KR101971251B1 - Diketopyrrolopyrrole-type pigment composition for color filters, colored composition for color filters, and color filter - Google Patents

Abstract

In the diketopyrrolopyrrole pigment composition for a color filter containing the diketopyrrolopyrrole pigment represented by the formula (1) and the diketopyrrolopyrrole pigment represented by the formula (A-2), the formula (A-2) Wherein the content of the diketopyrrolopyrrole pigment to be displayed is 1% by mass to 15% by mass based on the total mass of the diketopyrrolopyrrole pigment.

Description

TECHNICAL FIELD [0001] The present invention relates to a diketopyrrolopyrrole pigment composition for a color filter, a coloring composition for a color filter and a color filter for a color filter,

The present invention relates to diketopyrrolopyrrole-based pigment compositions for color filters, coloring compositions for color filters, and color filters formed using the same.

The liquid crystal display device is a display device that performs display by controlling the amount of light passing through the polarizer of the second sheet by controlling the degree of polarization of light passing through the polarizer of the first sheet as a liquid crystal layer sandwiched between two polarizers, ) -Type liquid crystal is the mainstream. Color display can be achieved by providing a color filter between these two polarizing plates. Recently, as used in televisions, personal computer monitors, and the like, demands for high clarity, high contrast, and high color reproducibility are increasing for color filters.

The color filter is formed by arranging fine filter strips of two or more different colors in a stripe pattern in parallel or crossing on the surface of a transparent substrate such as glass or by arranging fine filter segments in a regular arrangement have. In general, it is often formed of three color filter segments of red, green, and blue. These segments are fine, for example, several microns to several hundreds of microns, and are arranged regularly in a predetermined arrangement for each color.

Generally, in a color liquid crystal display device, a transparent electrode for driving a liquid crystal is formed on a color filter by vapor deposition or sputtering, and an alignment film for orienting the liquid crystal in a certain direction is formed thereon. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, a high-temperature treatment is generally performed at a temperature of 200 占 폚 or higher, preferably 230 占 폚 or higher, in a production process for forming a color filter. For this reason, at present, a method called a pigment dispersion method using a pigment having excellent light resistance and heat resistance as a coloring agent is the mainstream in the production method of a color filter.

In the pigment dispersion method, pigments excellent in light resistance and heat resistance such as diketopyrrolopyrrole pigments, anthraquinone pigments, perylene pigments or disazo pigments are generally used alone or in combination as the coloring agent in the red filter segment .

Of the diketopyrrolopyrrole pigments, C.I. Pigment Red 254 is a particularly bright pigment, but further improvement in brightness is desired. Further, in recent years, a demand for a high contrast for a color filter is also strong. For this purpose, it is considered desirable to miniaturize the primary particle size of the diketopyrrolopyrrole pigment as much as possible. However, the finely divided diketopyrrolopyrrole pigment has a property that crystal growth is easy due to its intermolecular hydrogen bonding, so that crystallization occurs in the heating process at the time of forming a color filter, and foreign substances are generated There was a problem.

On the other hand, diketopyrrolopyrrole pigments can be obtained by the processes disclosed in Patent Documents 1 and 2 (hereinafter referred to as "succinic acid ester synthesis process").

Patent Document 3 discloses a method for obtaining a mixture of at least two structurally different diketopyrrolopyrrole pigments by using a plurality of nitrile compounds as a raw material in a succinic ester synthesis method.

Patent Document 4 discloses that a mixture of at least two structurally different diketopyrrolopyrrole pigments obtained by a succinic ester synthesis method using a nitrile compound having a plurality of specific structural formulas as a raw material is used for a color filter.

Patent Documents 5 and 6 disclose that by using a diketopyrrolopyrrole pigment (mainly CI Pigment Red 254), at least one diaryldiketopyrrolopyrrole compound having a specific structural formula, and a pigment derivative together, A coloring composition for a color filter in which crystal precipitation by a heating process is suppressed is disclosed.

Patent Document 7 discloses a coloring composition for a color filter using a diketopyrrolopyrrole bromide pigment. Patent Document 8 discloses that a diketopyrrolopyrrole pigment composition is used for a color filter.

Japanese Patent Application Laid-Open No. S58-210084 Japanese Patent Application Laid-Open No. H07-90189 Japanese Patent Application Laid-Open No. S61-120861 Japanese Patent Publication No. 2007-514798 WO2009 / 081930 pamphlet Japanese Patent Application Laid-Open No. 2009-149707 Japanese Patent Application Laid-Open No. 1999-231516 WO2009 / 144115 pamphlet

A problem to be solved by the present invention is to provide a diketopyrrolopyrrole pigment composition for a color filter which is excellent in lightness and contrast and hardly causes crystal precipitation of a diketopyrrolopyrrole pigment even by a heating process, And a color filter using the same.

A first embodiment of the present invention is a diketopyrrolopyrrole pigment composition for a color filter comprising a diketopyrrolopyrrole pigment represented by formula (1) and a diketopyrrolopyrrole pigment represented by formula (A-2) , Wherein the content of the diketopyrrolopyrrole pigment represented by the formula (A-2) is 1% by mass to 15% by mass based on the total mass of the diketopyrrolopyrrole-based pigment, Pyrrole-based pigment compositions.

[Chemical Formula 1]

[In the formula (A-2)

A and B each independently represent a hydrogen atom, a fluorine atom, an iodine atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, a phenyl group which may have a substituent, -CF ₃ , -OR ¹ , -SR ² , -N ^{R 3) R 4, -COOR 5} , -CONH 2, -CONHR 6, -CON (R 7) R 8, -SO 2 NH 2, -SO 2 NHR 9, ^{_{or, -SO 2 N (R 10)}} R ¹¹ ,

R ₁ to R ₁₁ each independently represent an alkyl group having 1 to 12 carbon atoms, a phenyl group which may have a substituent or an aralkyl group which may have a substituent.

Provided that A and B are not hydrogen atoms at the same time.

The first embodiment is characterized in that the diketopyrrolopyrrole pigment represented by the above formula (A-2) is a pigment represented by the formula (A-2-1), the formula (A-2-2) 3) or formula (A-2-4). The present invention relates to a diketopyrrolopyrrole pigment composition for a color filter.

(2)

[Of the formulas (A-2-3) and (A-2-4)

R ⁶ to R ⁸ each independently represent an alkyl group having 1 to 12 carbon atoms or a phenyl group which may have a substituent.

Further, in the first embodiment, as the diketopyrrolopyrrole-based pigment, C.I. Pigment Red 254 as a coloring material for a color filter.

Further, the first embodiment is characterized in that, based on the total mass of the diketopyrrolopyrrole pigment, the diketopyrrolopyrrole pigment represented by the formula (1) and the C.I. Pigment Red 254 is 85% by mass to 99% by mass, based on the total amount of the pigment.

Further, the first embodiment is characterized in that the diketopyrrolopyrrole pigment represented by the formula (1) and the C.I. Pigment Red 254 in a weight ratio of 20:80 to 99: 1.

The first embodiment further relates to a diketopyrrolopyrrole pigment composition for a color filter, which further comprises a pigment derivative.

A second embodiment of the present invention relates to a diketopyrrolopyrrole pigment for a color filter containing a diketopyrrolopyrrole pigment represented by the formula (1) and a diketopyrrolopyrrole pigment represented by the formula (B-2) The diketopyrrolopyrrole pigment composition for a color filter is characterized in that the mass ratio of the formula (1) and the formula (B-2) in the composition is 97: 3 to 85:15.

(3)

[In the formula (B-2)

A and B are, each independently, a hydrogen atom, a fluorine atom, a chlorine atom, an iodine atom, a cyano group, an alkyl group of 1 to 12 carbon atoms, a phenyl group which may have a substituent ^{_{(s), -CF 3, -OR 1, -SR}} 2, ^{-N (R 3) R 4,} -COOR 5, -CONH 2, -CONHR 6, -CON (R 7) R 8, -SO 2 NH 2, -SO 2 NHR 9, or, -SO ₂ N (R ¹⁰ ) R < ¹¹ >

R ¹ to R ¹¹ each independently represent an alkyl group having 1 to 12 carbon atoms, a phenyl group which may have a substituent or an aralkyl group which may have a substituent.

Provided that A and B are not hydrogen atoms at the same time.

(B-2-1), (B-2-2), (B-2-3) and (B-2) Wherein the diketopyrrolopyrrole pigment composition for a color filter according to any one of (1) to (4), (B-2-5), (B- 2-6) .

[Chemical Formula 4]

Among the formulas (B-2-4), (B-2-6) and (B-2-7)

R ¹² to R ¹⁵ each independently represent an alkyl group having 1 to 12 carbon atoms or a phenyl group which may have a substituent.

The second embodiment further relates to a diketopyrrolopyrrole pigment composition for a color filter, which further comprises a pigment derivative.

A third embodiment of the present invention is a coloring composition comprising a colorant, a binder resin and an organic solvent, characterized in that the coloring agent contains the diketopyrrolopyrrole-based pigment composition of the first embodiment ≪ / RTI >

The third embodiment further relates to the coloring composition for a color filter, which further comprises a photopolymerizable monomer and / or a photopolymerization initiator.

A fourth embodiment of the present invention is a coloring composition comprising a colorant, a binder resin and an organic solvent, wherein the coloring agent contains the diketopyrrolopyrrole-based pigment composition of the second embodiment ≪ / RTI >

The fourth embodiment further relates to the coloring composition for a color filter, which further comprises a photopolymerizable monomer and / or a photopolymerization initiator.

A fifth embodiment of the present invention is a coloring composition for a color filter comprising a pigment (A), a binder resin (CB) and a solvent, wherein the pigment (A) ), And the binder resin (CB) comprises an alkali-soluble photosensitive resin (C-B1).

[Chemical Formula 5]

The fifth embodiment is characterized in that the pigment (A) is at least one selected from the group consisting of a diketopyrrolopyrrole pigment, an azo pigment, an anthraquinone pigment, a perylene pigment, a quinacridone pigment, a benzimidazolone pigment Based pigment and a quinoline-based pigment. The present invention also relates to the coloring composition for a color filter.

The fifth embodiment is further characterized by further comprising at least one photopolymerization initiator (CD) selected from the group consisting of an acetophenone compound, a phosphine compound, an imidazole compound and an oxime ester compound To a coloring composition for a color filter.

A sixth embodiment of the present invention is a coloring composition for a color filter comprising a pigment (A), a binder resin (DB) and a solvent, wherein the pigment (A) (D-B1) having the structural units (D-b1) to (D-b3), wherein the binder resin (DB) contains the structural units (D-b1) to (D-b3).

[Chemical Formula 6]

(D-b1) 2 to 60% by weight of a constituent unit having a carboxyl group

(D-b2) 2 to 80% by weight of a structural unit having an aromatic ring group represented by the formula (D-2) or (D-3)

(D-b3) 2 to 60% by weight of a constituent unit having an aliphatic ring group represented by the formula (D-4) or (D-5)

(7)

[Chemical Formula 8]

[In the formulas (D-2) and (D-3), R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a benzene ring. The broken line in formula (D-3) represents a cyclic structure adjacent to the benzene ring and containing at least one saturated or unsaturated heterocycle which may have a substituent.]

[Chemical Formula 9]

[Chemical formula 10]

The sixth embodiment is characterized in that the pigment (A) is at least one selected from the group consisting of diketopyrrolopyrrole pigments other than the pigment (A1), azo pigments, anthraquinone pigments, perylene pigments, quinacridone pigments, Based pigment and a quinoline-based pigment. The present invention also relates to the coloring composition for a color filter.

The sixth embodiment is further characterized by further comprising at least one photopolymerization initiator (DD) selected from the group consisting of an acetophenone compound, a phosphine compound, an imidazole compound and an oxime ester compound To a coloring composition for a color filter.

A seventh embodiment of the present invention relates to a color filter characterized by comprising a filter segment formed from the coloring composition for a color filter.

The disclosure of this application is based on Japanese Patent Application No. 2011-15874 filed on January 28, 2011, Japanese Patent Application No. 2011-76928 filed on March 31, 2011, Japanese Patent Application filed on March 31, 2011 Japanese Patent Application No. 2011-76929 filed on December 13, 2011, and Japanese Patent Application No. 2011-271836 filed on December 13, 2011, the disclosures of which are incorporated herein by reference.

Hereinafter, embodiments of the present invention will be described in detail.

On the other hand, "C.I." mentioned below means color index (C.I.). In the case of "(meth) acrylate", "(meth) acrylic acid" or "(meth) acrylamide", the terms "acrylate and / or methacrylate" Acrylic acid and / or methacrylic acid ", or " acrylamide and / or methacrylamide ".

[Dicetopyrrolopyrrole-based pigment composition]

First, the diketopyrrolopyrrole-based pigment composition which is an embodiment of the present invention will be described.

[First embodiment]

(Diketopyrrolopyrrole-based pigment composition)

The first embodiment relates to a diketopyrrolopyrrole pigment for a color filter containing a diketopyrrolopyrrole pigment represented by the following formula (1) and a specific heterodimeropyrrolopyrrole pigment represented by the following formula (A-2) Wherein the content of the specific diketopyrrolopyrrole pigment represented by the following formula (A-2) is 1% by mass to 15% by mass based on the total mass of the diketopyrrolopyrrole-based pigment, Pyrrole-based pigment composition.

As a result of intensive studies, the inventors of the present invention have found that C.I. It was found that the brightness was improved by applying the diketopyrrolopyrrole bromide pigment (formula (1)) to the color filter as compared to Pigment Red 254 (chlorinated diketopyrrolopyrrole pigment). Further, a diketopyrrolopyrrole pigment composition containing a diketopyrrolopyrrole pigment (represented by the formula (A-2) (hereinafter referred to as "specific diketopyrrolopyrrole pigment A") having a substituent group introduced thereto at an asymmetric specific structure It has been found that a color filter having high contrast as well as suppression of crystal precipitation by a heating process can be obtained by using the specific heterodimeropyrrolopyrrole pigment A. Since the specific heterodimeropyrrolopyrrole pigment A selected here has a small interaction with the resin component , It is possible to effectively cover the active surface of the diketopyrrolopyrrole bromide pigment and to suppress the thermal agglomeration of the pigment by the heating step so that a high contrast and an effect of suppressing the precipitation of crystals are exerted with a small amount of the content. The toiloprolopyrrole pigment A has better color characteristics and less amount of addition than the crystal precipitation inhibitor known so far To, and does not inhibit the excellent effect of improving the brightness bromide diketopyrrolopyrrole pigment. In addition, diketopyrrolo pyrrole pigment composition containing a specific hetero so diketopyrrolopyrrole pigment A, is excellent in viscosity stability.

According to the first embodiment, there is provided a diketopyrrolopyrrole pigment composition for a color filter which is excellent in brightness and contrast, is not only not precipitated by crystallization of the diketopyrrolopyrrole-based pigment by a heating step but also has excellent viscosity stability. .

(11)

[In the formula (A-2)

A and B each independently represent a hydrogen atom, a fluorine atom, an iodine atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, a phenyl group which may have a substituent, -CF ₃ , -OR ¹ , -SR ² , -N ^{R 3) R 4, -COOR 5} , -CONH 2, -CONHR 6, -CON (R 7) R 8, -SO 2 NH 2, -SO 2 NHR 9, ^{_{or, -SO 2 N (R 10)}} R ¹¹ ,

R ¹ to R ¹¹ each independently represent an alkyl group having 1 to 12 carbon atoms, a phenyl group which may have a substituent or an aralkyl group which may have a substituent.

Provided that A and B are not hydrogen atoms at the same time.

The alkyl group having 1 to 12 carbon atoms may be linear or branched and may specifically be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert- , A heptyl group, an octyl group, a decyl group, a dodecyl group, a 1,5-dimethylhexyl group, a 1,6-dimethylheptyl group, a 2-ethylhexyl group and the like.

Examples of the phenyl group which may have a substituent include substituents such as an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group, a halogen atom, a nitro group, a cyano group, a carbamoyl group, a sulfamoyl group and an alkoxyl group having 1 to 4 carbon atoms And the like. The phenyl group may have one or two or more of these substituents. More specifically, examples include a phenyl group, a p-methylphenyl group, a 4-tert-butylphenyl group, a p-nitrophenyl group, a p-methoxyphenyl group, But are not limited to these.

Examples of the aralkyl group which may have a substituent include substituents such as an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group, a halogen atom, a nitro group, a cyano group, a carbamoyl group, a sulfamoyl group, and an alkoxyl group having 1 to 4 carbon atoms , And the like. The aralkyl group may have one or two or more of these substituents. Specific examples thereof include a benzyl group, a 4-methylbenzyl group, a 4-tert-butylbenzyl group, a 4-methoxybenzyl group, a 4-nitrobenzyl group and a 2,4- But is not limited thereto.

Among the specific diketopyrrolopyrrole pigment A represented by the formula (A-2) used in the pigment composition of the first embodiment, the compounds represented by the formulas (A-2-1), (A-2-2) A-2-3) and formula (A-2-4) are preferable in terms of lightness, contrast and crystal precipitation inhibiting effect. R ⁶ to R ⁸ in the formulas (A-2-3) and (A-2-4) are preferably an alkyl group having 4 or more carbon atoms or a phenyl group which may have a substituent in terms of contrast and crystal precipitation inhibiting effect desirable. The reason why they exhibit the effect of high contrast and suppression of crystal precipitation is that they are produced by a bulky substituent such as a carbonamide group (carbamoyl group) having an alkyl group having 4 or more carbon atoms, a phenyl group or a t-butyl group It is considered that aggregation of the pigment is suppressed by the steric hindrance effect. The specific heterodimethopyrrolopyrrole pigment A having a carbamoide group (carbamoyl group), a phenyl group and a t-butyl group is also excellent in color characteristics, so that the excellent brightness of the diketopyrrolopyrrole bromide pigment is not impaired.

[Chemical Formula 12]

[Of the formulas (A-2-3) and (A-2-4)

R ⁶ to R ⁸ each independently represent an alkyl group having 1 to 12 carbon atoms or a phenyl group which may have a substituent.

Specific examples of the specific diketopyrrolopyrrole pigment A of formula (A-2) are shown below, but are not limited thereto.

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

The pigment composition is characterized in that the content of the specific heterodimeropyrrolopyrrole pigment A represented by the formula (A-2) is in the range of 1% by mass to 15% by mass based on the total weight of the diketopyrrolopyrrole pigment . And preferably 3% by mass to 10% by mass. When the proportion of the specific diketopyrrolopyrrole pigment A in the formula (A-2) exceeds 15% by mass, the crystal precipitation inhibiting effect can be obtained, but the excellent brightness of the diketopyrrolopyrrole bromide pigment of the formula (1) . On the other hand, if the proportion of the specific diketopyrrolopyrrole pigment A in the formula (A-2) is less than 1% by mass, the effect of suppressing high contrast and inhibiting the precipitation of crystals is not sufficient. When the effect of inhibiting the precipitation of crystals is insufficient, light scattering occurs due to a crystalline foreign matter precipitated on the surface of the coating film in the heating step, resulting in a decrease in brightness and contrast ratio. Therefore, by using the diketopyrrolopyrrole pigment composition containing the specific diketopyrrolopyrrole pigment A in the above ratio, it is possible to achieve high brightness and high contrast, Precipitation can be suppressed. Further, excellent viscosity stability can be obtained.

The pigment composition may be prepared by using a diketopyrrolopyrrole pigment of the formula (1) and a diketopyrrolopyrrole pigment other than the specific diketopyrrolopyrrole pigment A of the formula (A-2) in combination so long as the effect is not impaired It is possible. Specifically, C.I. Pigment Red 254, 255, 264, 272, C.I. Pigment Orange 71, 73, or 81, but the present invention is not limited to these pigments. Examples of the diketopyrrolopyrrole pigments usable in combination include C.I. Pigment Red 254 is preferred. C.I. Pigment Red 254 is preferable because it is usually contained when the specific diketopyrrolopyrrole pigment A of formula (A-2) is prepared by a synthesis method of succinic acid diester, and the pigment of the diketopyrrolopyrrole pigment of formula (1) This is because it is difficult to affect the excellent brightness.

Wherein the pigment composition is selected from the group consisting of C.I. When Pigment Red 254 is contained, the diketopyrrolopyrrole pigment represented by Formula (1) and the C.I. Pigment Red 254 is 85% by mass to 99% by mass. The diketopyrrolopyrrole pigment represented by the formula (1) and the C.I. When the total content of Pigment Red 254 is less than 85% by mass, the brightness enhancement effect may be reduced. When the content is more than 99% by mass, the content of the specific diketopyrrolopyrrole pigment A is small, The crystal precipitation inhibiting effect may not be sufficiently obtained. The diketopyrrolopyrrole pigment represented by the formula (1) and the C.I. The mass ratio of Pigment Red 254 is preferably 20:80 to 99: 1. More preferably, it is 50:50 to 99: 1. The diketopyrrolopyrrole pigment represented by the formula (1) and the C.I. When the content of the diketopyrrolopyrrole pigment represented by the formula (1) in the total of Pigment Red 254 is 20 mass% or more, it is preferable since the effect of improving brightness is increased.

As the diketopyrrolopyrrole pigment of the formula (1) and the diketopyrrolopyrrole pigment other than the specific heterodimeropyrrolopyrrole pigment A of the formula (A-2), the specific heterodimer of the formula (B-2) It is also possible to use a topirroropyrrole pigment. At this time, it is preferable that the weight ratio of the diketopyrrolopyrrole pigment of the formula (1) to the specific heterodimeropyrrolopyrrole pigment B of the formula (B-2) is 97: 3 to 85:15.

(Production method of diketopyrrolopyrrole pigment)

The diketopyrrolopyrrole pigment represented by the formula (1) can be obtained by a known method described in International Publication No. 2009/144115 pamphlet.

The diketopyrrolopyrrole pigment represented by the formula (1) can be produced by a succinic acid diester synthesis method. Namely, 2 moles of 4-bromobenzonitrile per mole of succinic acid diester is condensed in an inert organic solvent such as tert-amyl alcohol in the presence of an alkali metal or an alkali metal alkoxide at a high temperature of 80 to 110 ° C To produce an alkali metal salt of a diketopyrrolopyrrole compound. Subsequently, the alkali metal salt of the diketopyrrolopyrrole compound is protonated by using water, an alcohol, an acid, or the like to obtain a diketopyrrolopyrrole bromide pigment. At this time, the size of the obtained primary particle size can be controlled according to the kind, proportion or amount of the temperature, water, alcohol or acid in the protonation. The method for producing the diketopyrrolopyrrole pigment represented by the formula (1) is not limited to this method.

The specific heterodimeropyrrolopyrrole pigment A of formula (A-2) is described, for example, in Synth. Commun., 1988, 18, 1213 and Tetrahedron, 58 (2002) 5547-5565. The method for producing the specific heterodimeropyrrolopyrrole pigment A is not limited to this method.

