coating film in Example 5 of Embodiment V.

Fig. 2 is a view showing the spectrum of the coating film in Reference Example 1 of Embodiment V.

Fig. 3 is a spectroscopy of a coating film of Reference Example 3 of Embodiment V.

Fig. 4 is a view showing the spectrum of the coating film in Example 1 of Embodiment VIII.

Fig. 5 is a view showing the spectrum of the coating film in Reference Example 1 of Embodiment VIII.

Fig. 6 is a view showing the spectrum of the coating film of Reference Example 4 of Embodiment VIII.

Since the picture in this case is experimental data, it is not a representative figure of this case. Therefore, there is no designated representative map in this case.

Claims (10)

A coloring composition for a color filter, comprising: a coloring agent, a binder resin, and a solvent, wherein the coloring agent contains a coloring agent represented by the formula (1B), In the formula (1B), R ²⁹ to R ⁴³ each independently represent a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and an aryl group which may have a substituent , -SO ₃ H, -COOH, and a monovalent to trivalent metal salt of the acid group, an alkanolammonium salt, a sulfhydryl methyl group which may have a substituent, or an amine sulfonyl group which may have a substituent . The coloring composition for color filters according to claim 1, wherein the coloring agent further contains a coloring agent selected from the group consisting of the general formulae (8A) and (8B). Wherein, in the 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, and a substituent which may have a substituent a cyclic group, an alkoxy group which may have a substituent, 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 sulfhydryl methyl group which may have a substituent, or an amine sulfonyl 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, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent Or an aryloxy group which may have a substituent, and R may be bonded to 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, m ₁ + n ₁ , m ₂ + n ₂ , m ₃ + n ₃ , m ₄ + n ₄ each represent 0 to 4, which may be the same or different; Wherein, in the formula (8B), X ₅ to X ₁₂ 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, and a substituent which may have a substituent a cyclic group, an alkoxy group which may have a substituent, 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 sulfhydryl methyl group which may have a substituent, or an amine sulfonyl 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 -OP(=O)R ₁₀ -O-; R ₆ to R ₁₀ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, may be substituted An aryl group, an alkoxy group which may have a substituent, or an aryloxy group which may have a substituent; m ₅ to m ₁₂ , n ₅ to n ₁₂ each independently represent an integer of 0 to 4, m ₅ + n ₅ m ₆ + n ₆ , m ₇ + n ₇ , m ₈ + n ₈ , m ₉ + n ₉ , m ₁₀ + n ₁₀ , m ₁₁ + n ₁₁ , m ₁₂ + n ₁₂ each represent 0 to 4, which may be Same or different. The coloring composition for color filters according to claim 1, wherein the coloring agent further contains a dispersing agent. The coloring composition for a color filter according to claim 3, wherein the dispersing agent is an isocyanate of a vinyl polymer (A) having a hydroxyl group and a diisocyanate (B) having a hydroxyl group at a terminal end portion thereof. The isocyanate group of the urethane prepolymer (E) having an isocyanate group at both ends thereof, and the pigment dispersion obtained by reacting at least one of the amine compounds containing at least the polyamine (C) and/or the secondary amine group And the ethylene polymer (A) comprising an ethylenically unsaturated monomer having at least one of an ethylene oxide chain or a propylene oxide chain in the copolymer composition (a1) ). The coloring composition for color filters according to claim 1, wherein the coloring agent further contains a coloring agent represented by the formula (6). Wherein, in the 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 -OR ₇ ; and R ₇ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group; however, R ₁ to R _{6 are} not all hydrogen atoms. The coloring composition for color filters according to claim 1, wherein the coloring agent further contains a yellow coloring agent. The coloring composition for color filters according to claim 6, wherein the yellow coloring agent is: CI Pigment Yellow No. 138, CI Pigment Yellow No. 139, CI Pigment Yellow No. 150, and CI Pigment Yellow No. 185. The choice of the group. The coloring composition for a color filter according to any one of claims 1 to 7, further comprising a coloring agent selected from the group consisting of a green coloring agent, a blue coloring agent, and a red coloring agent. The coloring composition for a color filter according to any one of claims 1 to 7, further comprising a photopolymerizable monomer and/or a photopolymerization initiator. A color filter comprising a color filter segment formed by a coloring composition for a color filter according to any one of claims 1 to 9.