Further, the specific heterodimeropyrrolopyrrole pigment A of the formula (A-2) is preferably a C.I. Pigment Red 254 in the presence of a base. This can be achieved by using at least two structurally different benzonitrile compounds (hereinafter referred to as " succinic acid diester co-synthesis (co-synthesis) ") in the succinic acid diester synthesis method. Specifically, a plurality of benzonitrile compounds to be used are selected from 4-chlorobenzonitrile and benzonitrile compounds represented by the following formula (A-3) in the method described in WO2009 / 081930 pamphlet, The specific heterodimeropyrrolopyrrole pigment A of (A-2) was replaced with CI Pigment Red 254. ≪ / RTI >

[Chemical Formula 17]

[In the formula (A-3)

A and B each independently represent a hydrogen atom, a fluorine atom, an iodine atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, a phenyl group which may have a substituent, -CF ₃ , -OR ¹ , -SR ² , -N ^{R 3) R 4, -COOR 5} , -CONH 2, -CONHR 6, -CON (R 7) R 8, -SO 2 NH 2, -SO 2 NHR 9, ^{_{or, -SO 2 N (R 10)}} R ¹¹ ,

R ¹ to R ¹¹ each independently represent an alkyl group having 1 to 12 carbon atoms, a phenyl group which may have a substituent or an aralkyl group which may have a substituent.

Provided that A and B are not hydrogen atoms at the same time.

The alkyl group having 1 to 12 carbon atoms, the phenyl group which may have a substituent or the aralkyl group which may have a substituent is the same as the group in the formula (A-2).

The pigment composition can be used by mixing the diketopyrrolopyrrole pigment represented by the formula (1) and the specific diketopyrrolopyrrole pigment A separately prepared. Further, the specific heterocyclic pyrrolopyrrole pigment A synthesized by the succinic acid diester co-synthesis method and the C.I. Pigment Red 254 may also be mixed with the diketopyrrolopyrrole pigment represented by the formula (1). In these cases, the pigment may be simply mixed before the pigment is dispersed in the pigment carrier, or may be pulverized and mixed through a salt milling treatment.

In the pigment composition, the diketopyrrolopyrrole pigment represented by the formula (1), the specific diketopyrrolopyrrole pigment A of the formula (A-2), and the C.I. The mass ratio of Pigment Red 254 can be analyzed using TOF-MASS, FD-MASS, LC-MASS or NMR. Alternatively, as disclosed in Japanese Patent Application Laid-Open No. H08-199085, the diketopyrrolopyrrole-based pigment composition is mixed with di-tert-butyl dicarbonate and 4-dimethylaminopyridine in tetrahydrofuran, Of a diketopyrrolopyrrole compound, followed by analysis using NMR, MASS or LC-MASS. Alternatively, the above analysis may be performed after replacing the hydrogen of the NH group of the pyrrolopyrrole ring with an alkyl group using halogenated alkyl or the like and converting it into soluble diketopyrrolopyrrole.

(Pigment derivative)

The pigment composition may contain a pigment derivative for the purpose of inhibiting the growth of pigment crystals and improving pigment dispersibility. The pigment derivative used in the pigment composition may be at least one selected from the group consisting of diketopyrrolopyrrole derivatives, benzoisoindole derivatives, anthraquinone derivatives, dianthraquinone derivatives, thiazineindigo derivatives, azo dye derivatives, quinophthalone derivatives and quinacridone derivatives . Examples of the structure of the dye derivative include a dye derivative represented by the following formula (4), but the dye derivative is not limited thereto.

P-Lm Equation (4)

[In the formula (4)

P is a diketopyrrolopyrrole residue, a benzoisoindole residue, an anthraquinone residue, a dianthraquinone residue, a thiazineindigo residue, an azo dye residue, a quinophthalone residue, or a quinacridone residue,

m is an integer of 1 to 4,

L each independently represent -OH; -SO ₃ H, -COOH, monovalent to trivalent metal salts of these acid groups, alkylammonium salts; A phthalimidemethyl group which may have a substituent; Is a group represented by the following formula (a), (b), (c), (d), (e)

[Chemical Formula 18]

X _{is, -SO 2 -, -CO-, -CH} 2 -, -CH 2 NHCOCH 2 -, -CH 2 NHSO 2 CH 2 -, or a direct bond,

Y is -NH-, -O-, -S-, or a direct bond,

n is an integer of 1 to 10,

R ¹⁶ and R ¹⁷ are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms which may have a substituent, or an alkenyl group having 2 to 30 carbon atoms which may have a substituent, and R ¹⁶ and R ¹⁷ are integrated , Optionally forming a heterocyclic ring which may have a substituent, further containing nitrogen, oxygen or sulfur atom,

R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms,

R ²³ is a substituent represented by the formula (a) or (b)

R ²⁴ is a substituent group represented by a chlorine atom, -OH, an alkoxyl group, a group represented by the formula (a) or (b)

Z _{is, -CONH-, -NHCO-, -SO 2 NH-} , or -NHSO ₂ - and,

R ²⁵ represents a hydrogen atom, -NH ₂ , -NHCOCH ₃ , -NHR ²⁶ or a substituent represented by the formula (c), wherein R ²⁶ represents an alkyl group having 1 to 20 carbon atoms which may have a substituent, An alkenyl group having 2 to 20 carbon atoms which may have a substituent.]

Examples of the monovalent to trivalent metal include sodium, potassium, magnesium, calcium, iron, and aluminum. Examples of the alkylammonium salts include ammonium salts of long-chain monoalkylamines such as octylamine, laurylamine, and stearylamine; quaternary alkylamines such as palmityltrimethylammonium salt, dilauryldimethylammonium salt, and distearyldimethylammonium salt; Ammonium salts.

Examples of the substituent of the phthalimidemethyl group which may have a substituent, the alkyl group which may have a substituent, the alkenyl group which may have a substituent or the heterocyclic group which may have a substituent include a halogen atom, a nitro group, a cyano group, , An N-substituted carbamoyl group, a sulfamoyl group, an N-substituted sulfamoyl group, an alkoxyl group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, and the like.

The pigment derivative can be obtained by sulfonation reaction by heating in sulfuric acid or fuming sulfuric acid, phthalimidomethylation reaction in which sulfuric acid is dehydrated and condensed with N-hydroxymethylphthalimide, chlorosulfonation with chlorosulfonic acid and thionyl chloride Followed by a sulfonamidation reaction in which an amine component such as dimethylaminopropylamine is reacted.

Examples of the amine component used for forming the substituent represented by the above formulas (a), (b) and (c) include dimethylamine, diethylamine, methylethylamine, N, But are not limited to, isopropylamine, N, N-ethylpropylamine, N, N-methylbutylamine, N, N-methylisobutylamine, N, But are not limited to, amine, dipropylamine, N, N-sec-butylpropylamine, dibutylamine, di-sec-butylamine, diisobutylamine, N, N- N, N-diethylamine, diethylamine, diethylamine, diethylamine, diethylamine, diethylamine, diethylamine, diethylamine, diethylamine, diethylamine, diethylamine, N, N-dimethylaminoethylamine, N, N-dimethylaminoamylamine, N, N-dimethylaminoethylamine, N, N-dimethylaminoethylamine, N, N, N-dimethylaminobutylamine, N, N-diethylaminoethyl Amines such as N, N-diethylaminopropylamine, N, N-diethylaminohexylamine, N, N-diethylaminobutylamine, N, N-diethylaminopentylamine, Amines such as N, N-dibutylaminopropylamine, N, N-dibutylaminoethylamine, N, N-dibutylaminobutylamine, N, N-diisobutylaminopentylamine, N, N, N-dodecylaminobutylamine, N, N-dodecylaminobutylamine, N, N-dodecylaminobutylamine, N, Piperidine, 3-piperazines, 4-piperazines, 4-piperazines, 4-piperazines, But are not limited to, isonipecotic acid, methyl isonipecotate, ethyl isonipecotate, 2-piperidineethanol, pyrrolidine, 3-hydroxypyrrolidine, N-aminoethylpiperidine, Aminoethyl-4-piperolin, N-aminoethylmorpholine, N-aminopropyl Piperidine, N-aminopropyl-4-piperidinol, N-aminopropylmorpholine, N-methylpiperazine, N-butylpiperazine, N-methyl homopiperazine, But are not limited to, 1-cyclopentylpiperazine, 1-amino-4-methylpiperazine, 1-cyclopentylpiperazine, and the like.

Further, when a substituent is introduced into the azo dye, an azo dye derivative may be prepared by introducing a substituent into the diazo component or the coupling component in advance and then performing a coupling reaction.

The pigment derivative may be used not only by mixing the diketopyrrolopyrrole pigment composition with the pigment composition when dispersing the diketopyrrolopyrrole pigment composition in a pigment carrier, but also by a method of mixing in water or an organic solvent at the time of pigment preparation, . The method of mixing the pigment derivative in the water or the organic solvent during the preparation of the pigment or adding the pigment derivative in the salt milling treatment exhibits an effect of suppressing the crystal growth of the diketopyrrolopyrrole pigment, It is required that the dye derivative is efficiently adsorbed on the surface of the diketopyrrolopyrrole pigment and that the pigment derivative is not easily desorbed. Accordingly, the structure of the pigment derivative is often considered to partially have a chemical structure similar to that of the pigment to be used. For this reason, when a diketopyrrolopyrrole pigment is produced, a pigment derivative having a diketopyrrolopyrrole structure, a thiazineindigo structure, a benzoisoindole structure, or a quinacridone structure is generally effective.

When a pigment derivative is used, it is required that the color tone of the diketopyrrolopyrrole pigment composition is not reduced as much as possible. From the viewpoint of color, it is preferable to use a diketopyrrolopyrrole derivative, a benzoisoindole derivative, a thiazineindigo derivative, an azo dye derivative, or a quinophthalone derivative having a yellow color and an orange color.

The blending amount of the pigment derivative is preferably in the range of 0.5 to 40 parts by mass with respect to 100 parts by mass of the diketopyrrolopyrrole pigment composition. More preferably, it is in the range of 3 to 35 parts by mass based on 100 parts by mass of the diketopyrrolopyrrole pigment composition. When the amount is less than 0.5 parts by mass, the crystal growth inhibiting effect may be insufficient. When the amount is more than 40 parts by mass, the good tone of the diketopyrrolopyrrole pigment may be lowered.

Specific examples of the dye derivative used in the diketopyrrolopyrrole pigment composition are described below, but the present invention is not limited thereto.

(Specific examples of diketopyrrolopyrrole derivatives)

As the diketopyrrolopyrrole derivative, specifically, compounds represented by the following formula (5) or (6) can be used, but are not limited thereto.

[Chemical Formula 19]

[Chemical Formula 20]

(Specific examples of benzoisoindole derivatives)

As the benzoisoindole derivative, specifically, a compound represented by the following formula (7) can be used, but is not limited thereto.

[Chemical Formula 21]

(Specific examples of anthraquinone derivatives)

As the anthraquinone derivative, specifically, a compound represented by the following formula (8) can be used, but is not limited thereto.

[Chemical Formula 22]

(Specific Example of Dianthraquinone Derivative)

As the dianthraquinone derivative, specifically, a compound represented by the following formula (9) can be used, but is not limited thereto.

(23)

(Specific examples of thiazineindigo derivatives)

As the thiazineindigo derivative, specifically, a compound represented by the following formula (10) may be used, but is not limited thereto.

≪ EMI ID =

(Specific examples of azo dye derivatives)

Specific examples of the azo dye derivatives include, but are not limited to, compounds represented by the following formula (11), (12), or (13)

(25)

(26)

(27)

(Specific Example of Quinophthalone Derivative)

Specific examples of the quinophthalone derivative include, but are not limited to, compounds represented by the following formulas (14-1) to (14-13).

(28)

[Chemical Formula 29]

(30)

(Specific examples of quinacridone derivatives)

As the quinacridone derivative, specifically, a compound represented by the following formula (15) may be used, but is not limited thereto.

(31)

(Average primary particle diameter of pigment)

It is preferable that the pigment composition of the first embodiment has a very small primary particle diameter, narrow distribution width, and sharp particle size distribution. The average primary particle diameter (volume average particle diameter) determined by a TEM (transmission electron microscope) of the pigment composition of the first embodiment is preferably in the range of 5 to 70 nm. If it is smaller than 5 nm, dispersion in an organic solvent may become difficult. If it is larger than 70 nm, a sufficient contrast ratio may not be obtained. For this reason, a more preferable range is 10 to 40 nm. When pigments are synthesized and mixed, the pigments can be used as they are at the same stage as the pigment composition in the above-mentioned range. If not, the pigments are preferably finely smoothed and smoothed by a salt milling process or the like .

(Fineness of pigment)

The pigment comprising the diketopyrrolopyrrole-based pigment composition of the first embodiment is preferably used in finely divided form, and the finishing method is preferably a salt milling treatment.

The salt milling treatment is a treatment in which a pigment, a mixture of a water-soluble inorganic salt and a water-soluble organic solvent is kneaded using a kneader such as a kneader, a tri-mix, a two-roll mill, a three-roll mill, a ball mill, an attritor, , Mechanically kneading while heating, and then removing water-soluble inorganic salt and water-soluble organic solvent by washing with water. The water-soluble inorganic salt serves as a crushing aid, and it is considered that the pigment is broken by using the height of the hardness of the inorganic salt at the time of the salt milling, and accordingly the active surface is generated, and crystal growth is caused. Therefore, at the time of kneading, fracture of the pigment and crystal growth occur simultaneously, and the primary particle diameter of the pigment obtained by the kneading conditions is different.

In order to promote crystal growth by heating, the heating temperature is preferably 35 to 150 ° C. When the heating temperature is lower than 35 占 폚, the crystal growth does not sufficiently take place and the shape of the pigment particles may become amorphous. On the other hand, when the heating temperature exceeds 150 ° C, the crystal growth proceeds too much, and the primary particle diameter of the pigment sometimes becomes large. The kneading time of the salt milling treatment is preferably 2 to 24 hours from the viewpoint of balance between the particle size distribution of the primary particles of the obtained pigment and the cost required for the salt milling treatment.

By optimizing the conditions under which the pigment is subjected to the salt milling treatment, it is possible to obtain a pigment having a very fine primary particle diameter, a narrow distribution width and a sharp particle size distribution.

As the water-soluble inorganic salt used in the salt milling treatment, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but from the viewpoint of cost, it is preferable to use sodium chloride (salt). The water-soluble inorganic salt is preferably used in an amount of from 50 to 2000 parts by mass, and most preferably from 300 to 1200 parts by mass, based on 100 parts by mass of the pigment from both the treatment efficiency and the production efficiency.

The water-soluble organic solvent is not particularly limited as long as it has a function of wetting the pigment and the water-soluble inorganic salt, dissolves in water (miscible) and does not substantially dissolve the inorganic salt used. However, since the temperature rises at the time of salt milling and the solvent tends to evaporate, a high boiling point solvent having a boiling point of 120 ° C or higher is preferable from the viewpoint of safety.

For example, there can be mentioned 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl Diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, diethylene glycol monomethyl ether, Monoethyl ether, and liquid polypropylene glycol. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by mass, and most preferably 50 to 500 parts by mass with respect to 100 parts by mass of the pigment.

In the case of the salt milling treatment, a pigment derivative may be used in combination to improve the kneading efficiency, and it is very effective in miniaturizing and stabilizing the pigment. In the miniaturization of the diketopyrrolopyrrole-based pigment composition, it is preferable to use the above-mentioned dye derivative, but the present invention is not limited thereto. The amount of the pigment derivative to be used is preferably in the range of 0.5 to 40 parts by mass with respect to 100 parts by mass of the pigment so as not to affect the color tone.

In the case of the salt milling treatment, a resin may be added as needed. The type of the resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin used is preferably a solid at room temperature, preferably water-insoluble, and further preferably partially soluble in the organic solvent. The amount of the resin to be used is preferably in the range of 5 to 200 parts by mass with respect to 100 parts by mass of the pigment.

[Second Embodiment]

(Diketopyrrolopyrrole-based pigment composition)

A second embodiment is a diketopyrrolopyrrole pigment composition for a color filter containing a diketopyrrolopyrrole bromide pigment represented by the following formula (1) and a specific heterodimeropyrrolopyrrole pigment represented by the following formula (B-2) , And a mass ratio of the following formula (1) and the following formula (B-2) is in the range of 97: 3 to 85: 15.

As a result of intensive studies, the inventors of the present invention have found that C.I. It was found that brightness was improved by applying a diketopyrrolopyrrole bromide pigment (formula (1)) to a color filter in place of Pigment Red 254 (chlorinated diketopyrrolopyrrole pigment). And a diketopyrrolopyrrole pigment (formula (B-2)) (hereinafter referred to as "specific heterodimeropyrrolopyrrole pigment B") having a substituent group introduced asymmetrically with the diketopyrrolopyrrole pigment By using the pigment composition, it has been found that a color filter having high brightness, high contrast and suppressed of crystal precipitation by a heating process can be obtained.

According to the second embodiment, it is possible to provide a pigment composition for a color filter in which crystallinity of the diketopyrrolopyrrole-based pigment does not occur even by a heating process, with high brightness and high contrast.

(32)

[In the formula (B-2)

A and B are, each independently, a hydrogen atom, a fluorine atom, a chlorine atom, an iodine atom, a cyano group, an alkyl group of 1 to 12 carbon atoms, a phenyl group which may have a substituent ^{_{(s), -CF 3, -OR 1, -SR}} 2, ^{-N (R 3) R 4,} -COOR 5, -CONH 2, -CONHR 6, -CON (R 7) R 8, -SO 2 NH 2, -SO 2 NHR 9, or, -SO ₂ N (R ¹⁰ ) R < ¹¹ >

R ¹ to R ¹¹ each independently represent an alkyl group having 1 to 12 carbon atoms, a phenyl group which may have a substituent or an aralkyl group which may have a substituent.

Provided that A and B are not hydrogen atoms at the same time.

The alkyl group having 1 to 12 carbon atoms may be linear or branched and may specifically be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert- , A heptyl group, an octyl group, a decyl group, a dodecyl group, a 1,5-dimethylhexyl group, a 1,6-dimethylheptyl group, a 2-ethylhexyl group and the like.

Examples of the phenyl group which may have a substituent include substituents such as an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group, a halogen atom, a nitro group, a cyano group, a carbamoyl group, a sulfamoyl group and an alkoxyl group having 1 to 4 carbon atoms And the like. The phenyl group may have one or two or more of these substituents. More specifically, examples include a phenyl group, a p-methylphenyl group, a 4-tert-butylphenyl group, a p-nitrophenyl group, a p-methoxyphenyl group, But are not limited to these.

Examples of the aralkyl group which may have a substituent include substituents such as an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group, a halogen atom, a nitro group, a cyano group, a carbamoyl group, a sulfamoyl group, and an alkoxyl group having 1 to 4 carbon atoms , And the like. The aralkyl group may have one or two or more of these substituents. Specific examples thereof include a benzyl group, a 4-methylbenzyl group, a 4-tert-butylbenzyl group, a 4-methoxybenzyl group, a 4-nitrobenzyl group and a 2,4- But is not limited thereto.

Specific examples of the specific diketopyrrolopyrrole pigment B of the formula (B-2) are shown below, but are not limited thereto.

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(34)

(35)

(36)

(B-2-1), the formula (B-2-2), the formula (B-2-4a), the formula (B-2-6b), the formula (B-2-7) are preferable from the viewpoint of color, contrast, and crystal precipitation inhibiting effect.

The ratio of the formula (1) to the formula (B-2) in the pigment composition is in the range of 97: 3 to 85: 15 by mass. When the ratio of the formula (B-2) exceeds 15 mass%, the crystal precipitation inhibiting effect can be obtained, but the excellent color tone of the formula (1) is impaired. This is because the diketopyrrolopyrrole bromide pigment of formula (1) is superior in color tone to the specific diketopyrrolopyrrole pigment B of formula (B-2). On the other hand, if the ratio of the formula (B-2) is less than 3% by mass, the effect of suppressing high contrast and suppressing the precipitation of crystals is not sufficient. When the effect of inhibiting the precipitation of crystals is insufficient, light scattering occurs due to a crystalline foreign matter precipitated on the surface of the coating film in the heating step, resulting in a decrease in brightness and contrast ratio. Therefore, by using the diketopyrrolopyrrole pigment composition in the above mass ratio range, high brightness and high contrast can be achieved, and crystal precipitation of the diketopyrrolopyrrole pigment can be suppressed also by a heating process.

The pigment composition may be obtained by using a diketopyrrolopyrrole pigment of the formula (1) and a diketopyrrolopyrrole pigment other than the specific diketopyrrolopyrrole pigment B of the formula (B-2) in combination so long as the effect is not impaired It is possible.

As the diketopyrrolopyrrole pigment of the formula (1) and the diketopyrrolopyrrole pigment other than the specific heterodimeropyrrolopyrrole pigment B of the formula (B-2), the specific heterodimer of the formula (A-2) It is also possible to use a topirroropyrrole pigment. At this time, it is preferable that the content of the specific diketopyrrolopyrrole pigment represented by the formula (A-2) is 1% by mass to 15% by mass based on the total mass of the diketopyrrolopyrrole pigment.

(Production method of diketopyrrolopyrrole pigment)

The brominated diketopyrrolopyrrole pigment of the formula (1) can be produced by the same method as in the first embodiment.

The specific heterodimeropyrrolopyrrole pigment B of formula (B-2) can be prepared, for example, in literature Synth. Commun., 1988, 18, 1213 and Tetrahedron, 58 (2002) 5547-5565. The method of producing the specific heterodimethopyrrolopyrrole pigment B is not limited to this method.

In addition, the brominated diketopyrrolopyrrole pigment of the formula (1) and the specific heterodimeropyrrolopyrrole pigment B of the formula (B-2) can be simultaneously produced as a fine pigment composition. This can be achieved by using at least two kinds of structurally different benzonitrile compounds (hereinafter referred to as " succinic acid diester co-synthesis method ") in the succinic acid diester synthesis method. Specifically, in the method described in the WO2009 / 081930 pamphlet, a plurality of benzonitrile compounds to be used are selected from 4-bromobenzonitrile and a benzonitrile compound represented by the following formula (B-3) The diketopyrrolopyrrole pigment composition of the second embodiment can be produced.

(37)

[In the formula (B-3)

A and B are, each independently, a hydrogen atom, a fluorine atom, a chlorine atom, an iodine atom, a cyano group, an alkyl group of 1 to 12 carbon atoms, a phenyl group which may have a substituent ^{_{(s), -CF 3, -OR 1, -SR}} 2, ^{-N (R 3) R 4,} -COOR 5, -CONH 2, -CONHR 6, -CON (R 7) R 8, -SO 2 NH 2, -SO 2 NHR 9, or, -SO ₂ N (R ¹⁰ ) R < ¹¹ >

R ¹ to R ¹¹ each independently represent an alkyl group having 1 to 12 carbon atoms, a phenyl group which may have a substituent or an aralkyl group which may have a substituent.

Provided that A and B are not hydrogen atoms at the same time.

The alkyl group having 1 to 12 carbon atoms, the phenyl group which may have a substituent or the aralkyl group which may have a substituent is the same as the group in the formula (B-2).

Specific examples of the benzonitrile compound of the formula (B-3) usable in the second embodiment are shown below, but the present invention is not limited thereto.

(38)

The pigment composition may be prepared by separately mixing the diketopyrrolopyrrole bromide pigment and the specific heterodimeropyrrolopyrrole pigment B, but it is preferable to simultaneously prepare the pigment composition by the co-synthesis of succinic acid diester from the ease of production . In the case of using separately produced pigments, the two kinds of pigments may be simply mixed before being dispersed, or may be pulverized and mixed by a salt milling treatment.

In the case of preparing the pigment composition of the diketopyrrolopyrrole pigment of the formula (1) and the specific heterodimeropyrrolopyrrole pigment B of the formula (B-2) by the succinic acid diester co-synthesis method, 2 moles of a mixture of 4-bromobenzonitrile and the benzonitrile compound of formula (B-3) are reacted. In this step, the 4-bromobenzonitrile and the compound represented by the formula (B-3) are added so that the mass ratio of the formula (1) and the formula (B-2) in the resulting diketopyrrolopyrrole pigment composition is 97: 3-85: It is preferable to adjust the mixing ratio (molar ratio) of the benzonitrile compound. The mixing ratio (molar ratio) of 4-bromobenzonitrile to the compound represented by the formula (B-3) varies depending on the kind of the benzonitrile compound of the formula (B-3). The mixing ratio (molar ratio) of 4-bromobenzonitrile to the compound represented by the formula (B-3) is in the range of about 80:20 to 98: 2 in order to bring the mass ratio of the diketopyrrolopyrrole- In the succinic acid diester synthesis method, a diketopyrrolopyrrole pigment (that is, a diketopyrrolopyrrole pigment not containing a bromine atom) reacted with the benzonitrile compound of the formula (B-3) in an amount of 2 moles per mole of the succinic acid diester, Is generated, but there is little influence because it is an extremely small amount.

In the succinic acid diester synthesis method, the reaction ratio of the succinic acid diester to the benzonitrile compound is basically 2 mol of the benzonitrile compound per 1 mol of the succinic acid diester, but the amount of the succinic acid diester is 25 mol % Is effective in improving the yield.

The mass ratio of the diketopyrrolopyrrole bromide pigment and the specific diketopyrrolopyrrole pigment B in the pigment composition prepared by the succinic acid diester synthesis method can be analyzed in the same manner as the mass ratio analysis method in the first embodiment have.

(Pigment derivative)

In the pigment composition of the second embodiment, a pigment derivative may be used for the purpose of inhibiting the growth of pigment crystals and improving pigment dispersibility. Examples of the pigment derivative include the same pigment derivative as the pigment derivative of the first embodiment. The preferred amount of the dye derivative is also the same as in the first embodiment.

(Average primary particle diameter of pigment)

It is preferable that the diketopyrrolopyrrole-based pigment composition of the second embodiment has a very small primary particle diameter, a narrow distribution width, and a sharp particle size distribution. The average primary particle diameter (number average particle diameter) determined by a TEM (transmission electron microscope) of the diketopyrrolopyrrole-based pigment composition of the second embodiment is preferably in the range of 5 to 70 nm. If it is smaller than 5 nm, dispersion in an organic solvent may become difficult. If it is larger than 70 nm, a sufficient contrast ratio may not be obtained. For this reason, a more preferable range is 10 to 40 nm. When the diketopyrrolopyrrole-based pigment composition is produced by the above-mentioned synthesis method, the pigment may be used as it is when the average primary particle diameter falls within the above range. If not, the pigment may be finely refined and smoothed by a salt milling treatment or the like .

(Fineness of pigment)

The pigment containing the diketopyrrolopyrrole-based pigment composition of the second embodiment is preferably used in finely divided form, and the finishing method is preferably a salt milling treatment. The salt milling process can be performed in the same manner as in the first embodiment.

[Coloring composition for color filter]

Next, the coloring composition for a color filter which is an embodiment of the present invention will be described.

[Third embodiment]

(Coloring composition for color filter)

The color composition for a color filter of the third embodiment contains the diketopyrrolopyrrole-based pigment composition of the first embodiment. The diketopyrrolopyrrole-based pigment composition of the first embodiment can be used as a coloring composition by using it in combination with a binder resin and an organic solvent. In addition, a colorant other than the diketopyrrolopyrrole pigment composition of the first embodiment may be used in combination. For example, it is also possible to use the diketopyrrolopyrrole-based pigment composition of the second embodiment.

(Other coloring agent)

The coloring composition of the third embodiment may contain pigments or dyes other than the diketopyrrolopyrrole pigment composition of the first embodiment in the range of not lowering the effect of the coloring composition, Or may be used in combination.

When the colorant other than the diketopyrrolopyrrole pigment composition is used in combination, the content of the diketopyrrolopyrrole pigment composition of the first embodiment in the total amount of the colorant (100 mass%) is in the range of 30 mass% to 100 mass% desirable. More preferably, it is in the range of 50 mass% to 100 mass%. When the diketopyrrolopyrrole pigment composition of the first embodiment is contained in an amount of less than 30% by mass, the excellent effect of lightness may not be sufficiently exhibited.

(Binder resin)

As the binder resin contained in the coloring composition, conventionally known thermoplastic resins and thermosetting resins can be mentioned. The binder resin (CB) containing the alkali-soluble photosensitive resin (C-B1) in the fifth embodiment can also be used as the binder resin. The constituent unit (D-b1) (D-B1) having (D-b3) to (D-b3) can be used.

Examples of the thermoplastic resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane- (HDPE, LDPE), polybutadiene and polyimide resins, and the like can be given as examples of the resin composition of the present invention. Examples of the resin include polyolefin resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins,

When used as a coloring composition for a color filter, the spectral transmittance is preferably 80% or more, more preferably 95% or more, in the entire wavelength range of 400 to 700 nm, which is a visible light region. In the case of using in the form of an alkali developing type colored resist, it is preferable to use an alkali-soluble vinyl-based resin obtained by copolymerizing an ethylenically unsaturated monomer containing an acidic group. In order to further improve the photosensitivity, an energy ray curable resin having an ethylenically unsaturated active double bond may be used.

Examples of the alkali-soluble vinyl-based resin in which the ethylenically unsaturated monomer containing an acidic group is copolymerized include resins having an acidic group such as a carboxyl group and a sulfone group. Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an? -Olefin / (maleic anhydride) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or an isobutylene / Maleic acid copolymer, and the like. Among them, at least one resin selected from an acrylic resin having an acidic group and a styrene / styrenesulfonic acid copolymer, particularly an acrylic resin having an acidic group, is suitably used because it has high heat resistance and transparency.

As the energy ray-curable resin having an ethylenically unsaturated active double bond, a (meth) acrylic compound or cinnamic acid having a reactive substituent such as an isocyanate group, an aldehyde group or an epoxy group is reacted with a polymer having a reactive substituent group such as a hydroxyl group, a carboxyl group or an amino group , A (meth) acryloyl group, and a styryl group are introduced into the polymer. In addition, a polymer containing an acid anhydride such as styrene-maleic anhydride copolymer or -olefin-maleic anhydride copolymer is copolymerized with a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) It is also used.

As the thermoplastic resin, those having both an alkali-soluble ability and an energy ray curing property are also preferable as a photosensitive coloring composition for a color filter.

Examples of the monomer constituting the thermoplastic resin include the following. (Meth) acrylate, isopropyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (Meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (Meth) acrylate, phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (Meth) acrylate, N, N-dimethyl (meth) acrylamide, N, N-di (meth) acrylamide, Ethyl (meth) acrylamide, N- (Meth) acrylamides such as isopropyl (meth) acrylamide, diacetone (meth) acrylamide or acryloylmorpholine, styrenes such as styrene and? -Methylstyrene, ethylvinylether, n- Vinyl ethers such as vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether; and vinyl alcohols such as vinyl acetate and vinyl propionate.

Alternatively, there may be mentioned cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane, 1,6-bismaleimidehexane, 3-maleimidepropionic acid, 6,7-methylenedioxy Maleimide coumarin, 4,4'-bismaleimide diphenylmethane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, N, N'- N, N'-1,4-phenylenedimaleimide, N- (1-pyrenyl) maleimide, N- (2,4,6-trichlorophenyl) maleimide, N- -Aminophenyl) maleimide, N- (4-nitrophenyl) maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimide benzoate , N-succinimidyl-3-maleimide propionate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide hexanoate, N- [4- Imidazolyl) phenyl] maleimide, 9-maleimideacridine, etc. Maleimide.

Examples of the thermosetting resin include an epoxy resin, a benzoguanamine resin, a rosin-modified maleic resin, a rosin-modified fumaric acid resin, a melamine resin, a urea resin and a phenol resin. Above all, an epoxy resin and a melamine resin are more suitably used from the viewpoint of improvement in heat resistance.

The mass average molecular weight (Mw) of the binder resin is preferably in the range of 5,000 to 80,000, and more preferably in the range of 7,000 to 50,000 in order to disperse the colorant preferably. 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.

Here, the mass average molecular weight (Mw) and the number average molecular weight (Mn) were determined by gel permeation chromatography "HLC-8120GPC" manufactured by Tosoh Corporation, in which four separation columns were connected in series, (Molecular weight in terms of polystyrene) measured with tetrahydrofuran as a mobile phase using "TSK-GEL SUPER H5000", "H4000", "H3000" and "H2000".

When the binder resin is used as a coloring composition for a color filter, consideration is given to the balance between a pigment adsorber and a carboxyl group serving as an alkali-soluble group at the time of development, an aliphatic group and an aromatic group serving as affinity groups for the pigment carrier and the solvent . From the viewpoint of pigment dispersibility, developability and further durability, it is preferable to use a resin having an acid value of 20 to 300 mg KOH / g. If the acid value is less than 20 mg KOH / g, the solubility in a developing solution is low, and it may become difficult to form a fine pattern. If it exceeds 300 mgKOH / g, fine patterns may not be left at the time of development.

The binder resin may be used in an amount of 20 to 500 parts by mass based on 100 parts by mass of the colorant. When the amount is less than 20 parts by mass, the film formability and various resistance may be insufficient. When the amount is more than 500 parts by mass, the pigment concentration may be low and color characteristics may not be exhibited.

(Organic solvent)

An organic solvent is contained in the coloring composition in order to easily disperse and penetrate the coloring agent in the coloring agent carrier and to form a filter segment on the substrate such as a glass substrate so as to have a dry film thickness of 0.2 to 5 μm. The organic solvent is selected in consideration of solubility and safety of each component of the coloring composition, in addition to good applicability of the coloring composition.

The organic solvent is preferably used in an amount of 500 to 4000 parts by mass with respect to 100 parts by mass of the colorant in that the coloring composition can be adjusted to an appropriate viscosity to form a filter segment having a desired uniform film thickness.

(Production method of coloring composition)

The coloring composition is obtained by mixing the diketopyrrolopyrrole-based pigment composition with a coloring agent carrier made of the binder resin and an organic solvent by a kneader, a twin roll mill, a three roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, , Or an attritor or the like. In addition, the coloring composition may be obtained by dispersing the diketopyrrolopyrrole-based pigment composition and other coloring agents simultaneously in the colorant carrier, or separately dispersing the colorant carrier in the colorant carrier.

(Dispersion auxiliary)

When the colorant is dispersed in the colorant carrier, it may suitably contain a dispersion aid such as a pigment derivative, a resin type dispersant, a surfactant and the like. Since the dispersing aid has a large effect of preventing re-aggregation of the coloring agent after dispersion, the coloring composition obtained by dispersing the coloring agent in the coloring agent carrier using the dispersing aid improves the contrast and viscosity stability.

When a resinous dispersant and a surfactant are added, the amount is preferably 0.1 to 55 parts by mass, more preferably 0.1 to 45 parts by mass, based on 100 parts by mass of the colorant. When the blending amount of the resin type dispersant and the surfactant is less than 0.1 part by mass, it is difficult to obtain the added effect, and when the blending amount is more than 55 parts by mass, the dispersion may be affected by the excessive dispersion auxiliary.

(Optional component)

The coloring composition may further contain, for example, the following components in addition to the dispersion aid as optional components. Specific examples of the arbitrary components are as follows.

(Photopolymerizable monomer and / or photopolymerization initiator)

The coloring composition can be used as a photosensitive coloring composition by further adding a photopolymerizable monomer and / or a photopolymerization initiator.

The photopolymerizable monomer used in the photosensitive coloring composition includes a monomer or an oligomer which is cured by ultraviolet rays or heat to produce a transparent resin. These may be used alone or in combination of two or more.

The blending amount of the monomer is preferably 5 to 400 parts by mass with respect to 100 parts by mass of the colorant, and more preferably 10 to 300 parts by mass from the viewpoint of photocurability and developability.

When the composition is cured by ultraviolet irradiation and the filter segment is formed by photolithography, a photopolymerization initiator may be added to the photosensitive coloring composition to prepare a solvent-developing type or alkali-developing type coloring resist composition .

The photopolymerization initiator is preferably 2 to 200 parts by mass based on 100 parts by mass of the colorant in the photosensitive color composition, more preferably 3 to 150 parts by mass from the viewpoint of photocurability and developability.

(Sensitizer)

The sensitizing coloring composition may contain a sensitizer.

When the sensitizer is used, the blending amount is preferably 3 to 60 parts by mass with respect to 100 parts by mass of the photopolymerization initiator contained in the photosensitive coloring composition, and more preferably 5 to 50 parts by mass from the viewpoint of photocurability and developability.

(Polyfunctional thiol)

The photosensitive coloring composition may contain a polyfunctional thiol which acts as a chain transfer agent. The polyfunctional thiol is preferably a compound having two or more thiol groups.

The content of the polyfunctional thiol is preferably from 0.1 to 30 mass%, more preferably from 1 to 20 mass%, based on the mass of the total solid content of the photosensitive coloring composition (100 mass%). If the content of the polyfunctional thiol is less than 0.1% by mass, the effect of adding the polyfunctional thiol may not be sufficiently obtained. If the content of the polyfunctional thiol is more than 30% by mass, the sensitivity may be too high.

(Antioxidant)

The coloring composition may contain an antioxidant. The antioxidant prevents the photopolymerization initiator and the thermosetting compound contained in the coloring composition from being oxidized by the thermal process during the thermosetting or ITO annealing, thereby increasing the transmittance of the coating film. Therefore, by including an antioxidant, it is possible to prevent yellowing due to oxidation during the heating step, and to obtain a high transmittance of the coating film.

The content of the antioxidant is more preferably 0.5 to 5.0% by mass based on the solid content of the coloring composition (100% by mass), since the lightness and sensitivity are good.

(Amine compound)

The coloring composition may contain an amine compound having an action of reducing dissolved oxygen.

(Leveling agent)

In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the coloring composition. The content of the leveling agent is usually preferably 0.003 to 0.5 mass% based on the total mass of the coloring composition (100 mass%).

(Hardener, hardening accelerator)

The coloring composition may contain a curing agent, a curing accelerator or the like, if necessary, to assist curing of the thermosetting resin. The content of the curing accelerator is preferably 0.01 to 15 parts by mass relative to 100 parts by mass of the thermosetting resin.

(Other additives)

The coloring composition may contain a storage stabilizer to stabilize the viscosity over time. Further, in order to improve the adhesion with the transparent substrate, an adhesion improving agent such as a silane coupling agent may be contained.

The storage stabilizer can be used in an amount of 0.1 to 10% by mass based on the total amount of the colorant (100% by mass).

The adhesion promoter can be used in an amount of 0.01 to 10% by mass, preferably 0.05 to 5% by mass based on the total amount of the colorant in the coloring composition (100% by mass).

Further, in addition to the above optional components, any of the following optional components may be contained.

(Removal of coarse particles)

The coloring composition can be obtained by coarse separation, sintering filter, filtration with a membrane filter, or the like, and coarse particles of 5 mu m or more, preferably coarse particles of 1 mu m or more, more preferably coarse particles of 0.5 mu m or more, It is preferable to carry out the removal. It is preferable that the coloring composition does not contain particles substantially 0.5 mu m or more. More preferably 0.3 mu m or less.

[Fourth Embodiment]

(Coloring composition for color filter)

The coloring composition for a color filter of the fourth embodiment contains the diketopyrrolopyrrole-based pigment composition of the second embodiment. The diketopyrrolopyrrole-based pigment composition of the second embodiment can be used as a coloring composition by using in combination with a binder resin and an organic solvent. In addition, a colorant other than the diketopyrrolopyrrole-based pigment composition of the second embodiment may be used in combination. For example, it is also possible to use the diketopyrrolopyrrole-based pigment composition of the first embodiment.

(Other coloring agent)

The coloring composition may be used alone or in combination of two or more pigments or dyes other than the diketopyrrolopyrrole-based pigment composition of the second embodiment within the range of not deteriorating the effect for the purpose of preparing chromaticity and the like.

When the colorant other than the diketopyrrolopyrrole pigment composition is used in combination, the diketopyrrolopyrrole pigment composition of the second embodiment is in the range of 40% by mass to 100% by mass in the total amount of the colorant (100% by mass) desirable. More preferably, it is in the range of 60% by mass to 100% by mass. When the diketopyrrolopyrrole-based pigment composition of the second embodiment is 40 mass% or less, excellent effects of brightness and contrast ratio may not be sufficiently exhibited.

(Binder resin)

As the binder resin contained in the coloring composition, conventionally known thermoplastic resins and thermosetting resins can be mentioned. Examples of the binder resin include the same binder resin as the binder resin in the third embodiment. The preferable amount of the binder resin used is also the same as in the third embodiment.

(Organic solvent)

An organic solvent is contained in the coloring composition in order to easily disperse and penetrate the coloring agent in the coloring agent carrier and to form a filter segment on the substrate such as a glass substrate so as to have a dry film thickness of 0.2 to 5 μm. The organic solvent can be selected in the same manner as the selection method in the third embodiment. The preferable amount of the organic solvent used is also the same as in the third embodiment.

(Production method of coloring composition)

The coloring composition of the fourth embodiment can be produced by the same production method as the coloring composition of the third embodiment.

(Optional component)

The coloring composition of the fourth embodiment may contain optional components such as a dispersion aid, a photopolymerizable monomer and / or a photopolymerization initiator, a sensitizer, a polyfunctional thiol, an antioxidant, an amine compound, a leveling agent, a curing agent, a curing accelerator, May be contained. Specific examples of these optional components are the same as in the third embodiment. Preferred examples, preferred amounts and the like are also the same as in the third embodiment.

(Removal of coarse particles)

The coloring composition of the fourth embodiment is preferably subjected to removal of coarse particles in the same manner as the coloring composition of the third embodiment.

[Fifth Embodiment]

(Coloring composition for color filter)

The coloring composition for a color filter according to the fifth embodiment comprises a pigment (A), a binder resin (CB) and a solvent, wherein the pigment (A) comprises the pigment (A1) , And the binder resin (CB) includes an alkali-soluble photosensitive resin (C-B1). The coloring composition for a color filter of the fifth embodiment can be used as a photosensitive coloring composition.

As a result of intensive studies, the inventors of the present invention have found that C.I. By using a coloring composition comprising a diketopyrrolopyrrole bromide pigment (formula (1)) and an alkali-soluble photosensitive resin in place of Pigment Red 254 (chlorinated diketopyrrolopyrrole pigment), high brightness and high contrast ratio can also be obtained by heating It is possible to obtain a color filter having a high definition filter segment in which crystal precipitation is suppressed.

According to the fifth embodiment, crystal precipitation of the diketopyrrolopyrrole pigment is not caused even by a heating process at a high brightness and a high contrast ratio, and the performance required for forming a good filter segment such as sensitivity and linearity It is possible to provide a coloring composition for a color filter excellent in balance.

(Pigment (A))

 The pigment (A) includes the pigment (A1) shown in the formula (1).

&Quot; Pigment (A1) "

[Chemical Formula 39]

The brominated diketopyrrolopyrrole pigment, which is the pigment (A1) shown in the formula (1), can be produced by the same method as in the first embodiment. By using the pigment (A1) shown in the formula (1), a red coloring composition having high brightness and a high contrast ratio can be obtained.

As the pigment (A), the diketopyrrolopyrrole-based pigment composition according to the first embodiment may be used, or the diketopyrrolopyrrole-based pigment composition according to the second embodiment may be used.

"Other pigment"

As the coloring composition, pigments other than the pigment (A1) may be used in combination. As such pigments, organic or inorganic pigments may be used alone or in combination of two or more. Among the pigments, pigments having a high coloring property and a high heat resistance are preferable, and organic pigments are generally used.

Examples of usable organic pigments include diketopyrrolopyrrole pigments other than the pigment (A1); Azo pigments such as azo, disazo and polyazo; Phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine, and non-metal phthalocyanine; Anthraquinone pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavanthrone, anthanthrone, indanthrone, pyranthrone, violanthrone and the like; Quinacridone pigments; Dioxazine pigments; Perinone pigments; Perylene pigments; Thioindigo pigments; Isoindoline pigments; Isoindolinone pigments; Quinophthalone pigments; Threne pigments; Metal complex system pigments, and the like.

Among these pigments, pigments selected from the group consisting of diketopyrrolopyrrole pigments other than the pigment (A1), azo pigments, anthraquinone pigments, perylene pigments, quinacridone pigments, benzimidazolone pigments and quinoline pigments It is preferable to include at least one kind or more. As in the case of the pigment (A1), they can be easily adjusted in color by adjusting the compounding ratio of the red pigment. Further, they are preferable since they have excellent light resistance and heat resistance.

Examples of the inorganic pigments include barium sulfate, zinc oxide, lead sulfate, yellow lead, zinc sulfur, spinach (red iron oxide (III)), cadmium red, Metal oxide powders such as chrome green, cobalt green, umber, titanium black, synthetic iron black, titanium oxide, and tetrahedral iron, metal sulfide powders, and metal powders. The inorganic pigment is used in combination with an organic pigment in order to ensure good coating properties, sensitivity, developability and the like while balancing the saturation and lightness.

The content of the pigment (A1) represented by the formula (1) is preferably 40 to 100% by weight, more preferably 50 to 100% by weight, of the total amount of the pigment (A) , And more preferably 60 to 100 wt%. This content range is preferable in that it can sufficiently express the color characteristic of the pigment (A1) represented by the formula (1).

The content of the preferable pigment (A) component is 10% by weight or more, more preferably 15% by weight or more, and most preferably 20% by weight or less, from the viewpoint of obtaining sufficient color reproducibility out of 100% by weight of the total nonvolatile component of the coloring composition. By weight or more. Further, the content of the pigment (A) is preferably 90% by weight or less, more preferably 80% by weight or less, and most preferably 70% by weight or less, from the standpoint of improving the stability of the coloring composition.

The photosensitive coloring composition may contain a dye within a range that does not lower the heat resistance for coloring.

"Minification of pigment"

The pigment (A1) and other pigments are preferably used after being finely ground.

The primary particle size of the finely divided pigment is preferably 20 nm or more in view of good dispersion in the colorant carrier. Further, it is preferably 100 nm or less in that a filter segment having a high contrast ratio can be formed. A particularly preferable range is 25 to 85 nm.

On the other hand, the primary particle size of the pigment can be measured by a method of directly measuring the size of primary particles from an electron microscope photograph of the pigment by a TEM (transmission electron microscope). Specifically, the minor axis diameter and the major axis diameter of the primary particles of each pigment are measured, and the average is defined as the particle diameter of the pigment particles. Next, for 100 or more pigment particles, the volume of each particle is obtained by approximating the cubic of the obtained particle size to the average volume, and the length of one side of the cube having the average volume is defined as the average primary particle diameter.

Further, the specific surface area by the BET method of these finely divided pigment is preferably from ^{60m 2 / g ~ 130m 2 /} g. When the specific surface area of the pigment (A) is smaller than the lower limit value, the luminance and the contrast ratio of the color filter may be lowered. When the specific surface area is larger than the upper limit value, pigment dispersion becomes difficult, and stability as a coloring composition is maintained and fluidity may become difficult to secure. As a result, the characteristics of the luminance and the contrast ratio of the color filter tend to deteriorate.

Examples of means for controlling the specific surface area of the pigment include a method in which the pigment is mechanically pulverized to control the specific surface area (hereinafter referred to as a "grinding method") and the pigment is dissolved in a good solvent (a good solvent) A method of depositing a pigment having a surface area (referred to as a precipitation method) and a method of producing a pigment having a desired specific surface area at the time of synthesis (referred to as a synthetic precipitation method). Depending on the method of synthesis and chemical properties of the pigment to be used, an appropriate method can be selected for each pigment. As a method of controlling the specific surface area of the pigment contained in the coloring composition, one of the above methods may be used.

The pigment used in the fifth embodiment is preferably finely ground by a salt milling treatment in a printing method. By using such a pigment, a filter segment having a higher contrast ratio can be formed. The salt milling treatment can be carried out in the same manner as in the diketopyrrolopyrrole pigment composition.

(Binder resin (C-B))

The binder resin (C-B) disperses the pigment (A) and contains an alkali-soluble photosensitive resin (C-B1).

&Quot; Alkali-soluble photosensitive resin (C-B1) "

Examples of the alkali-soluble photosensitive resin (C-B1) include a resin into which an ethylenically unsaturated double bond is introduced by the following method (C-i) or (C-ii).

≪ Method (Ci) >

Examples of the method (Ci) include a method in which a carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond is added to a side chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group and at least one other monomer There is a method of reacting a produced hydroxyl group with a polybasic acid anhydride to introduce an ethylenically unsaturated double bond to give a photosensitive resin function and introducing a carboxyl group having an alkali soluble function.

Examples of the ethylenically unsaturated monomer having an epoxy group include glycidyl (meth) acrylate, methylglycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, 3,4- Butyl (meth) acrylate, and 3,4-epoxycyclohexyl (meth) acrylate. These may be used alone or in combination of two or more. From the viewpoint of reactivity with an unsaturated monobasic acid in the next step, glycidyl (meth) acrylate is preferred.

Examples of the unsaturated monobasic acid include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl, alkoxyl, halogen, nitro, cyano And a monocarboxylic acid such as a substituent. These may be used alone or in combination of two or more.

Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc. These may be used alone or in combination of two or more. If necessary, by using a tricarboxylic acid anhydride such as trimellitic anhydride or by using a tetracarboxylic acid dianhydride such as pyromellitic dianhydride to hydrolyze the remaining anhydride group It is possible. Further, as the polybasic acid anhydride, use of tetrahydrophthalic anhydride having an ethylenically unsaturated double bond, or maleic anhydride can further increase the ethylenically unsaturated double bond.

As a method similar to the method (Ci), for example, an ethylenically unsaturated monomer having an epoxy group is added to a part of side chain carboxyl groups of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group with one or more other monomers, To introduce an ethylenically unsaturated double bond and a carboxyl group.

≪ Method (C-ii) >

As the method (C-ii), an ethylenic unsaturated monomer having a hydroxyl group is used, and a copolymer of an unsaturated monobasic acid having another carboxyl group and another monomer is added to the side chain hydroxyl group of the copolymer, There is a method of reacting an isocyanate group of an unsaturated monomer.

Examples of the ethylenic unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (Meth) acrylates such as glycerol (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, and the like. . Also, polyether mono (meth) acrylates obtained by addition polymerization of the above hydroxyalkyl (meth) acrylates with ethylene oxide, propylene oxide and / or butylene oxide, (poly) gamma -valerolactone, (poly) ester mono (meth) acrylate to which? -caprolactone and / or (poly) 12-hydroxystearic acid is added can also be used. 2-hydroxyethyl (meth) acrylate, or glycerol (meth) acrylate is preferable from the standpoint of coating layer inhibition.

Examples of the ethylenically unsaturated monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate and 1,1-bis [(meth) acryloyloxy] ethyl isocyanate. , Or two or more types may be used in combination.

Examples of the alkali-soluble photosensitive resin (C-B1) include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, and? -Chloroacrylic acid, and unsaturated monocarboxylic acids such as maleic acid and unsaturated dicarboxylic acids such as fumaric acid, And a resin obtained by using a monomer having an ethylenically unsaturated double bond. Examples of the other ethylenic unsaturated monomer which is a precursor of the alkali-soluble photosensitive resin (C-B1) include methyl (meth) acrylate, ethyl (meth) acrylate, n- (Meth) acrylate, isobutyl (meth) acrylate, isobutyl (meth) acrylate, isobutyl (meth) acrylate, (Meth) acrylate, hepta (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (Meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, isostearyl Acrylate, or oleyl (meth) There can be mentioned an alkyl or alkenyl (meth) acrylates such as methacrylate, according to the purposes, and also select a different ethylenically unsaturated monomer is not limited to these, it may be used in combination of two or more. Of these, methyl (meth) acryl methacrylate or ethyl (meth) acrylate is preferable from the viewpoint of pigment dispersibility.

The weight average molecular weight (Mw) of the alkali-soluble photosensitive resin (C-B1) is preferably in the range of 5,000 to 100,000, more preferably 5,000 to 80,000, and still more preferably 5,000 to 30,000. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw / Mn is preferably 10 or less. When the weight average molecular weight (Mw) of the alkali-soluble photosensitive resin (C-B1) exceeds 100,000, the interaction between the resins becomes strong and the viscosity of the coloring composition for a color filter becomes high. When the weight-average molecular weight (Mw) is less than 5,000, developability and adhesiveness to substrates such as glass may be deteriorated.

The acid value of the alkali-soluble photosensitive resin (C-B1) is preferably 20 to 300 KOH-mg / g from the viewpoints of dispersibility, permeability, developability and resistance of the pigment. If the acid value is less than 20 KOH-mg / g, solubility in a developing solution is low, and it may become difficult to form a fine pattern. If it exceeds 300 KOH-mg / g, a fine pattern may not be left.

The content of the alkali-soluble photosensitive resin (C-B1) is preferably 10 to 100% by weight, more preferably 20 to 100% by weight, and still more preferably 40 to 100% by weight, based on the total 100% by weight of the binder resin (CB) 100% by weight. When the content of the alkali-soluble photosensitive resin (C-B1) in the binder resin (C-B) is 10% by weight or more, the effect of high coloring composition and high contrast ratio is easily obtained.

"Other resin"

The binder resin (C-B) may contain other resin than the alkali-soluble photosensitive resin (C-B1). As the other resin, a resin having a transmittance of preferably 80% or more, more preferably 95% or more is preferable in the entire wavelength range of 400 to 700 nm which is a visible light region. For example, a thermoplastic resin, a thermosetting resin and the like, which may be used alone or in combination of two or more.

Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, polyester resin , Acrylic resin, alkyd resin, polystyrene, polyamide resin, rubber resin, cyclic rubber resin, cellulose, polyethylene, polybutadiene, polyimide resin and the like. Examples of the thermosetting resin include an epoxy resin, a benzoguanamine resin, a rosin-modified maleic resin, a rosin-modified fumaric acid resin, a melamine resin, a urea resin, and a phenol resin.

Examples of the thermosetting resin include benzoguanamine resin, rosin-modified maleic resin, rosin-modified fumaric acid resin, melamine resin, urea resin and phenol resin.

Further, it is also possible to use an alkali-soluble resin copolymerized with an ethylenically unsaturated monomer containing an acidic group in combination. Examples of such an alkali-soluble resin include resins having an acidic group such as a carboxyl group and a sulfone group. Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an? -Olefin / (maleic anhydride) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or an isobutylene / Maleic acid copolymer, and the like. Among them, at least one resin selected from an acrylic resin having an acidic group and a styrene / styrenesulfonic acid copolymer, particularly an acrylic resin having an acidic group, is suitably used because it has high heat resistance and transparency.

The binder resin (C-B) may be used in an amount of 20 to 400 parts by weight, preferably 50 to 250 parts by weight, based on 100 parts by weight of the pigment (A) in the coloring composition.

(solvent)

The solvent is used for easily dispersing the pigment (A) in the binder resin (CB) and coating the colored composition on a substrate such as a glass substrate so as to have a dry film thickness of 0.2 to 5 μm to facilitate formation of filter segments do. As the solvent, an organic solvent is preferable.

The content of the solvent is preferably 800 to 4000 parts by weight with respect to 100 parts by weight of the pigment (A), and it is possible to form a filter segment having a desired uniform film thickness by controlling the coloring composition to an appropriate viscosity .

(Production of photosensitive coloring composition)

The photosensitive coloring composition is obtained by dispersing the pigment (A) in a pigment carrier such as a binder resin (CB) and a solvent, preferably with a pigment dispersing agent, in various dispersion such as a three roll mill, a two roll mill, a sand mill, a kneader, (CD), a binder resin (CB), a photopolymerizable compound, and optionally, a sensitizer (CE), a polyfunctional thiol, an ultraviolet ray Absorbing agent, polymerization inhibitor, storage stabilizer, and other components may be mixed and stirred. Further, the coloring composition comprising two or more kinds of pigments may be prepared by mixing the respective pigment dispersions separately finely dispersed in a pigment carrier and / or a solvent, and further adding a photopolymerization initiator (CD), a photopolymerizable compound, .

(Pigment dispersant (C-C))

When the pigment (A) is dispersed in the binder resin (C-B) and / or the solvent, a pigment dispersant (C-C) such as a resin type pigment dispersant, a pigment derivative or a surfactant can be suitably contained. The pigment dispersant (CC) is excellent in the dispersion of the pigment and has an effect of preventing the re-aggregation of the pigment after dispersion. Therefore, the pigment is dispersed in the binder resin (CB) and / or the solvent by using the pigment dispersant When a colored composition is used, a color filter having excellent transparency can be obtained.

The coloring composition preferably contains an acidic resin type pigment dispersant, in particular, from the viewpoint of stability of the coloring composition. Use of an acidic resin pigment dispersant and a basic pigment derivative are preferable because a filter segment having excellent fluidity and stability as well as high brightness and a high contrast ratio can be obtained by using the colored pigment derivative in combination.

The pigment dispersant (C-C) may be used in an amount of 0.1 to 40 parts by weight, preferably 0.1 to 30 parts by weight, based on 100 parts by weight of the pigment (A).

&Quot; Resin type pigment dispersant, surfactant "

Examples of the resin type pigment dispersant and the surfactant are as follows.

"Dye derivative"

Examples of the pigment derivative include a compound in which a phthalimide methyl group, which may have a basic substituent, an acidic substituent or a substituent, is introduced into an organic pigment, anthraquinone, acridone or triazine. The structure thereof is, for example, a compound represented by the following formula (50), among which a pigment derivative is preferable.

P-Lm Equation (50)

[In the formula (50)

P is an organic pigment residue, an anthraquinone residue, an acridone residue or a triazine residue

L: a basic substituent, an acidic substituent, or a phthalimide methyl group which may have a substituent

m is an integer of 1 to 4]

The pigment derivative is disclosed in, for example, Japanese Patent Publication S63-305173, Japanese Patent Publication S57-15620, Japanese Patent Publication S59-40172, Japanese Patent Publication S63-17102, Japanese Patent Publication H5- 9469 can be used. These may be used alone or in admixture of two or more.

Among the organic pigments constituting the organic pigment residue of P in the formula (50), the following are listed.

Examples of the organic pigments constituting the organic pigment residue of P include diketopyrrolopyrrole pigments; Azo pigments such as azo, disazo and polyazo; Phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine, zinc phthalocyanine, halogenated zinc phthalocyanine and non-metal phthalocyanine; Anthraquinone pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavanthrone, anthanthrone, indanthrone, pyranthrone, and biorantrone; Quinacridone pigments; Dioxazine pigments; Perinone pigments; Perylene pigments; Thioindigo pigments; Isoindoline pigments; Isoindolinone pigments; Threne pigments; Quinophthalone pigments; Dioxazine pigments; Metal complex system pigments, and the like.

Among them, a dye derivative having a basic substituent, in which L in the formula (50) is a basic substituent, can be preferably used. By including a pigment derivative having a basic substituent, even a pigment which is difficult to disperse without a pigment derivative having a basic substituent is preferable because it can be made into a pigment composition excellent in dispersibility, fluidity and storage stability. The pigment composition can be effectively dispersed by the synergistic effect of the acidic resinous dispersant and the pigment derivative having a basic substituent to provide a pigment composition excellent in fluidity and storage stability.

Among the basic substituents, L is preferably a substituent selected from the group represented by formulas (51), (52) and (53).

(40)

(41)

(42)

[Of the formulas (51) to (53)

X _{is, -SO 2 -, -CO-, -CH} 2 -, -CH 2 NHCOCH 2 -, -CH 2 NHSO 2 CH 2 -, or a direct bond,

Y is -NH-, -O-, or a direct bond,

k is an integer of 1 to 10,

Y ¹ is -NH-, -NR ⁵⁸ -Z-NR ⁵⁹ -, or a direct bond,

R ⁵⁸ and R ⁵⁹ are each independently a hydrogen bond, an alkyl group having 1 to 36 carbon atoms which may have a substituent, an alkenyl group having 2 to 36 carbon atoms which may have a substituent, or a phenyl group which may have a substituent,

Z is an alkylene group which may have a substituent or an arylene group which may have a substituent,

R ⁵⁰ and R ⁵¹ each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, or R ⁵⁰ and R ⁵¹ , Is a heterocycle which may have a substituent, including nitrogen, oxygen, or a sulfur atom,

R ⁵² , R ⁵³ , R ⁵⁴ and R ⁵⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, An arylene group having 6 to 20 carbon atoms,

R ⁵⁶ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent,

R ⁵⁷ is a substituent represented by the formula (51) or a substituent represented by the formula (52)

Q is a hydroxyl group, an alkoxyl group, a substituent represented by the formula (51), or a substituent represented by the formula (52).

Examples of the amine component used for forming the substituent represented by the formulas (51) to (53) include the same amine component as the amine component in the first embodiment.

The pigment derivative having a basic substituent can be synthesized by various synthetic routes. For example, it is possible to introduce the substituent represented by the formulas (54) to (57) into the organic pigment and then react with the substituent to form the substituent represented by the formulas (51) to (53) For example, N, N-dimethylaminopropylamine, N-methylpiperazine, diethylamine or 4- [4-hydroxy-6- [3- (dibutylamino) propylamino] Triazin-2-ylamino] aniline, and the like.

Equation (54): -SO ₂ Cl

Equation (55): -COCl

Equation _{(56): -CH 2 NHCOCH 2} Cl

Formula (57): -CH ₂ Cl

In the reaction of the substituents of the formulas (54) to (56) with the amine component, some of the substituents of the formulas (54) to (57) may be hydrolyzed to replace the chlorine substituted by a hydroxyl group. In this case, the formulas (54) and (55) are a sulfonic acid group and a carboxylic acid group, respectively, but they may be in the form of a free acid or may be a salt with a mono- to trivalent metal or with the monoamine have.

When the organic pigment is an azo-based pigment, the substituent represented by the formulas (51) to (53) is introduced in advance into the diazo component or the coupling component, and then the coupling reaction is carried out to obtain the azo- .

The triazine derivative having a basic substituent can be synthesized by various synthetic routes. For example, an amine component that uses cyanuric chloride as a starting material and forms a substituent represented by any of formulas (51) to (53) in at least one of chlorine atoms in cyanuric chloride, such as N, N-dimethylamino Propylamine or N-methylpiperazine, and then reacting the remaining chlorine of cyanuric chloride with various amines or alcohols.

(Optional component)

In addition to the pigment dispersant, the coloring composition of the fifth embodiment may further contain, for example, the following components as optional components. Specific examples of the arbitrary components are as follows.

(Photopolymerization initiator (CD))

The photosensitive coloring composition can be prepared in the form of an alkali developing photosensitive coloring composition by adding the photopolymerization initiator (C-D) to cure the composition by ultraviolet irradiation and form a filter segment by photolithography.

The content of the photopolymerization initiator (C-D) is preferably 5 to 200 parts by weight based on 100 parts by weight of the pigment (A), more preferably 10 to 150 parts by weight from the viewpoint of photocurability and developability.

(Sensitizer)

The sensitizing coloring composition may contain a sensitizer.

The content of the sensitizer is preferably 3 to 60 parts by weight based on 100 parts by weight of the photopolymerization initiator (C-D) contained in the photosensitive coloring composition, more preferably 5 to 50 parts by weight from the viewpoint of photocurability and developability.

(Photopolymerizable compound)

The photosensitive coloring composition may contain a photopolymerizable compound. The photopolymerizable compound includes a monomer or an oligomer which is cured by ultraviolet rays or heat to generate a resin.

The content of the photopolymerizable monomer (C-C) is preferably 10 to 300 parts by weight based on 100 parts by weight of the pigment (A), more preferably 10 to 200 parts by weight from the viewpoint of photocurability and developability.

(Polyfunctional thiol)

The photosensitive coloring composition may contain a polyfunctional thiol (C-F). The polyfunctional thiol is a compound having two or more thiol (SH) groups. The multifunctional thiol is used together with the above-mentioned photopolymerization initiator (CD) to generate a thiyl radical which acts as a chain transfer agent in the radical polymerization process after light irradiation and is unlikely to be inhibited by polymerization due to oxygen, The resulting photosensitive coloring composition has a high sensitivity. Particularly, a polyfunctional aliphatic thiol in which an SH group is bonded to an aliphatic group such as methylene or ethylene group is preferable.

The content of the polyfunctional thiol is preferably from 0.05 to 100 parts by weight, more preferably from 1.0 to 50.0 parts by weight, based on 100 parts by weight of the pigment (A). By using the polyfunctional thiol in an amount of 0.05 parts by weight or more, it is possible to obtain better developing resistance. In the case of using a monofunctional thiol having one thiol (SH) group, such phenomenon resistance improvement is not obtained.

(Ultraviolet absorber)

The photosensitive coloring composition may contain an ultraviolet absorber. By containing an ultraviolet absorber, the shape and resolution of the pattern can be controlled.

The content of the ultraviolet absorber may be 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight, based on 100 parts by weight of the pigment (A). By using 0.01 parts by weight or more of the ultraviolet absorber, better resolution can be obtained.

(Polymerization inhibitor)

The photosensitive coloring composition may contain a polymerization inhibitor. By containing a polymerization inhibitor, the shape and resolution of the pattern can be controlled.

The content of the polymerization inhibitor may be 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight, based on 100 parts by weight of the pigment (A). By using at least 0.01 part by weight of the polymerization inhibitor, better resolution can be obtained.

(Storage stabilizer)

The photosensitive coloring composition may contain a storage stabilizer. By containing a storage stabilizer, the viscosity of the composition over time can be stabilized.

The content of the storage stabilizer may be 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight, based on 100 parts by weight of the pigment (A). By using the storage stabilizer in an amount of 0.01 part by weight or more, the stability with time of the colored composition is improved.

(Other additives)

The photosensitive coloring composition may contain an adhesion improving agent such as a silane coupling agent or an amine compound having a function of reducing dissolved oxygen in order to improve adhesion with a transparent substrate.

The adhesion-improving agent may be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the pigment (A).

Further, in addition to the above optional components, any of the following optional components may be contained.

(Removal of coarse particles)

The coloring composition of the fifth embodiment is preferably subjected to removal of coarse particles in the same manner as the coloring composition of the third embodiment.

[Sixth Embodiment]

The coloring composition for a color filter according to the sixth embodiment is a coloring composition for a color filter comprising a pigment (A), a binder resin (DB) and a solvent, wherein the pigment (A) (D-B1) containing the pigment (A1) and the binder resin (DB) having the following constitutional units (D-b1) to (D-b3). The coloring composition for a color filter of the sixth embodiment can be used as a photosensitive coloring composition.

As a result of intensive studies, the inventors of the present invention have found that C.I. By using a coloring composition comprising a diketopyrrolopyrrole bromide pigment and a binder resin having a specific structure in place of Pigment Red 254 (a chlorinated diketopyrrolopyrrole pigment), crystal precipitation can be achieved by a heating process with high definition, high contrast, It has been found that a color filter having a suppressed fixed three filter segments is obtained.

According to the sixth embodiment, crystal precipitation of the diketopyrrolopyrrole pigment is not caused even by a heating process at a high brightness and a high contrast ratio, and when it is used as a photosensitive coloring composition, It is possible to provide a coloring composition for a color filter which is excellent in balance of performance required when forming the filter segments.

(Pigment (A))

The pigment (A) is the same pigment as the pigment (A) in the fifth embodiment, and can be obtained by the same method as the production method in the fifth embodiment.

By using the combination of the pigment (A1) and the resin (D-B1) shown in the formula (1), a red coloring composition having high brightness and a high contrast ratio can be obtained.

The colorant composition of the sixth embodiment can be used in combination with the pigment (A1) and other pigments in the same manner as the colorant composition of the fifth embodiment. Further, the pigment (A1) and other pigments are used in finely divided form desirable.

(Binder resin (D-B))

&Quot; Resin (D-B1) "

The binder resin (D-B) contained in the coloring composition for a color filter is characterized by containing a resin (D-B1) having the following structural units (D-b1) to (D-b3).

(D-b1) 2 to 60% by weight of a constituent unit having a carboxyl group

(D-b2) 2 to 80% by weight of a structural unit having an aromatic ring group represented by the formula (D-2) or (D-3)

(D-b3) 2 to 60% by weight of a constituent unit having an aliphatic ring group represented by the formula (D-4) or (D-5)

(43)

(44)

[In the formulas (D-2) and (D-3), R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a benzene ring. The broken line in formula (D-3) represents a cyclic structure adjacent to the benzene ring and containing at least one saturated or unsaturated heterocycle which may have a substituent.]

[Chemical Formula 45]

(46)

Hereinafter, the structural unit (D-b1), the structural unit (D-b2) and the structural unit (D-b3) will be described in order. In this embodiment, the content by weight% of each constituent unit is the weight percentage of the precursor which brings each constituent unit to the resin (D-b1).

≪ Construction unit (D-b1) >

The structural unit (D-b1) has a carboxyl group and functions as an alkali-soluble site at the time of development. Based on the weight of all the constituent units of the binder resin (D-B1), the constituent unit (D-b1) is from 2 to 60% by weight from the viewpoints of developability and dispersion stability. If it is less than 2% by weight, the removability of the unexposed portion due to the alkaline developer becomes insufficient and the dispersion stability deteriorates. On the other hand, if it exceeds 60% by weight, the dissolution rate with respect to the alkali developing solution becomes faster and the photosensitive part is dissolved up to the exposed part.

Examples of the precursor of the structural unit (D-b1) having a carboxyl group include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, and? -Chloroacrylic acid, and carboxyl groups such as unsaturated dicarboxylic acids such as maleic acid and fumaric acid And compounds having an ethylenically unsaturated double bond. Further, an unsaturated dicarboxylic acid anhydride such as maleic anhydride may be used which has been half-esterified with a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. Among them, (meth) acrylic acid is more preferable, and methacrylic acid is most preferable from the viewpoint of polymerizability (ease of control such as molecular weight). This can be used alone or in combination of two or more kinds.

(D-b1) even when the carboxyl group is converted to an ester bond or the like in the step of forming the binder resin (D-B) even in the precursor containing a carboxyl group in the raw material stage.

≪ Structural unit (D-b2) >

The structural unit (D-b2) has a cyclic structure of an aromatic ring group represented by the formula (D-2) or (D-3) and functions as an affinity site for a pigment composition comprising a pigment or a pigment and a dispersant . Based on the weight of all the constituent units of the binder resin (D-B), the constituent unit (D-b2) is from 20 to 80% by weight from the viewpoint of the developability and the quality of the filter segment. If it is less than 20% by weight, there is a problem that the affinity for a pigment composition composed of a pigment or a pigment and a dispersing agent is insufficient and a high quality color filter is not obtained or the resistance of the filter segment deteriorates. If the amount exceeds the above range, the dissolution rate with respect to the alkali developing solution becomes slow, and the developing time is long and the productivity of the color filter deteriorates.

The bromine atom contained in the structure of the pigment (A1) shown in the formula (1) has a higher polarization ratio than a chlorine atom. Accordingly, it is expected that the constituent unit (D-b2) containing an aromatic ring group exhibits a strong interaction such as affinity with respect to the π electromagnetic field for the chlorinated diketopyrrolopyrrole pigment (CI Pigment Red 254) have.

(47)

(48)

[In the formulas (D-2) and (D-3), R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a benzene ring. The broken line in formula (D-3) represents a cyclic structure adjacent to the benzene ring and containing at least one saturated or unsaturated heterocycle which may have a substituent.]

Examples of the precursor of the structural unit (D-b2) include styrene,? -Methylstyrene, divinylbenzene, indene, acetylnaphthene, benzyl acrylate, benzyl methacrylate, bisphenol A diglycidyl ether di (meth) (Meth) acrylic acid ester of methylol melamine, ethylenically unsaturated monomer represented by the formula (D-6), and the like.

(49)

Wherein R ¹ is a hydrogen atom or a methyl group, R ² is an alkylene group having 2 or 3 carbon atoms, R ³ is an alkyl group having 1 to 20 carbon atoms which may have a benzene ring , and n is an integer of 1 to 15.]

As the ethylenically unsaturated monomer represented by the formula (D-6), for example,

R ^{1 is a} hydrogen atom, R ^{2 is an} ethylene group, R ^{3 is a} methyl group, n is 1 or 2, and NP-2 is an alkyl group having ^{1 to 10} carbon atoms. n-nonylphenoxypolyethylene glycol acrylate, R ¹ : hydrogen atom, R ² : ethylene group, R ³ : n-nonyl group, n = 2], N-177E ^1: a hydrogen atom, R ^2: an ethylene group, R ^3: n- nonyl, n = 16 ~ 17] or PHE [phenoxyethyl acrylate, R ^1: a hydrogen atom, R ^2: an ethylene group, R ^3: Hydrogen atom, n = 1],

(EO 1 mol), R ¹ : hydrogen atom, R ² : ethylene group, R ³ : hydrogen atom, n = 1] or Ebecryl 110 [ethoxylated phenyl acrylate 2mol), R ^1: a hydrogen atom, R ^2: an ethylene group, R ^3: a hydrogen atom, n = 2],

Toagosei Co., Ltd. The Aronix M-101A [phenol EO-modified (n ≒ 2) acrylate, R ^1: a hydrogen atom, R ^2: an ethylene group, R ^3: a hydrogen atom, n ≒ 2], [M-102 (N? 4) acrylate, R ^{1 is a} hydrogen atom, R ^{2 is an} ethylene group, R ^{3 is a} hydrogen atom, n is about 4, M-110 is para-cumylphenol EO- , R ^1: a hydrogen atom, R ^2: an ethylene group, R ^3: p-cumyl, n ≒ 1], 111 [M-n- nonyl phenol EO-modified (n ≒ 1) acrylate, R ^1: a hydrogen atom, R ² : an ethylene group, R ^3: n- nonyl, n ≒ 1], 113 [M-n- nonyl phenol EO-modified (n ≒ 4) acrylates, R ^1: a hydrogen atom, R ^2: an ethylene group, R ^3: (n? 2.5) acrylate, R ^{1 is a} hydrogen atom, R ^{2 is a} propylene group, R ^{3 is an} n-nonyl group, n is an n-nonyl group, 2.5,

Kyoeisha Chemical Co. (Phenoxyethyl acrylate, R ¹ : hydrogen atom, R ² : ethylene group, R ³ : hydrogen atom, n = 1), P-200A [phenoxypolyethylene glycol acrylate, R ^1: a hydrogen atom, R ^2: an ethylene group, R ^3: a hydrogen atom, n ≒ 2], NP-4EA [nonylphenol EO adduct acrylate, R ^1: a hydrogen atom, R ^2: an ethylene group , R ³ : n-nonyl group, n ≒ 4) or NP-8EA [[nonylphenol EO adduct acrylate, R ¹ : hydrogen atom, R ² : ethylene group, R ³ : n- 8] or light ester PO [phenoxyethyl methacrylate, R ¹ : methyl group, R ² : propylene group, R ³ : hydrogen atom, n = 1]

A nonylphenoxypolyethylene glycol acrylate, R ¹ : hydrogen atom, R ² : ethylene group, R ³ : n-nonyl group, n ≒ 5), ANP-300 glycol acrylate, R ^1: a hydrogen atom, R ^2: a propylene group, R ^3: n- nonyl, n ≒ 5], 43ANEP-500 [nonylphenoxy-polyethylene glycol-polypropylene glycol acrylates, R ^1: Polyethylene glycol-polypropylene glycol-acrylate, R ¹ : a hydrogen atom, R ² : an ethylene group and a propylene group, R ³ : n-nonyl group, n ≒ 5 + , R ^2: an ethylene group and a propylene group, R ^3: n- nonyl, n ≒ 9 + 3], 75ANEP-600 [nonylphenoxy-polyethylene glycol-polypropylene glycol acrylates, R ^1: a hydrogen atom, R ^2: an ethylene group and a propylene group, R ^3: n- nonyl, n ≒ 5 + 2], AAE-50 [phenoxy polyethylene glycol acrylate, R ^1: a hydrogen atom, R ^2: an ethylene group, R ^3: may Atom, n = 1], AAE-300 [phenoxy polyethylene glycol acrylate, R ^1: a hydrogen atom, R ^2: an ethylene group, R ^3: a hydrogen atom, n ≒ 5.5], PAE-50 [phenoxy polyethylene glycol meta dimethacrylate, R ^1: a methyl group, R ^2: an ethylene group, R ^3: a hydrogen atom, n = 1], PAE-100 [phenoxy polyethylene glycol methacrylate, R ^1: a methyl group, R ^2: an ethylene group, R ³ : Hydrogen atom, n = 2) or 43PAPE-600B [phenoxy-polyethylene glycol-polypropylene glycol-methacrylate, R ¹ : methyl group, R ² : ethylene group and propylene group, R ³ : 6 + 6],

(1 mol of phenoxyethylene glycol acrylate (EO 1 mol), R ¹ : hydrogen atom, R ² : ethylene group, R ³ : hydrogen atom, n = 1) manufactured by Shin Nakamura Chemical Co., Ltd., AMP -20G [phenoxyethylene glycol acrylate (EO 2mol), R ¹ : hydrogen atom, R ² : ethylene group, R ³ : hydrogen atom, n ≒ 2], AMP-60G [phenoxyethylene glycol acrylate ), R ^1: a hydrogen atom, R ^2: an ethylene group, R ^3: a hydrogen atom, n ≒ 6], PHE-1G [phenoxy glycol methacrylate (EO 1mol), R ^1: a methyl group, R ^2: an ethylene Group, R ³ : hydrogen atom, n = 1]

Viscoat # 192 [phenoxyethyl acrylate, R ¹ : hydrogen atom, R ² : ethylene group, R ³ : hydrogen atom, n = 1] made by Osaka Organic Chemical Industry Co.,

(2-phenoxyethyleneglycol acrylate, R ¹ : hydrogen atom, R ² : ethylene group, R ³ : hydrogen atom, n = 1) or SR-504 (manufactured by Nippon Kayaku Co., 2-naphthylphenol acrylate, R ¹ : hydrogen atom, R ² : ethylene group, and R ³ : n-nonyl group), but they are not limited thereto and two or more kinds may be used in combination.

In the ethylenically unsaturated monomer represented by the formula (D-6), the alkyl group of R ³ has 1 to 20 carbon atoms, and more preferably 1 to 10 carbon atoms. The alkyl group includes not only a straight chain alkyl group, but also a branched alkyl group and an alkyl group having a benzene ring as a substituent. When the alkyl group of R < ³ > has 1 to 10 carbon atoms, the alkyl group is disturbed to inhibit the resin from approaching to promote adsorption / orientation of the resin to the pigment. When the number of carbon atoms exceeds 10, the steric hindrance effect of the alkyl group increases , Even the adsorption / orientation to the pigment of the benzene ring is inhibited. This tendency becomes remarkable as the carbon chain length of the alkyl group of R ³ becomes longer. When the carbon number exceeds 20, the adsorption / orientation of the benzene ring is extremely lowered. Examples of the alkyl group having a benzene ring represented by R ³ include a benzyl group and a 2-phenyl (isopropyl) group. As the number of the side chain benzene rings increases, the solvent affinity and the pigment orientation are further improved, and not only the dispersibility but also the developability are improved.

In the ethylenically unsaturated monomer represented by the formula (D-6), n is preferably an integer of 1 to 15. When n is more than 15, the hydrophilic property increases, the effect of solvation decreases, the viscosity of the vinyl resin increases, and the viscosity of the coloring composition using the viscosity increases, which may affect the flowability. From the viewpoint of solvation, n is particularly preferably 1 to 4.

As the precursor of the constituent unit (D-b2), styrene,? -Methylstyrene, benzyl acrylate, benzyl methacrylate, or a monomer represented by the formula (D-6) is preferably used in view of copolymerization with other precursors and pigment dispersibility. Is preferably an ethylenically unsaturated monomer. By introducing a benzene ring into the side chain of the resin (D-B1), the side chain benzene ring is oriented to the pigment, thereby promoting the adsorption of the resin to the pigment and further suppressing aggregation of the pigment. Further, benzyl acrylate and / or benzyl methacrylate are most preferable from the viewpoints of developability and dispersion stability.

≪ Construction unit (D-b3) >

The constituent unit (D-b3) has a cyclic structure of an aliphatic ring group represented by the following formulas (D-4) and (D-5) and is an affinity site for a pigment composition comprising a pigment or a pigment and a dispersant , And functions as a hydrophobic region for the alkali developing solution. The structural unit (D-b3), based on the weight of all the structural units of the resin (D-B1), is from 2 to 60% by weight from the viewpoints of developability and filter segment quality and dispersion stability. If the content is less than 2% by weight, there arises a problem that the affinity for the pigment composition composed of the pigment or the pigment and the dispersing agent is insufficient and a high quality color filter is not obtained or the storage stability of the coloring composition for a color filter is deteriorated, There is a problem of pattern peeling or defects in the pixel portion because of insufficient hydrophobicity during development. If it exceeds 60% by weight, the dissolution rate with respect to the alkali developer becomes slow, and the developing time is long and the productivity of the color filter deteriorates.

It is expected that the dicyclopentane moiety contained in the structure of the structural unit (D-b3) gives steric hindrance to the aggregation state of the molecules in the filter segment without the ring having a planar structure.

(50)

(51)

Examples of the precursor of the constituent unit (D-b3) include an ethylenically unsaturated monomer represented by the following formula (D-7) or an ethylenically unsaturated monomer represented by the following formula (D-8).

(52)

(53)

Wherein R ¹ is a hydrogen atom or a methyl group, R ² is an alkylene group having 2 or 3 carbon atoms, and m is an integer of 0 to 2, in the formula (D-7) and the formula (D-8) ]

Examples of the ethylenic unsaturated monomer represented by the formula (D-7) include Fancryl FA-513A [dicyclopentanyl acrylate, R ¹ : hydrogen atom, R ² : = 0] or FA-513M [dicyclopentyl methacrylate, R ¹ : hydrogen atom, R ² : absent, m = 0], and the like. It is possible.

Examples of the ethylenic unsaturated monomer represented by the formula (D-8) include Fancryl FA-511A [dicyclopentenyl acrylate, R ¹ : hydrogen atom, R ² : m = 0], FA-512A [dicyclopentenyl oxyethyl acrylate, R ^1: a hydrogen atom, R ^2: an ethylene group, m = 1], FA-512M [dicyclopentenyl oxyethyl methacrylate, R ¹ : methyl group, R ² : ethylene group, m = 1] or FA-512MT [dicyclopentenyloxyethyl methacrylate, R ¹ : methyl group, R ² : ethylene group, m = 1] , But they are not limited to these, and two or more types may be used in combination.

<Other constituent units>

The other structural unit is a structural unit other than the structural unit (D-b1), the structural unit (D-b2) and the structural unit (D-b3).

As the precursor of the other constituent unit, for example,

(Meth) acrylate, isobutyl (meth) acrylate, isobutyl (meth) acrylate, isopropyl (meth) acrylate, (Meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl acrylate, neopentyl (Meth) acrylate, hexyl (meth) acrylate, hepta (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate such as stearyl (meth) acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) acrylate, allyl 2-hydroxyethyl (meth) acrylate, (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, 2-hydroxypropyl (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, 1,6-hexane diol diglycidyl ether di (meth) acrylate, tripropylene glycol di Acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, isobonyl (meth) acrylate, ester acrylate, epoxy (meth) acrylate, urethane acrylate , And other acrylic acid esters and methacrylic acid esters. Depending on the purpose, other ethylenically unsaturated monomers may be selected without being limited thereto, Two or more types may be used in combination.

As the other ethylenic unsaturated monomer, for example,

(Meth) acrylates having a heterocyclic substituent group such as tetrahydrofurfuryl (meth) acrylate or 3-methyloxetanyl (meth) acrylate;

Alkoxypolyalkylene glycol (meth) acrylates such as methoxypolypropylene glycol (meth) acrylate and ethoxypolyethylene glycol (meth) acrylate; or,

(Meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (Meth) acrylamides such as morpholine, N-hydroxymethyl (meth) acrylamide and N-vinylformamide, and acrylonitrile.

As the precursors of the constituent units other than the above, for example,

Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, hydroxyethyl vinyl ether, ethylene glycol divinyl ether and pentaerythritol trivinyl ether; or,

Vinyl acetate, and fatty acid vinyls such as vinyl propionate.

Furthermore, it is also possible to use dimethyl-2,2'- [oxybis (methylene)] bis-2-propenoate, diethyl-2,2 '- [oxybis Bis (2-propenyl) -2,2'- [oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2 '- [oxybis It is also possible. The structural unit other than the acrylic structural unit may be used in combination with the acrylic structural unit.

<Introduction of ethylenically unsaturated double bond>

An ethylenically unsaturated monomer having an epoxy group or an ethylenically unsaturated monomer having a hydroxyl group may also be used to introduce an ethylenically unsaturated double bond by the following methods (D-i) and (D-ii). (D-b1), the constituent unit (D-b2) and the constituent unit (D-b3) in consideration of the possibility of being a constituent unit other than the other constituent units depending on the modification .

&Lt; Method (D-i) >

As the method (Di), for example, there may be mentioned a method of reacting an unsaturated monobasic acid having an ethylenically unsaturated double bond with a side chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group with another one or more ethylenically unsaturated monomers There is a method in which a carboxyl group is subjected to an addition reaction and then the resulting hydroxyl group is reacted with a polybasic acid anhydride to introduce an ethylenically unsaturated double bond to give a photosensitive resin function and to introduce a carboxyl group having an alkali soluble function.

Since the carboxyl group of the unsaturated monobasic acid used in this step forms an ester bond after the addition reaction with respect to the epoxy group, it does not correspond to the structural unit (D-b1) of the resin (D-B1) The polybasic acid anhydride forms a carboxyl group after the reaction with the hydroxyl group, and thus corresponds to the constituent unit (D-b1) of the resin (D-B1).

Examples of the ethylenically unsaturated monomer having an epoxy group, the unsaturated monobasic acid and the polybasic acid anhydride include the same ethylenically unsaturated monomers as the ethylenically unsaturated monomer, the unsaturated monobasic acid and the polybasic acid anhydride in the fifth embodiment, the unsaturated monobasic acid, Polybasic acid anhydrides.

As a method analogous to the method (Di), for example, a method in which an ethylenically unsaturated monomer having an epoxy group is added to a part of side chain carboxyl groups of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group and another ethylenic unsaturated monomer Is subjected to an addition reaction to introduce an ethylenically unsaturated double bond and a carboxyl group. In this case, only the constituent unit corresponding to the carboxyl group which is not used for the addition reaction with the epoxy group corresponds to the constituent unit (D-b1) of the resin (D-B1).

&Lt; Method (D-ii) >

As the method (D-ii), an ethylenic unsaturated monomer having a hydroxyl group is used, and an ethylenic unsaturated monomer having an isocyanate group is added to the side chain hydroxyl group of the copolymer obtained by copolymerizing an unsaturated monobasic acid having another carboxyl group or another ethylenic unsaturated monomer There is a method of reacting an isocyanate group of an unsaturated monomer.

Examples of the ethylenic unsaturated monomer having a hydroxyl group and the ethylenic unsaturated monomer having an isocyanate group include the ethylenic unsaturated monomer having a hydroxyl group and the ethylenic unsaturated monomer having the same hydroxyl group as the ethylenic unsaturated monomer having an isocyanate group in the fifth embodiment And an ethylenically unsaturated monomer having an isocyanate group.

The weight average molecular weight (Mw) of the resin (D-B1) is preferably in the range of 5,000 to 100,000, more preferably 5,000 to 80,000, and still more preferably 5,000 to 30,000. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw / Mn is preferably 10 or less. When the weight-average molecular weight (Mw) of the resin (D-B1) exceeds 100,000, the interaction between the resins becomes strong and the viscosity of the coloring composition for a color filter becomes high. When the weight-average molecular weight (Mw) is less than 5,000, developability and adhesiveness to substrates such as glass may be deteriorated.

The content of the resin (D-B1) is preferably 30 parts by weight or more based on 100 parts by weight of the pigment (A1) shown in the formula (1) from the viewpoint of good film- Is used in an amount of not more than 500 parts by weight from the standpoint of exhibiting good color characteristics. More preferably 50 to 250 parts by weight.

"Other resin"

The coloring composition may further contain other resin than the resin (D-B1). As the other resin, a resin having a transmittance of preferably 80% or more, more preferably 95% or more is preferable in the entire wavelength range of 400 to 700 nm which is a visible light region. Other resins include thermoplastic resins, thermosetting resins and photosensitive resins, which may be used alone or in combination of two or more. Examples of the resin include the same resin as the resin in the fifth embodiment.

As the photosensitive resin, a (meth) acrylic compound having a reactive substituent such as an isocyanate group, an aldehyde group or an epoxy group, or cinnamic acid (cinnamic acid) is reacted with a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, A resin obtained by introducing a photo-crosslinkable group such as a diol or a styryl group into the linear polymer is used. Further, a linear polymer containing an acid anhydride such as styrene-maleic anhydride copolymer or -olefin-maleic anhydride copolymer may be copolymerized with a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) Esterification is also used.

(solvent)

The solvent is used to facilitate the formation of filter segments by dispersing the pigment (A) sufficiently in the binder resin (DB) and applying the colored composition on a substrate such as a glass substrate so that the dry film thickness becomes 0.2 to 5 mu m do. As the solvent, an organic solvent is preferable. The preferred amount of the solvent used is the same as in the fifth embodiment.

(Production of photosensitive coloring composition)

The coloring composition of the sixth embodiment can be produced by the same production method as the coloring composition of the fifth embodiment.

(Optional component)

The coloring composition of the sixth embodiment may contain optional components such as a pigment dispersant (DC), a photopolymerization initiator (DD), a sensitizer, a photopolymerizable compound, a polyfunctional thiol, an ultraviolet absorber, a polymerization inhibitor, a storage stabilizer, . Specific examples of these optional components are the same as in the fifth embodiment. In addition, preferred examples, preferred amounts and the like are the same as in the fifth embodiment.

(Removal of coarse particles)

The coloring composition of the sixth embodiment is preferably subjected to removal of coarse particles in the same manner as the coloring composition of the third embodiment.

[Solvent, optional ingredient]

Specific examples of the solvent and optional components used in the coloring composition for a color filter are described below.

(Other colorants (other pigments))

Other coloring agents (other pigments) that can be used in the coloring composition include, for example, C.I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 48: 81, 81, 81, 81, 81, 81, 81, 81, 81, 81, 81, 81, 81, 81, : 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, , 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 192, 193, 194, 200, 202, 206, 207 , 208, 209, 210, 214, 215, 216, 217, 220, 221, 223, 224, 226, 227, 228, 240, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 243, 245, 246, 247, 249, 250, 251, 272, 273, 274, 275, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, or 287. Examples of the red dye include a xanthene system, a monoazo system (pyridon system, barbituric system, metal complex system, etc.), a disazo system, and an anthraquinone system. Specifically, C.I. And acid salts of acidic dyes such as Acid Red 52, 87, 92, 289, 338 and the like. These may be used alone or in combination of two or more.

For example, C.I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 51, 55, 59, 61 , 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78 or 79, and / or CI Pigment Yellow 1, 1, 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1 , 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 60, 61, 62, 62: 1, 63, 65, 73, 74, 75, 77, 81 , 83, 87, 93, 94, 95, 97, 98, 100, 101, 104, 105, 106, 108, 109, 110, 111, 113, 114, 115, 116, 117, 118, 119, 120, 123 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 152, 153, 154, 155, 156, 157, 158, 159, 160 , 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 183, 184, 185, 187 , 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, , 219, 220, or 221 can be used in combination. Examples of the colorant and / or yellow dye include quinoline, monoazo (pyridone, barbituric, metal complex, etc.), disazo, and methine. These may be used alone or in combination of two or more.

Of these, preferred examples of the coloring agent to be used in combination include anthraquinone pigments, monoazo pigments, disazo pigments, and xanthene dyes. Specifically, from the viewpoint of brightness and contrast, C.I. Pigment Red 48: 1, 122, 168, 176, 177, 185, 202, 206, 207, 209, 224, 242, 254, C.I. Pigment Orange 38, 71, C.I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, and C.I. Preferred is the salt-forming compound of Acid Red 52. More preferably, C.I. Pigment Red 177, 209, 224, 242, or 254, C.I. Pigment Yellow 83, 138, 139, 150, or 180.

(Organic solvent)

Examples of the organic solvent that can be used in the coloring composition include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5 Methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutylacetate, 3- M-xylene, m-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl But are not limited to, alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o- dichlorobenzene, p- , sec-butylbenzene, tert-butylbenzene,? -butyrolactone, isobutyl alcohol, isophorone, ethylene glycol Ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol mono tert-butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monobutyl ether acetate, , Ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl Ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetone, cyclohexanone, dipropylene glycol Methyl 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 Propylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, Propyleneglycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, acetic acid isoamyl acetate, Propyl acetate, isobutyl acetate, propyl acetate, dibasic acid ester and the like. These solvents may be used singly or in combination of two or more kinds in an optional ratio as required.

Among them, alkyl lactates such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate and the like are preferable from the viewpoint of good dispersibility of the colorant, , And glycol acetates such as ethylene glycol monoethyl ether acetate; alcohols such as benzyl alcohol and diacetone alcohol; and ketones such as cyclohexanone.

(Resinous dispersant)

The resinous dispersant has a pigment affinity site having a property of adsorbing to a colorant and a site compatible with the colorant carrier and adsorbed on the colorant to stabilize the dispersion of the colorant on the colorant carrier. Specific examples of the resinous dispersing agent include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, Amides or their salts formed by the reaction of a polysiloxane, a long chain polyaminoamide phosphate, a hydroxyl group-containing polycarboxylic acid ester, a modification thereof, a poly (lower alkyleneimine) and a polyester having a free carboxyl group A water-soluble resin or a water-soluble polymer compound such as an oil-based dispersant, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, Polyester type, modified polyacrylate type, ethylene oxide / propylene oxide addition compound, phosphoric acid ester type, etc. All. These may be used singly or in combination of two or more, but are not limited thereto.

Examples of the resinous dispersant commercially available include Disperbyk-101, 103, 107, 108, 110, 111, 112, 116, 130, 140, 142, 154, 161, 162, 163, 164, 165, 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, SOLSPERSE-3000, 9000 manufactured by The Lubrizol Corporation, such as Lactimon, WS-2164 or Anti-Terra-U, 203, 204 or BYK-P104, P104S, 220S, 6919, 21116, 21324, 21407, 21715 or Lactimon, Lactimon- , 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 , EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 53095, 55000, 56000, 76500 and the like manufactured by Ciba Japan KK , 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501 , 1502, 1503, etc., Kusumoto DISPARLON 3600N, DISPARLON 1850 manufactured by Chemicals, Ltd. and Ajisper PA111, PB711, PB821, PB822, PB824 manufactured by Ajinomoto Fine-Techno Co., These may be used alone or in combination of two or more.

Of these, Disperbyk-108, 110, 111, 112, 116, 142, 180, 2000, 2001 of BYK Chemie Japan KK, which is a resin type pigment dispersant having an acidic functional group, or SOLSPERSE- 4401, 4550 from Ciba Japan KK, or DISPARLON 3600N, DISPARLON 1850 from Kusumoto Chemicals, Ltd., or Ajisper PA111 from Ajinomoto Fine-Techno Co., Inc. But are not limited thereto.

(Surfactants)

Examples of the surfactant include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalenesulfonate, sodium alkyldiphenylether disulfonate, Anionic surfactants such as monoethanolamine, triethanolamine lauryl sulfate, ammonium lauryl sulfate, stearic acid monoethanolamine, monoethanolamine of styrene-acrylic acid copolymer, and polyoxyethylene alkyl ether phosphate ester; Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; Cationic surfactants such as alkyl quaternary ammonium salts or ethylene oxide adducts thereof; Alkyl betaine such as alkyldimethylaminoacetic acid betaine, and amphoteric surfactant such as alkylimidazoline. These may be used singly or in combination of two or more, but are not limited thereto.

(Photopolymerizable monomer)

Examples of the monomer or oligomer which is cured by ultraviolet rays or heat to generate a transparent resin include oligomers such as methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) Carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene Acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6- (Meth) acrylate, hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (Meth) acrylates of dipentaerythritol penta (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, methylol melamine, epoxy (meth) acrylate, (Meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N- (Meth) acrylamide, N-vinylformamide, acrylonitrile, and the like, but are not limited thereto. These photopolymerizable compounds may be used singly or as a mixture of two or more kinds in an optional ratio as required.

(Photopolymerization initiator)

Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2- 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2- (dimethylamino) -2 - [(4 (4-morpholinophenyl) -1-butanone, or 2-benzyl-2-dimethylamino-1- -Acetophenone-based compounds; Benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; Benzophenone, benzoyl benzoyl benzoate, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3 ', 4,4'- benzophenone-based compounds such as t-butylperoxycarbonyl) benzophenone; Thioxanthone such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4- compound; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s- triazine, 2- (p- methoxyphenyl) (Trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho- (Trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) - (4-methoxy-naphthol- Triazine-based compounds such as 6-triazine, or 2,4-trichloromethyl- (4'-methoxystyryl) -6-triazine; Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -, 1- (O- acetyloxime) - (phenylthio) -, 2- (O-benzoyloxime) or O- (acetyl) -N- (1-phenyl- Oxime ester-based compounds such as hydroxylamine; Phosphine compounds such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; Quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethyl anthraquinone; Borate compounds; Carbazole-based compounds; Imidazole-based compounds; Alternatively, a titanocene compound or the like is used. These photopolymerization initiators may be used singly or as a mixture of two or more kinds in an optional ratio as required.

Among these, as the photopolymerization initiator, it is preferable to include at least one photopolymerization initiator selected from the group consisting of an acetophenone-based compound, a phosphine-based compound, an imidazole-based compound and an oxime ester-based compound. By including these photopolymerization initiators, the pattern shape and linearity of the filter segments become better.

(Sensitizer)

Examples of the sensitizer include unsaturated ketones represented by chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, Acetimine derivatives, azine derivatives such as xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives and oxolin derivatives , Thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squalilium derivatives, porphyrin derivatives, tetraphenylporphyrine derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Derivatives, phthalocyanine derivatives, tetraazapolpyrazine derivatives, tetraquinazolinopolpyrazine derivatives, naphthalocyanine derivatives, Wherein the metal complex is at least one selected from the group consisting of naphthalene derivatives, naphthalene derivatives, naphthene derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetrapyrine derivatives, Derivatives, imidazole derivatives,? -Acyloxy esters, acylphosphine oxides, methylphenylglyoxylate valero, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone, 4,4'- Tallophenone, 3,3 'or 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, and 4,4'-diethylaminobenzophenone. Two or more kinds of sensitizers may be used at an arbitrary ratio as required.

More specifically, it is described in OKAWARA Makoto et al., "Coloring Handbook" (Kodansha Ltd., 1986), OKAWARA Makoto et al., "Functional dye chemistry" (CMC Publishing Co., Ltd., 1981), IKEMORI Chuzaburo et al. , And the sensitizers described in &quot; Special Functional Materials &quot; (CMC Publishing Co., Ltd., 1986). In addition, it is also possible to add a sensitizer which exhibits absorption of light from ultraviolet to near infrared.

(Polyfunctional thiol)

The polyfunctional thiol may be, for example, hexanediol, decanediol, 1,4-butanediol bis-thiophosphate, 1,4-butanediol bisthioglycolate, ethylene glycol bis-thioglycolate, (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), trimethylolpropane tris (Mercapto propionate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptofuro Tris (2-hydroxyethyl) isocyanurate, 1,4-dimethyl mercaptan benzene, 2, 4,6-trimercapto-s-triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s-triazine and the like. These polyfunctional thiols may be used singly or as a mixture of two or more kinds in an optional ratio as required.

(Ultraviolet absorber)

Examples of the ultraviolet absorber include 2- [4 - [(2-hydroxy-3- (dodecyl and tridecyl) oxypropyl) oxy] -2- hydroxyphenyl] (4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] Hydroxyphenyltriazine type such as 1,3,5-triazine, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2H-benzotriazol- Benzotriazole based compounds such as bis (1-methyl-1-phenylethyl) phenol and 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) Benzophenones such as hydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone and 2,2 ', 4,4'-tetrahydroxybenzophenone, phenyl salicylate, p-tert- Cyanoacrylates such as salicylate and ethyl-2-cyano-3,3'-diphenylacrylate and the like, 2,2,6,6-tetramethylpiperidin-1- Oxyl (triacetone-ah (2,2,6,6-tetramethyl-4-piperidyl) -s sebacate, poly [[6 - [(1,1,3,3-tetrabutyl) amino] -1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidinyl) imino]. These ultraviolet absorbers may be used singly or as a mixture of two or more kinds in an optional ratio as required.

(Polymerization inhibitor)

Examples of the polymerization inhibitor include methylhydroquinone, t-butylhydroquinone, 2,5-di-t-butylhydroquinone, 4-benzoquinone, 4-methoxyphenol, 4-methoxy- t-butylcatechol and the like, and amine compounds such as phenol compounds, phenothiazine, bis- (1-dimethylbenzyl) phenothiazine and 3,7-dioctylphenothiazine, dibutyldithiocarbamic acid copper , Copper diethyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate and manganese diphenyldithiocarbamate, and copper and manganese compounds such as 4-nitrosophenol, N-nitroso diphenylamine, N-nitrosoocyclo Nitroso compounds such as hexylhydroxylamine and N-nitrosophenylhydroxylamine, and ammonium salts and aluminum salts thereof. These polymerization inhibitors may be used singly or as a mixture of two or more kinds in an optional ratio as required.

(Antioxidant)

The "antioxidant" may be any compound having an ultraviolet ray absorbing function, a radical replenishing function, or a peroxide decomposing function. Specifically, examples of the antioxidant include hindered phenol type, hindered amine type, phosphorus type, sulfur type, benzotriazole type, Benzophenone-based compounds, hydroxylamine-based compounds, salicylic acid ester-based compounds and triazine-based compounds, and known ultraviolet absorbers and antioxidants can be used. These antioxidants may be used singly or as a mixture of two or more kinds in an optional ratio as required.

Of these antioxidants, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferable from the viewpoint of compatibility between the transmittance and sensitivity of the coating film. More preferably, it is a hindered phenol-based antioxidant, a hindered amine-based antioxidant, or a phosphorus-based antioxidant.

(Amine compound)

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4- 2-ethylhexyl dimethylamino benzoate, and N, N-dimethyl paratoluidine. These amine compounds may be used singly or as a mixture of two or more kinds in an optional ratio as required.

(Leveling agent)

The leveling agent is preferably a dimethylsiloxane having a polyether structure or a polyester structure in the main chain. Specific examples of the dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Dow Corning Toray Co., Ltd. and BYK-333 manufactured by BYK-Chemie. Specific examples of the dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK-Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain may be used in combination.

Particularly preferred as a leveling agent is one kind of so-called surfactant having a hydrophobic group and a hydrophobic group in the molecule and has a low hydrophilicity and low solubility in water and a low surface tension lowering ability when added to a coloring composition And that the wettability to the glass plate is good even though the surface tension lowering ability is low, and that the chargeability can be suppressed sufficiently at an addition amount at which defects of the coating film due to bubbling do not appear. As the leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. The polyalkylene oxide unit includes a polyethylene oxide unit and a polypropylene oxide unit, and the dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

The mode of bonding of the polyalkylene oxide units to the dimethylpolysiloxane may be a pendant in which the polyalkylene oxide unit is bonded to the repeating unit of the dimethylpolysiloxane, a terminal modification in which the terminal is bonded to the terminal of the dimethylpolysiloxane, alternating with the dimethylpolysiloxane And may be any of the straight-chain block copolymer type combined therewith. The dimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., and is commercially available, for example, as FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ- -2203, and FZ-2207, but are not limited thereto. The leveling agent may be used singly or as a mixture of two or more kinds in an optional ratio as required.

It is also possible to add anionic, cationic, nonionic, or amphoteric surfactant to the leveling agent. The surfactants may be used in combination of two or more. Examples of the anionic surfactant added as an auxiliary to the leveling agent include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, sodium alkyldiphenylether disulfonate, Monoethanolamine sulfate, monoethanolamine sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer and polyoxyethylene alkyl ether phosphate ester have.

Examples of the cationic surfactant to be added as an auxiliary to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Examples of the nonionic surfactant to be added as a supplement to the leveling agent include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate Such as polyethylene glycol monolaurate; Alkyl betaines such as alkyldimethylaminoacetic acid betaine; amphoteric surfactants such as alkylimidazoline; and fluorine-based or silicone-based surfactants.

(Hardener, hardening accelerator)

Examples of the curing agent include phenol resin, amine compound, acid anhydride, active ester, carboxylic acid compound, sulfonic acid compound, etc. However, Available. Among them, a compound having two or more phenolic hydroxyl groups in one molecule and an amine-based curing agent are preferably used. Examples of the curing accelerator include amine compounds such as dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, Benzylamine, 4-methyl-N, N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (such as triethylbenzylammonium chloride), block isocyanate compounds (such as dimethylamine) (Such as imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenyl Imidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, etc.), phosphorus compounds (for example, triphenylphosphine And the like), guanamine compounds (e.g., melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (for example, 2,4-diamino-6-methacryloyl Oxyethyl-S-tri Vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino- Trioctane isocyanuric acid adduct, etc.) and the like can be used. These may be used alone, or two or more of them may be used in combination.

(Storage stabilizer)

Examples of the storage stabilizer include 2,6-bis (1,1-dimethylethyl) -4-methylphenol, pentaerythritol-tetrakis [3- (3,5- (N-octylthio) -6- (4-hydroxy-3,5-di-t-butyl anilino) 1,3,5-triazine , t-butyl pyrocatechol, etc., organic phosphine such as tetraethylphosphine, triphenylphosphine and tetraphenylphosphine, zinc dimethyldithiophosphate, zinc dipropyldithiophosphate, dibutyldithiophosphate, And organic acids such as quaternary ammonium chloride such as benzyltrimethyl chloride and diethylhydroxyamine, lactic acid and oxalic acid, and methyl ethers thereof, and the like can be used. have. These storage stabilizers may be used singly or as a mixture of two or more kinds in an optional ratio as required.

(Adhesion improver)

Examples of the adhesion improver include vinylsilanes such as vinyltris (? -Methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, and? -Methacryloxypropyltrimethoxysilane (3,4-epoxycyclohexyl) ethyltrimethoxysilane,? - (3,4-epoxycyclohexyl) methyltrimethoxysilane,? - (3,4-epoxycyclohexyl) Epoxysilanes such as ethyltriethoxysilane,? - (3,4-epoxycyclohexyl) methyltriethoxysilane,? -Glycidoxypropyltrimethoxysilane and? -Glycidoxypropyltriethoxysilane, (Aminoethyl)? - aminopropyltrimethoxysilane, N -? (Aminoethyl)? - aminopropyltriethoxysilane, N -? Aminopropyltriethoxysilane,? -Aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltri Amino silanes such as sisilran, γ- mercaptopropyltrimethoxysilane, γ- mercaptopropyl the tree may be a silane coupling agent such as thio silanes such as silane. These adhesion promoting agents may be used singly or in combination of two or more kinds in an optional ratio as required.

[Color Filter]

The color filter of the seventh embodiment will be described.

[Seventh Embodiment]

(Color filter)

The color filter of the seventh embodiment is formed using the coloring composition for a color filter. According to the seventh embodiment, it is possible to provide a fixed color filter having excellent brightness and contrast ratio. The color filter of the seventh embodiment is applicable to a color liquid crystal display device, a color image pickup tube device and the like.

The color filter comprises a red filter segment, a green filter segment and a blue filter segment, wherein a red filter segment is formed from the coloring composition. In addition, the color filter may further comprise a magenta filter segment, a cyan filter segment and a yellow filter segment.

The color filter generally comprises the filter segments on a transparent substrate. As the transparent substrate, glass plates such as soda lime glass, low alkali borosilicate glass, and alkali-free alumino-borosilicate glass, and resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate are used. Further, a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or resin plate for liquid crystal driving after paneling.

The dry film thickness of the filter segment is preferably 0.2 to 10 mu m, more preferably 0.2 to 5 mu m. For drying the coating film, a vacuum dryer, a convection oven, an IR oven, a hot plate, or the like may be used.

The green filter segment can be formed using conventional green coloring compositions including a green pigment and a colorant carrier. As the green pigment, for example, C.I. Pigment Green 7, 10, 36, 37 and 58 and the like are used.

Further, a yellow pigment or a yellow dye may be used in combination with the green coloring composition. As yellow pigments which can be used in combination, C.I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: , 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101 , 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153 , 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188 , 193, 194, 198, 199, 213, 214, 218, 219, 220, or 221. Examples of the yellow dye that can be used in combination include quinoline, monoazo (pyridone, barbituric, metal complex, etc.), disazo, and methine.

The blue filter segment can be formed using a conventional blue coloring composition including a blue pigment and a colorant carrier. As the blue pigment, for example, C.I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, Further, a purple pigment can be used in combination with the blue coloring composition. As the purple pigment which can be used in combination, C.I. Violet pigments such as Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, In addition, a basic dye having a blue or violet color or a salt-forming compound of an acid dye may be used. When a dye is used, a xanthene dye is preferable from the viewpoint of heat resistance and brightness.

(Manufacturing Method of Color Filter)

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

The formation of the filter segment by the printing method can be performed by simply repeating printing and drying of the coloring composition prepared as the printing ink, so that the manufacturing method of the color filter is preferably a low cost and excellent in mass productivity (mass productivity) Do. Further, as the printing technique is developed, fine pattern printing with high dimensional accuracy and smoothness can be performed. In order to perform printing, it is preferable that the composition is such that the ink does not dry and solidify on a printing plate or on a blanket. It is also preferable to control the flowability of the ink on the printing machine, and the viscosity of the ink by the dispersing agent or the extender pigment may be adjusted.

When the filter segments are formed by the photolithography method, the coloring composition prepared as the solvent-developing type or alkali-developing type coloring resist material is applied onto a transparent substrate by a coating method such as a spray coat, a spin coat, a slit coat, To a dry film thickness of 0.2 to 10 mu m, preferably 0.2 to 5 mu m. The dried film is subjected to ultraviolet exposure through a mask having a predetermined pattern provided in contact with or in contact with the film. Thereafter, a desired pattern is formed by dipping in a solvent or an alkaline developing solution, or spraying the developing solution by spraying or the like to remove un-hardened portions, and then the same operation can be repeated for different colors to produce a color filter. Further, in order to accelerate the polymerization of the colored resist material, heating may be performed if necessary. According to the photolithography method, a color filter having a degree (accuracy) higher than that of the printing method can be manufactured.

Thereafter, the filter layer may be formed by dipping in a solvent or an alkaline developing solution, or spraying a developing solution by spraying or the like to remove un-hardened portions to form a desired pattern. Further, in order to accelerate the polymerization of the filter segment formed by the development, heating may be carried out if necessary. According to the photolithography method, it is possible to form a filter segment having a degree higher than that of the printing method.

At the time of development, an aqueous solution of sodium carbonate, sodium hydroxide, or the like is used as an alkaline developer, and organic alkalis such as dimethylbenzylamine and triethanolamine may be used. Further, a defoaming agent or a surfactant may be added to the developing solution. As the development processing method, a shower development method, a spray development method, a dip (immersion) development method, a puddle (liquid) deposition development method, or the like can be applied.

On the other hand, in order to increase the ultraviolet exposure sensitivity, a film is formed which is applied and dried with the above-mentioned colored resist, and a water-soluble or alkali-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to prevent polymerization inhibition by oxygen , And ultraviolet exposure may be performed.

The color filter can be produced by an electrodeposition method, a transfer method, etc. in addition to the above-mentioned method, and the above-described coloring composition or photosensitive coloring composition can be used in any method. On the other hand, the electrodeposition method is a method of manufacturing a color filter by electrodepositing colloidal particles on a transparent conductive film formed on a substrate and electro-depositing each color filter segment on a transparent conductive film. The transfer method is a method in which filter segments are formed in advance on the surface of a releasable transfer base sheet, and the filter segments are transferred onto a desired substrate.

The coloring composition can be used in any method. In particular, the coloring composition of the embodiments 5 and 6 is most suitable for photolithography.

A black matrix may be formed in advance before the respective color filter segments are formed on the transparent substrate or the reflective substrate. As the black matrix, a multilayer film of chromium, chromium / chromium oxide, an inorganic film such as titanium nitride, or a resin film in which a light shielding agent is dispersed is used, but the present invention is not limited thereto. In addition, thin film transistors (TFTs) may be formed on the transparent substrate or the reflective substrate in advance, and color filter segments may be formed thereafter. On the color filter, an overcoat film, a transparent conductive film, a columnar spacer, a liquid crystal alignment film and the like are formed if necessary.

The color filter is prepared by sticking the polarizing film or the retardation film to the outside of the substrate as required, by sealing the injection port after injecting the liquid crystal from the injection port provided in the sealing section, using the sealing agent, A liquid crystal display panel is manufactured.

Such a liquid crystal display panel has been widely used in various fields such as twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), optical converbend bend In the liquid crystal display mode in which coloring is performed by using the color filter of FIG.

Example

Hereinafter, embodiments of the present invention will be described with reference to examples, but the present invention is not limited thereto.

[Example A]

Unless specifically stated, "part" and "%" mean "part by mass" and "% by mass", respectively. (6-3), a benzoisoindole derivative of the formula (7-1), an anthraquinone derivative of the formula (8-5) and an anthraquinone derivative of the formula Quinophthalone derivatives of formula (14-1) were used.

(Average primary particle diameter of pigment)

The average primary particle size of the pigment composition thus prepared was measured (calculated) by the following method.

The average primary particle diameter of the pigment was measured by a method of directly measuring the size of primary particles from an electron microscope photograph using a transmission electron microscope (TEM). Specifically, the minor axis diameter and the major axis diameter of the primary particles of each pigment were measured, and the average was determined as the particle diameter of the pigment primary particles. Subsequently, the volume (weight) of each particle was determined with respect to 100 or more pigment particles to approximate the cubic of the obtained particle diameter, and the volume average particle diameter was determined as the average primary particle diameter.

(Mass average molecular weight of binder resin)

The mass average molecular weight of the acrylic resin was measured by the following method.

The mass average molecular weight (Mw) of the acrylic resin was measured using GPC (Tosoh Corporation, HLC-8120GPC) equipped with a RI detector using a TSKgel column (manufactured by Tosoh Corporation) and using THF as a developing solvent (Mw) in terms of polystyrene.

 First, the diketopyrrolopyrrole pigment, the diketopyrrolopyrrole pigment composition, the other pigment, the binder resin solution, and the method for producing the green and blue photosensitive coloring compositions used in Examples and Reference Examples are explained.

&Lt; Production method of diketopyrrolopyrrole pigment >

(Brominated diketopyrrolopyrrole pigment formula (1))

200 parts of tert-amyl alcohol dehydrated by molecular sieve and 140 parts of sodium-tert-amyl alkoxide were added to a stainless steel reaction vessel equipped with a reflux condenser and heated to 100 占 폚 with stirring, Alcoholate solution was prepared. On the other hand, 88 parts of diisopropyl succinate and 153.6 parts of 4-bromobenzonitrile were added to a glass flask and dissolved by heating at 90 占 폚 with stirring to prepare a solution of these mixtures. The heated solution of the mixture was slowly dropped into the above alcoholate solution heated to 100 占 폚 at a constant rate over 2 hours while stirring vigorously. After completion of the dropwise addition, heating and stirring were continued at 90 占 폚 for 2 hours to obtain an alkali metal salt of a diketopyrrolopyrrole compound. Then, 600 parts of methanol, 600 parts of water and 304 parts of acetic acid were added to a reaction vessel equipped with a glass jacket and cooled to -10 ° C. The thus cooled mixture was cooled to 75 deg. C while rotating a share disk having a diameter of 8 cm at 4000 rpm using a high-speed stirring disperser, and the alkali of the diketopyrrolopyrrole compound thus obtained The metal salt solution was added in small portions. At this time, while cooling the mixture of methanol, acetic acid and water to keep the temperature at -5 ° C or lower at all times, while adjusting the rate of addition of the alkali metal salt of the diketopyrrolopyrrole compound at 75 ° C, Min. &Lt; / RTI &gt; After addition of the alkali metal salt, red crystals precipitated and a red suspension was formed. Subsequently, the obtained red suspension was washed with an ultrafiltration apparatus at 5 캜, and filtered (separated by filtration) to obtain a red paste. This paste was re-dispersed in 3500 parts of methanol cooled to 0 占 폚 to prepare a suspension having a methanol concentration of about 90% and stirred at 5 占 폚 for 3 hours to perform grain sizing and cleaning following the crystal transition. Subsequently, the water (water) paste of the obtained diketopyrrolopyrrole compound was dried at 80 DEG C for 24 hours and pulverized to obtain 150.8 parts of a diketopyrrolopyrrole bromide pigment represented by the formula (1) .

(Specific heterodimeropyrrolopyrrole pigment A formula (A-2-1))

220 parts of tert-amyl alcohol was placed in the reaction vessel 1, 32 parts of 60% NaH was added while cooling with water bath, and the mixture was heated and stirred at 90 占 폚. Next, 100 parts of tert-amyl alcohol, 85.0 parts of the compound of the following formula (A-16) synthesized by the method of Tetrahedron, 58 (2002) 5547-5565 and 60.9 parts of 4-cyanobiphenyl were dissolved by heating in the reaction vessel 2 , And this was dropped into the reaction vessel 1 over 2 hours. After reacting at 120 DEG C for 10 hours, the reaction mixture was cooled to 60 DEG C, 400 parts of methanol and 50 parts of acetic acid were added, followed by washing with water and methanol to obtain the specific heterodimeropyrrolopyrrole represented by the formula (A-2-1) 88.1 parts of pigment A was obtained.

(54)

(Specific heterodimethopyrrolopyrrole pigment A formula (A-2-2))

(A-2-1) was carried out in the same manner as in the production of the specific heterodimeropyrrolopyrrole pigment A formula (A-2-1), except that 60.9 parts of 4-cyanobiphenyl was changed to 54.1 parts of 4-tert-butylbenzonitrile, 2 &lt; -2 &gt;) was obtained in the same manner as in Example 1, except that 83.9 parts of the specific diketopyrrolopyrrole pigment A was used.

(Specific heterodimeropyrrolopyrrole pigment A formula (A-2-3a))

Except that 60.9 parts of 4-cyanobiphenyl was changed to 68.7 parts of N-butyl-4-cyanobenzamide, the same procedure as in the production of the specific diketopyrrolopyrrole pigment A formula (A-2-1) 87.0 parts of a specific heterodimeropyrrolopyrrole pigment A represented by the formula (A-2-3a) was obtained.

(Specific heterodimethopyrrolopyrrole pigment A formula (A-2-3b))

Except that 60.9 parts of 4-cyanobiphenyl was changed to 75.5 parts of N-phenyl-4-cyanobenzamide, the same procedure as in the production of the specific diketopyrrolopyrrole pigment A formula (A-2-1) 86.9 parts of a specific heterodimeropyrrolopyrrole pigment A represented by the formula (A-2-3b) was obtained.

(Specific heterodimeropyrrolopyrrole pigment A formula (A-2-4a))

Except that 60.9 parts of 4-cyanobiphenyl was changed to 87.8 parts of N, N-dibutyl-4-cyanobenzamide, the same procedure as in the preparation of the specific diketopyrrolopyrrole pigment A formula (A-2-1) To obtain 87.1 parts of the specific heterodimeropyrrolopyrrole pigment A represented by the formula (A-2-4a).

(Specific heterodimethopyrrolopyrrole pigment A formula (A-2-4b))

Except that 60.9 parts of 4-cyanobiphenyl was changed to 87.8 parts of N, N-dibutyl-3-cyanobenzamide, the same procedure as in the preparation of the specific diketopyrrolopyrrole pigment A formula (A-2-1) To obtain 83.8 parts of a specific heterodimeropyrrolopyrrole pigment A represented by the formula (A-2-4b).

(Specific heterodimethopyrrolopyrrole pigment A formula (A-2-9a))

Except that 60.9 parts of 4-cyanobiphenyl was changed to 84.1 parts of 4- (octylthio) benzonitrile, the same procedure as in the production of the specific heterodimeropyrrolopyrrole pigment A formula (A-2-1) -2 &gt; - 9a) was obtained in an amount of 85.5 parts by weight.

(Specific heterodimethopyrrolopyrrole pigment A formula (A-2-8))

Except that 60.9 parts of 4-cyanobiphenyl was changed to 58.1 parts of 4- (trifluoromethyl) benzonitrile, the same procedure as in the production of the specific heterodimeropyrrolopyrrole pigment A formula (A-2-1) To obtain 85.8 parts of the specific heterodimethopyrrolopyrrole pigment A represented by the general formula (A-2-8).

&Lt; Process for producing diketopyrrolopyrrole-based pigment composition >

(Specific Heterodiketopyrrolopyrrole Pigment Mixture 1 (RC-1))

200 parts of tert-amyl alcohol dehydrated by molecular sieves and 140 parts of sodium-tert-amyl alkoxide were added to a stainless steel reaction vessel equipped with a reflux tube and heated to 100 占 폚 with stirring to obtain an alcoholate solution Lt; / RTI &gt; On the other hand, 88 parts of diisopropyl succinate, 104.5 parts of 4-chlorobenzonitrile and 15.1 parts of 4-cyanobiphenyl were added to a glass flask and dissolved by heating at 90 占 폚 with stirring to prepare a solution of these mixtures. The heated solution of the mixture was slowly dropped into the above alcoholate solution heated to 100 占 폚 at a constant rate over 2 hours while stirring vigorously. After completion of the dropwise addition, heating and stirring were continued at 90 占 폚 for 2 hours to obtain an alkali metal salt of a diketopyrrolopyrrole compound. Then, 600 parts of methanol, 600 parts of water and 304 parts of acetic acid were added to a reaction vessel equipped with a glass jacket and cooled to -10 占 폚. The cooled mixture was subjected to the addition of a small amount of an alkali metal salt solution of the diketopyrrolopyrrole compound obtained in the previous step in which a common disk having a diameter of 8 cm was rotated at 4000 rpm using a high- Respectively. At this time, while cooling the mixture of methanol, acetic acid and water to keep the temperature at -5 ° C or lower at all times, while adjusting the rate of addition of the alkali metal salt of the diketopyrrolopyrrole compound at 75 ° C, Min. &Lt; / RTI &gt; After addition of the alkali metal salt, red crystals precipitated and a red suspension was formed. Subsequently, the obtained red suspension was washed with an ultrafiltration device at 5 DEG C, and filtered to obtain a red paste. This paste was redispersed in 3500 parts of methanol cooled to 0 DEG C to obtain a suspension having a methanol concentration of about 90% and stirred at 5 DEG C for 3 hours to effect particle sizing and cleaning following the crystal transition. Subsequently, the resulting mixture was filtered with an ultrafilter, and the obtained water paste of the diketopyrrolopyrrole compound was dried at 80 DEG C for 24 hours and pulverized to obtain 143.6 parts of a specific diketopyrrolopyrrole pigment mixture 1 (RC-1). The obtained C.I. The content of the specific diketopyrrolopyrrole pigment A represented by Pigment Red 254 and the formula (A-2-1) was quantitatively analyzed by HPLC. The content of the specific diketopyrrolopyrrole pigment A represented by Pigment Red 254 and the formula (A-2-1) was 90.9% by mass and 9.1% by mass, respectively.

(Specific Heterodimethopyrrolopyrrole Pigment Mixture 2 (RC-2))

(RC-1) except that 15.1 parts of 4-cyanobiphenyl and 13.4 parts of 4-tert-butylbenzonitrile were used in place of the specific diketopyrrolopyrrole pigment mixture 1 (RC-1) 142.2 parts of pigment mixture 2 (RC-2) was obtained. The obtained C.I. The content of the specific diketopyrrolopyrrole pigment A represented by Pigment Red 254 and the formula (A-2-2) was quantitatively analyzed by HPLC. The content of the specific diketopyrrolopyrrole pigment A represented by Pigment Red 254 and the formula (A-2-2) was 90.7% by mass and 9.3% by mass, respectively.

(Specific heterodimethopyrrolopyrrole pigment mixture 3 (RC-3))

Except that 15.1 parts of 4-cyanobiphenyl was changed to 19.3 parts of N, N-dibutyl-4-cyanobenzamide, the same procedure as in the preparation of the specific diketopyrrolopyrrole pigment mixture 1 (RC-1) 142.9 parts of a specific heterodimethopyrrolopyrrole pigment mixture 3 (RC-3) were obtained. The obtained C.I. The content of the specific diketopyrrolopyrrole pigment A represented by Pigment Red 254 and the formula (A-2-4a) was quantitatively analyzed by HPLC. The content of the specific diketopyrrolopyrrole pigment A represented by Pigment Red 254 and the formula (A-2-4a) was 90.8% by mass and 9.2% by mass, respectively.

<Method for producing binder resin solution>

(Preparation of acrylic resin solution 1)

196 parts of cyclohexanone was charged into a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introducing tube, a dropping tube and a stirrer, the temperature was raised to 80 ° C, Thereafter, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, and 0.2 part of para-cumylphenol ethylene oxide-modified acrylate (manufactured by Toagosei Co., Aronix M110 &quot;) and 1.1 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for another 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 heated and dried at 180 ° C for 20 minutes to measure the non-volatile content. Methoxy propyl acetate was added to the resin solution so as to have a non-volatile content of 20 mass% To prepare Resin Solution 1. The mass average molecular weight (Mw) was 26,000.

(Preparation of acrylic resin solution 2)

207 parts of cyclohexanone was added to a detachable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introducing tube, a dropping tube and a stirrer, and the temperature was raised to 80 DEG C. After the inside of the flask was replaced with nitrogen, 20 parts of acrylic acid-modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 20 parts of 2,2'- And 1.33 parts of azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for another 3 hours to obtain a copolymer resin solution. Next, with respect to the total amount of the obtained copolymer solution, the nitrogen gas was stopped and the mixture was stirred while injecting dry air for 1 hour. After cooling to room temperature, 2-methacryloyloxyethyl isocyanate (Showa Denko KK Karenz MOI ), 0.08 part of dibutyltin laurate, and 26 parts of cyclohexanone was added dropwise at 70 占 폚 over 3 hours. About 2 g of the resin solution was sampled and heated and dried at 180 占 폚 for 20 minutes to measure the nonvolatile content. Cyclohexanone was added to the resin solution so that the nonvolatile content was 20 mass% to prepare the acrylic resin solution 2. The weight average molecular weight (Mw) was 18,000.

&Lt; Preparation method of green and blue photosensitive coloring composition >

(Preparation of green photosensitive coloring composition 1 (GR-1)

The following mixture was stirred and mixed, and then dispersed for 5 hours with an Eiger mill ("mini model M-250 MKII" manufactured by Eiger Japan Co., Ltd.) using zirconia beads having a diameter of 0.5 mm, Mu] m filter to prepare a green colored composition 1 (GP-1).

Green pigment (CI Pigment Green 36) 6.8 parts

Yellow pigment (CI Pigment Yellow 150) 5.2 parts

1.0 part of a resinous dispersant ("EFKA4300" manufactured by Ciba Japan K.K.)

Acrylic resin solution 1 35.0 parts

Propylene glycol monomethyl ether acetate 52.0 parts

Subsequently, the mixture of the following composition was stirred and mixed so as to be uniform, and then filtered with a filter of 1 mu m to prepare a green photosensitive coloring composition 1 (GR-1).

Green coloring composition 1 (GP-1) 42.0 parts

Acrylic resin solution 2 13.2 parts

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

Photopolymerization initiator ("Irgacure-907" manufactured by Ciba Japan K.K.) 2.0 parts

(EAB-F manufactured by Hodogaya Chemical Co., Ltd.) 0.4 part

Ethylene glycol monomethyl ether acetate 39.6 parts

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

The following mixture was stirred and mixed, and then dispersed for 5 hours with an Eiger mill ("mini model M-250 MKII" manufactured by Eiger Japan Co., Ltd.) using zirconia beads having a diameter of 0.5 mm, Mu] m filter to obtain a blue coloring composition 1 (BP-1).

Blue pigment (CI Pigment Blue 15: 6) 7.2 parts

Purple pigment (CI Pigment Violet 23) 4.8 parts

1.0 part of a resinous dispersant ("EFKA4300" manufactured by Ciba Japan K.K.)

Acrylic resin solution 1 35.0 parts

Propylene glycol monomethyl ether acetate 52.0 parts

Subsequently, the mixture having the following composition was stirred and mixed so as to be uniform, and then filtered with a filter of 1 mu m to prepare a blue photosensitive coloring composition 1 (BR-1).

Blue coloring composition 1 (BP-1) 34.0 parts

Acrylic resin solution 2 15.2 parts

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

Photopolymerization initiator ("Irgacure-907" manufactured by Ciba Japan K.K.) 2.0 parts

(EAB-F manufactured by Hodogaya Chemical Co., Ltd.) 0.4 part

Ethylene glycol monomethyl ether acetate 45.1 parts

[Example 1]

(Preparation of pigment composition 1 (R-1)

99.0 parts of the brominated diketopyrrolopyrrole pigment of the formula (1), 1.0 part of the specific diketopyrrolopyrrole pigment A of the formula (A-2-1), 1000 parts of sodium chloride and 120 parts of diethylene glycol were charged into a stainless steel first gallon kneader Manufactured by Inoue Manufacturing Co., Ltd.) and kneaded at 60 占 폚 for 10 hours. Next, the kneaded mixture was put into hot water and stirred for 1 hour while being heated to about 80 DEG C to form a slurry, followed by filtration and washing with water to remove sodium chloride and diethylene glycol, followed by stirring at 80 DEG C for one day and one night Dried and pulverized to obtain 96.9 parts of diketopyrrolopyrrole pigment composition 1 (R-1). The average primary particle diameter was 37.0 nm.

[Example 2]

(Production of pigment composition 2 (R-2)

99.0 parts of the brominated diketopyrrolopyrrole pigment of the formula (1) and 1.0 part of the specific diketopyrrolopyrrole pigment A of the formula (A-2-1) were added to 97.0 parts of the brominated diketopyrrolopyrrole pigment of the formula (1) (R-1) was prepared in the same manner as in the preparation of pigment composition 1 (R-1), except that 3.0 parts of the specific diketopyrrolopyrrole pigment A of Example A- 2). The average primary particle diameter was 36.8 nm.

[Example 3]

(Preparation of pigment composition 3 (R-3)

99.0 parts of the brominated diketopyrrolopyrrole pigment of the formula (1) and 1.0 part of the specific diketopyrrolopyrrole pigment A of the formula (A-2-1), 95.0 parts of the brominated diketopyrrolopyrrole pigment of the formula (1) (R-1) was obtained in the same manner as in the preparation of pigment composition 1 (R-1), except that 5.0 parts of the specific diketopyrrolopyrrole pigment A of Example A- 3). The average primary particle diameter was 30.5 nm.

[Example 4]

(Preparation of pigment composition 4 (R-4)

99.0 parts of the brominated diketopyrrolopyrrole pigment of the formula (1) and 1.0 part of the specific diketopyrrolopyrrole pigment A of the formula (A-2-1), 90.0 parts of the brominated diketopyrrolopyrrole pigment of the formula (1) Except that the diketopyrrolopyrrole pigment composition 4 (R-1) was prepared in the same manner as in the preparation of the pigment composition 1 (R-1), except that 10.0 parts of the specific diketopyrrolopyrrole pigment A of Example A- 4). The average primary particle size was 28.5 nm.

[Example 5]

(Preparation of pigment composition 5 (R-5)

99.0 parts of the brominated diketopyrrolopyrrole pigment of the formula (1) and 1.0 part of the specific diketopyrrolopyrrole pigment A of the formula (A-2-1) were added to 85.0 parts of the brominated diketopyrrolopyrrole pigment of the formula (1) Except that the diketopyrrolopyrrole pigment composition 5 (R-1) was prepared in the same manner as in the preparation of the pigment composition 1 (R-1), except that the specific diketopyrrolopyrrole pigment A (15.0 parts) 5). The average primary particle diameter was 29.5 nm.

[Example 6]

(Preparation of pigment composition 6 (R-6)

Pigment composition 3 (R-3) was prepared in the same manner as in pigment preparation 1 except that the specific heterodimeropyrrolopyrrole pigment A of the formula (A-2-1) was changed to the specific heterodimeropyrrolopyrrole pigment A of the formula (A- 3), whereby 98.1 parts of diketopyrrolopyrrole pigment composition 6 (R-6) was obtained. The average primary particle diameter was 29.9 nm.

[Example 7]

(Preparation of pigment composition 7 (R-7)

Pigment Composition 3 (R-3) was prepared in the same manner as in Pigment Composition A except that the specific heterodimeropyrrolopyrrole pigment A of the formula (A-2-1) was changed to the specific heterodimeropyrrolopyrrole pigment A of the formula (A- 3), thereby obtaining 98.0 parts of diketopyrrolopyrrole pigment composition 7 (R-7). The average primary particle diameter was 30.7 nm.

[Example 8]

(Preparation of pigment composition 8 (R-8)

Pigment composition 3 (R-3) was prepared in the same manner as in pigment preparation 3 except that the specific heterodimeropyrrolopyrrole pigment A of the formula (A-2-1) was changed to the specific heterodimeropyrrolopyrrole pigment A of the formula (A- 3), whereby 98.4 parts of diketopyrrolopyrrole pigment composition 8 (R-8) was obtained. The average primary particle diameter was 31.2 nm.

[Example 9]

(Preparation of pigment composition 9 (R-9)

Pigment Composition 3 (R-2) was prepared in the same manner as Pigment Composition 1 except that the specific heterodimeropyrrolopyrrole pigment A of the formula (A-2-1) was changed to the specific heterodimeropyrrolopyrrole pigment A of the formula (A- 3), 97.5 parts of diketopyrrolopyrrole pigment composition 9 (R-9) was obtained. The average primary particle diameter was 35.4 nm.

[Example 10]

(Preparation of pigment composition 10 (R-10)

Pigment Composition 3 (R-3) was prepared in the same manner as in Pigment Composition 1 except that the specific heterodimeropyrrolopyrrole pigment A of the formula (A-2-1) was changed to the specific heterodimeropyrrolopyrrole pigment A of the formula (A- 3), 96.6 parts of diketopyrrolopyrrole pigment composition 10 (R-10) was obtained. The average primary particle diameter was 35.8 nm.

[Example 11]

(Preparation of pigment composition 11 (R-11)

Pigment Composition 3 (R-3) was prepared in the same manner as Pigment Composition 1 except that the specific heterodimeropyrrolopyrrole pigment A of the formula (A-2-1) was changed to the specific heterodimeropyrrolopyrrole pigment A of the formula (A- 3), 93.9 parts of diketopyrrolopyrrole pigment composition 11 (R-11) was obtained. The average primary particle diameter was 32.4 nm.

[Example 12]

(Preparation of pigment composition 12 (R-12)

The pigment composition 3 (R-3) was prepared in the same manner as in the pigment composition 3 except that the specific heterodimeropyrrolopyrrole pigment A of the formula (A-2-1) was changed to the specific heterodimeropyrrolopyrrole pigment A of the formula (A- 3), 95.7 parts of diketopyrrolopyrrole pigment composition 12 (R-12) was obtained. The average primary particle diameter was 29.8 nm.

[Example 13]

(Preparation of pigment composition 13 (R-13)

98.0 parts of the brominated diketopyrrolopyrrole pigment of the formula (1); 1.0 part of Pigment Red 254 (Irgaphor Red B-CF manufactured by Ciba Specialty Chemicals Inc.), 1.0 part of the specific diketopyrrolopyrrole pigment A of the formula (A-2-1), 1000 parts of sodium chloride and 120 parts of diethylene glycol 120 Were put into a stainless steel first gallon kneader (manufactured by Inoue Manufacturing Co., Ltd.) and kneaded at 60 DEG C for 10 hours. Next, the kneaded mixture was charged into hot water and stirred for 1 hour while heating at about 80 DEG C to form a slurry, followed by filtration and washing with water to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 DEG C, Thereby obtaining 96.7 parts of diketopyrrolopyrrole pigment composition 13 (R-13). The average primary particle diameter was 33.2 nm.

[Example 14]

(Preparation of pigment composition 14 (R-14)

98.0 parts of the brominated diketopyrrolopyrrole pigment of the formula (1); 1.0 part of Pigment Red 254 ("Irgaphor Red B-CF" manufactured by Ciba Specialty Chemicals Inc.) and 1.0 part of specific diketopyrrolopyrrole pigment A of formula (A-2-1) Lt; / RTI &gt; pigment, 80.0 parts of &lt; RTI ID = 18.0 parts of Pigment Red 254 ("Irgaphor Red B-CF" manufactured by Ciba Specialty Chemicals Inc.) and 2.0 parts of the specific diketopyrrolopyrrole pigment A of the formula (A-2-1) (R-13) was repeated to obtain 98.3 parts of diketopyrrolopyrrole pigment composition 14 (R-14). The average primary particle size was 30.2 nm.

[Example 15]

(Production of pigment composition 15 (R-15)

98.0 parts of the brominated diketopyrrolopyrrole pigment of the formula (1); 1.0 part of Pigment Red 254 ("Irgaphor Red B-CF" manufactured by Ciba Specialty Chemicals Inc.) and 1.0 part of specific diketopyrrolopyrrole pigment A of formula (A-2-1) 50.0 parts of a pyrrolopyr pigment, a commercially available CI 45.0 parts of Pigment Red 254 ("Irgaphor Red B-CF" manufactured by Ciba Specialty Chemicals Inc.) and 5.0 parts of the specific diketopyrrolopyrrole pigment A of the formula (A-2-1) (R-13), 97.0 parts of diketopyrrolopyrrole pigment composition 15 (R-15) was obtained. The average primary particle diameter was 26.7 nm.

[Example 16]

(Preparation of pigment composition 16 (R-16)

98.0 parts of the brominated diketopyrrolopyrrole pigment of the formula (1); 1.0 part of Pigment Red 254 ("Irgaphor Red B-CF" manufactured by Ciba Specialty Chemicals Inc.) and 1.0 part of specific diketopyrrolopyrrole pigment A of formula (A-2-1) 20.0 parts of a pyrrolopyr pigment, a commercially available CI Except that 72.0 parts of Pigment Red 254 ("Irgaphor Red B-CF" manufactured by Ciba Specialty Chemicals Inc.) and 8.0 parts of specific diketopyrrolopyrrole pigment A of formula (A-2-1) (R-13) was repeated to obtain 94.8 parts of diketopyrrolopyrrole pigment composition 16 (R-16). The average primary particle diameter was 28.0 nm.

[Example 17]

(Preparation of pigment composition 17 (R-17)

98.0 parts of the brominated diketopyrrolopyrrole pigment of the formula (1); 1.0 part of Pigment Red 254 ("Irgaphor Red B-CF" manufactured by Ciba Specialty Chemicals Inc.) and 1.0 part of specific diketopyrrolopyrrole pigment A of formula (A-2-1) 20.0 parts of a pyrrolopyr pigment, a commercially available CI Except that 65.0 parts of Pigment Red 254 ("Irgaphor Red B-CF" manufactured by Ciba Specialty Chemicals Inc.) and 15.0 parts of specific diketopyrrolopyrrole pigment A of formula (A-2-1) (R-13), 96.2 parts of diketopyrrolopyrrole pigment composition 17 (R-17) was obtained. The average primary particle diameter was 29.3 nm.

[Example 18]

(Preparation of pigment composition 18 (R-18)

20.0 parts of a specific diketopyrrolopyrrole pigment mixture 1 (RC-1), 1000 parts of sodium chloride and 120 parts of diethylene glycol were mixed with 80.0 parts of a brominated diketopyrrolopyrrole pigment of the formula (1), a stainless steel first gallon kneader (Inoue Manufacturing Co., Ltd.) and kneaded at 60 占 폚 for 10 hours. Next, the kneaded mixture was charged into hot water and stirred for 1 hour while heating at about 80 DEG C to form a slurry, followed by filtration and washing with water to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 DEG C, Thereby obtaining 96.9 parts of diketopyrrolopyrrole pigment composition 18 (R-18). The average primary particle size was 29.2 nm.

[Example 19]

(Preparation of pigment composition 19 (R-19)

Was the same as the preparation of pigment composition 18 (R-18), except that the specific heterodimeropyrrolopyrrole pigment mixture 1 (RC-1) was changed to a specific heterodimeropyrrolopyrrole pigment mixture 2 (RC-2) To obtain 96.1 parts of diketopyrrolopyrrole pigment composition 19 (R-19). The average primary particle diameter was 30.5 nm.

[Example 20]

(Preparation of pigment composition 20 (R-20)

(R-18), except that the specific heterodimeropyrrolopyrrole pigment mixture 1 (RC-1) was changed to a specific heterodimeropyrrolopyrrole pigment mixture 3 (RC-3) To obtain 95.4 parts of diketopyrrolopyrrole pigment composition 20 (R-20). The average primary particle diameter was 31.1 nm.

[Example 21]

(Preparation of pigment composition 21 (R-21)

95.0 parts of the brominated diketopyrrolopyrrole pigment of the formula (1), 5.0 parts of the specific diketopyrrolopyrrole pigment A of the formula (A-2-1), 5.0 parts of the dye derivative of the formula (7-1), 1000 parts of sodium chloride and 120 parts of diethylene glycol were put into a stainless steel first gallon kneader (manufactured by Inoue Manufacturing Co., Ltd.) and kneaded at 60 DEG C for 10 hours. Next, the kneaded mixture was charged into hot water and stirred for 1 hour while heating at about 80 DEG C to form a slurry, followed by filtration and washing with water to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 DEG C, Thereby obtaining 91.8 parts of diketopyrrolopyrrole pigment composition 21 (R-21). The average primary particle size was 27.4 nm.

[Example 22]

(Preparation of pigment composition 22 (R-22)

80.0 parts of a brominated diketopyrrolopyrrole pigment of the formula (1); , 18.0 parts of Pigment Red 254 ("Irgaphor Red B-CF" manufactured by Ciba Specialty Chemicals Inc.), 2.0 parts of the specific diketopyrrolopyrrole pigment A of the formula (A-2-1) , 5.0 parts of a derivative, 1000 parts of sodium chloride and 120 parts of diethylene glycol were put into a stainless steel first gallon kneader (manufactured by Inoue Manufacturing Co., Ltd.) and kneaded at 60 DEG C for 10 hours. Next, the kneaded mixture was charged into hot water and stirred for 1 hour while heating at about 80 DEG C to form a slurry, followed by filtration and washing with water to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 DEG C, Thereby obtaining 91.3 parts of diketopyrrolopyrrole pigment composition 22 (R-22). The average primary particle diameter was 29.1 nm.

[Referential Example 1]

(Preparation of pigment composition 23 (R-23)

The brominated diketopyrrolopyrrole pigment of the formula (1) is dissolved in a commercially available C.I. (R-4) was prepared in the same manner as in the preparation of the pigment composition 4 (R-4), except that Pigment Red 254 (Irgaphor Red B-CF, manufactured by Ciba Specialty Chemicals Inc.) was used instead of the diketopyrrolopyrrole pigment composition 23 (R-23). The average primary particle diameter was 30.9 nm.

[Reference Example 2]

(Preparation of pigment composition 24 (R-24)

100.0 parts of the brominated diketopyrrolopyrrole pigment of the formula (1), 1000 parts of sodium chloride and 120 parts of diethylene glycol were put into a stainless steel first gallon kneader (manufactured by Inoue Manufacturing Co., Ltd.) and kneaded at 60 DEG C for 10 hours . Next, the kneaded mixture was charged into hot water and stirred for 1 hour while heating at about 80 DEG C to form a slurry, followed by filtration and washing with water to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 DEG C, Thereby obtaining 96.9 parts of diketopyrrolopyrrole pigment composition 24 (R-24). The average primary particle diameter was 33.1 nm.

[Referential Example 3]

(Preparation of pigment composition 25 (R-25)

95.0 parts of the brominated diketopyrrolopyrrole pigment of the formula (1) and 5.0 parts of the specific diketopyrrolopyrrole pigment A of the formula (A-2-1) were mixed with 70.0 parts of the brominated diketopyrrolopyrrole pigment of the formula (1) (R-1) was prepared in the same manner as in the preparation of the pigment composition 1 (R-1), except that 30.0 parts of the specific diketopyrrolopyrrole pigment A of Example A-2-1 was changed to 30.0 parts of the diketopyrrolopyrrole pigment composition 25 25). The average primary particle diameter was 28.6 nm.

[Reference Example 4]

(Preparation of pigment composition 26 (R-26)

98.0 parts of the brominated diketopyrrolopyrrole pigment of the formula (1); 1.0 part of Pigment Red 254 ("Irgaphor Red B-CF" manufactured by Ciba Specialty Chemicals Inc.) and 1.0 part of specific diketopyrrolopyrrole pigment A of formula (A-2-1) 15.0 parts of a pyrrolopyr pigment, commercially available CI Except that 65.0 parts of Pigment Red 254 ("Irgaphor Red B-CF" manufactured by Ciba Specialty Chemicals Inc.) and 20.0 parts of the specific diketopyrrolopyrrole pigment A of formula (A-2-1) (R-13), 95.1 parts of diketopyrrolopyrrole pigment composition 26 (R-26) was obtained. The average primary particle diameter was 29.5 nm.

[Reference Example 5]

(Preparation of pigment composition 27 (R-27)

The brominated diketopyrrolopyrrole pigment of the formula (1) is dissolved in a commercially available C.I. (R-24) was prepared in the same manner as in the preparation of the pigment composition 24 (R-24), except that Pigment Red 254 (Irgaphor Red B-CF, manufactured by Ciba Specialty Chemicals Inc.) was used instead of the diketopyrrolopyrrole pigment composition 27 (R-27). The average primary particle diameter was 34.9 nm.

[Referential Example 6]

(Preparation of pigment composition 28 (R-28)

Was synthesized in the same manner as in Example 1016 of Japanese Patent Publication No. 2011-523433 to obtain a pigment composition 28 (R-28) comprising a diketopyrrolopyrrole pigment of the formula (1) and the following formula (A-17).

(55)

[Reference Example 7]

(Preparation of pigment composition 29 (R-29)

Was synthesized in the same manner as in Example 1039 of Japanese Patent Publication No. 2011-523433 to obtain a pigment composition 29 (R-29) comprising a diketopyrrolopyrrole pigment of the formula (1) and the following formula (A-18).

(56)

The contents of the pigment compositions 1 to 29 (R-1 to 29) thus prepared are shown in Table A-1. &Quot; PR254 &quot; Pigment Red 254 &quot;.

[Table A-1]

[Example 23]

(Preparation of coloring composition 1 (RP-1)) [

The following mixture was stirred and mixed, and then dispersed for 5 hours with an Eiger mill ("mini model M-250 MKII" manufactured by Eiger Japan Co., Ltd.) using zirconia beads having a diameter of 0.5 mm, Mu] m filter to obtain Coloring Composition 1 (RP-1).

Diketopyrrolopyrrole pigment composition 1 (R-1) 11.0 parts

Coloring matter derivative (14-1) 1.0 part

Acrylic resin solution 1 40.0 parts

Propylene glycol monomethyl ether acetate 48.0 parts

[Examples 24 to 44]

(Preparation of colored compositions 2 to 22 (RP-2 to 22)

2 to 22 (RP-2 to 22) were produced in the same manner as in Coloring Composition 1 (RP-1) except that Pigment Composition 1 (R-1) was changed to the pigment composition shown in Table A- Respectively.

[Example 45]

(Preparation of coloring composition 23 (RP-23)

The following mixture was stirred and mixed, and then dispersed for 5 hours with an Eiger mill ("mini model M-250 MKII" manufactured by Eiger Japan Co., Ltd.) using zirconia beads having a diameter of 0.5 mm, Mu] m filter to obtain Coloring Composition 23 (RP-23).

Diketopyrrolopyrrole pigment composition 2 (R-2) 11.0 parts

Dye derivative (6-3) 1.0 part

Resin dispersant 6.0 parts

(BYK161 (30% solution) manufactured by BYK-Chemie)

Acrylic resin solution 1 31.0 parts

Propylene glycol monomethyl ether acetate 51.0 parts

[Example 46]

(Preparation of coloring composition 24 (RP-24)

The following mixture was stirred and mixed, and then dispersed for 5 hours with an Eiger mill ("mini model M-250 MKII" manufactured by Eiger Japan Co., Ltd.) using zirconia beads having a diameter of 0.5 mm, Mu] m filter to obtain Coloring Composition 24 (RP-24).

12.0 parts of diketopyrrolopyrrole pigment composition 2 (R-2)

Resin type dispersant 3.6 parts

(Ajisper PB821 made by Ajinomoto Fine-Techno Co., Inc.)

Acrylic resin solution 1 23.0 parts

Propylene glycol monomethyl ether acetate 61.4 parts

[Reference Examples 8 to 14]

(Preparation of Coloring Composition 25 to 31 (RP-25 to 31)

Coloring compositions 25 to 31 (RP-25 to 31) were prepared in the same manner as in Coloring Composition 1 (RP-1) except that Pigment Composition 1 (R-1) was changed to the pigment composition shown in Table A- Respectively.

&Lt; Evaluation of coloring composition >

(Preparation of contrast measurement substrate)

The coloring compositions obtained in Examples 23 to 46 and Reference Examples 8 to 14 were applied on a glass substrate having a thickness of 100 mm x 100 mm and a thickness of 0.7 mm to a thickness of x = 0.640 in a C light source and dried. Then, the red coating film was obtained by heating at 230 占 폚 for 60 minutes.

(Evaluation of contrast ratio of coating film)

A method of measuring the contrast ratio of the coating film will be described. Light emitted from a backlight unit for a liquid crystal display passes through a polarizing plate, is polarized, passes through a dried coating film of a colored composition applied on a glass substrate, and reaches a polarizing plate. When the polarizing planes of the polarizing plate and the polarizing plate are parallel, the light is transmitted through the polarizing plate, but when the polarizing plane is straight (orthogonal), the light is blocked by the polarizing plate. However, when light polarized by the polarizing plate passes through the dried coating film of the coloring composition, scattering by the pigment particles occurs, and when a part of the polarizing plane is shifted, the amount of light transmitted through the polarizing plate is reduced when the polarizing plate is parallel, A part of the light is transmitted through the polarizing plate. The transmitted light was measured with the brightness on the polarizing plate, and the brightness when the polarizing plate was parallel and the ratio between the brightness when the polarizing plate was parallel (contrast ratio) were calculated.

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

Therefore, when scattering is caused by the pigment in the coating film, the luminance at the time of paralleling decreases and the luminance at the time of directing increases, so that the contrast ratio is lowered.

On the other hand, a color intensity meter ("BM-5A" manufactured by Topcon Corporation) was used as the luminance meter and a polarizing plate ("NPF-G1220DUN" manufactured by Nitto Denko Corporation) was used as the polarizer. On the other hand, at the time of measurement, a black mask having a hole of 1 cm in length and 1 cm was attached to the measurement portion in order to shield unnecessary light.

&Lt; Evaluation of viscosity stability &

(Measurement of initial viscosity and time-dependent increase rate)

On the day when the coloring composition was prepared, the viscosity of the coloring composition was measured using an E-type viscometer ("ELD type viscometer" manufactured by Toki Sangyo Co., Ltd.) at 25 ° C. Then, the coloring composition was allowed to stand at 40 占 폚 for 7 days from the day when the coloring composition was prepared, and the sample temperature was returned to 25 占 폚 and the viscosity at the elapsed time was measured according to the viscosity measurement method. Respectively.

(Initial Viscosity) x 100 (%) &lt; tb &gt;

(Evaluation of initial viscosity and time-dependent increase rate)

With respect to the viscosity stability, evaluation was carried out based on the time-dependent increase ratio. If the time-dependent increase rate is 80% or more and less than 120%, it can be practically tolerated. If the coloring composition is applied to a glass substrate in the same manner as above, the coating composition can not be applied under the same coating conditions, resulting in a problem in productivity. More preferably, it is in the range of 90% or more and less than 110%.

○: Increase over time 90% or more and less than 110%

DELTA: Increased over time 80% or more and less than 90%, or 110% or more and less than 120%

X: Less than 80%, or more than 120%

[Table A-2]

&Lt; Production method of other coloring composition >

(Preparation of coloring composition 32 (RP-32)

The following mixture was stirred and mixed, and then dispersed for 5 hours with an Eiger mill ("mini model M-250 MKII" manufactured by Eiger Japan Co., Ltd.) using zirconia beads having a diameter of 0.5 mm, Mu] m filter to obtain Coloring Composition 32 (RP-32).

Dianthraquinone-based pigment (PR177-1) 10.8 parts

Pigment derivative formula (8-5) 1.2 parts

Acrylic resin solution 1 40.0 parts

Propylene glycol monomethyl ether acetate 48.0 parts

[Example 47]

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

The mixture having the following composition was stirred and mixed so as to be uniform, and then filtered with a filter of 1 mu m to prepare a photosensitive coloring composition 1 (RR-1).

Coloring composition 1 (RP-1) 38.4 parts

Coloring composition 32 (RP-32) 3.6 parts

Acrylic resin solution 2 13.2 parts

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

Photopolymerization initiator ("Irgacure-907" manufactured by Ciba Japan K.K.) 2.0 parts

(EAB-F manufactured by Hodogaya Chemical Co., Ltd.) 0.4 part

Ethylene glycol monomethyl ether acetate 39.6 parts

[Examples 48 to 72]

(Preparation of photosensitive coloring compositions 2 to 24 (RR-2 to 24)

2 to 24 (RP-2 to 24) and the coloring composition (RP-2 to 24) were changed to the coloring compositions 2 to 24 Sensitive coloring compositions 2 to 24 (RP-2 to 24) were prepared in the same manner as in Example 47, except that the proportions of 32 (RP-32) were adjusted.

[Reference Examples 15 to 21]

(Preparation of Photosensitive Coloring Composition 25 to 31 (RR-25 to 31)

25 to 31 (RP-25 to 31) and the coloring composition (RP-25 to 31) were changed so that the coloring composition 1 (RP-1) was changed to the coloring compositions 25 to 31 Sensitive coloring compositions 25 to 31 (RR-25 to 31) were prepared in the same manner as in Example 47, except that the proportions of 32 (RP-32) were adjusted.

&Lt; Evaluation of Photosensitive Coloring Composition >

(Color characteristic, contrast ratio (CR) evaluation)

The photosensitive coloring compositions obtained in Examples 47 to 72 and Reference Examples 15 to 21 were applied on a glass substrate having a thickness of 100 mm x 100 mm and a thickness of 0.7 mm at a film thickness of x = 0.640 and y = 0.328 in a C light source After drying, ultraviolet rays of 300 mJ / cm &lt; 2 &gt; were irradiated using an ultra-high pressure mercury lamp. Then, the red coating film was obtained by heating at 230 占 폚 for 60 minutes. Then, the brightness (Y) and the contrast ratio (CR) of the obtained coating film were measured.

On the other hand, the chromaticity and brightness (Y) were measured with a brown spectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.).

(Evaluation of crystal precipitation on the coating film surface)

The photosensitive coloring composition obtained in Examples 47 to 72 and Reference Examples 15 to 21 was applied on a glass substrate having a thickness of 100 mm x 100 mm and 0.7 mm to a thickness of x = 0.640 in a C light source After drying, ultraviolet rays of 300 mJ / cm &lt; 2 &gt; were irradiated using an ultra-high pressure mercury lamp. Subsequently, the heat treatment was performed at 230 캜 for 60 minutes, and then the heat treatment was repeated twice at 240 캜 for 60 minutes. After the heat treatment, the surface of the coated film of the substrate was observed with an optical microscope, and the presence or absence of crystal precipitation was judged according to the following criteria.

⊚: After the heat treatment at 230 占 폚 for 60 minutes, additionally, after the heat treatment at 240 占 폚 for 60 minutes and additionally at 240 占 폚 for 60 minutes,

?: No crystal precipitation after heat treatment at 230 占 폚 for 60 minutes and additionally at 240 占 폚 for 60 minutes (crystal precipitation in second heat treatment at 240 占 폚 for 60 minutes)

DELTA: no crystal precipitation after the heat treatment at 230 DEG C for 60 minutes, but further crystallization by heat treatment at 240 DEG C for 60 minutes

×: Crystalline precipitation after heat treatment at 230 ° C. for 60 minutes

[Table A-3]

From the results in Table A-3, it can be seen that in the diketopyrrolopyrrole-based pigment composition containing the diketopyrrolopyrrole bromide pigment and the specific diketopyrrolopyrrole pigment A in the color filter formation, the specific diketopyrrolopyrrole pigment A In which the content of the diketopyrrolopyrrole pigment composition is from 1% by mass to 15% by mass, based on the total mass of the diketopyrrolopyrrole pigments, is particularly excellent in lightness, has a high contrast, It was possible to suppress the crystal precipitation of the diketopyrrolopyrrole-based pigment by the process.

&Lt; Fabrication of color filter &

A green photosensitive coloring composition and a blue photosensitive resin composition used for producing a color filter were produced. On the other hand, the photosensitive coloring composition 2 (RR-2) of this Example A was used for the red color.

A black matrix was patterned on a glass substrate, and photosensitive coloring composition 2 (RR-2) was coated thereon with a spin coater to a thickness of x = 0.640 and y = 0.328 to form a colored film. This coating film was irradiated with ultraviolet rays of 300 mJ / cm &lt; 2 &gt; through a photomask using an ultra-high pressure mercury lamp. Subsequently, an unexposed portion was removed by spray development using an alkali developer containing 0.2% by mass of an aqueous solution of sodium carbonate, followed by washing with ion-exchanged water. The substrate was heated at 230 ° C for 20 minutes to form a red filter segment. X = 0.150 and y = 0.060 were obtained by using the blue photosensitive coloring composition 1 (BR-1) at a film thickness of x = 0.300 and y = , And a green filter segment and a blue filter segment were formed to obtain a color filter.

By using the photosensitive coloring composition 2 (RR-2), it was possible to produce a color filter having high definition and high contrast, and free from crystal precipitation in the heating process.

[Example B]

Unless specifically stated, "part" and "%" mean "part by mass" and "% by mass", respectively. (6-3), a benzoisoindole derivative of the formula (7-1), an anthraquinone derivative of the formula (8-5) and an anthraquinone derivative of the formula Quinophthalone derivatives of formula (14-1) were used.

(Average primary particle diameter of pigment)

The average primary particle size of the pigment composition thus prepared was measured (calculated) by the following method.

Propylene glycol monomethyl ether acetate was added to the powder of the pigment composition, a small amount of Disperbyk-161 as a resinous dispersant was added, and the mixture was treated with ultrasonic waves for 1 minute to prepare a sample for measurement. This sample was photographed with a transmission electron microscope (TEM) to take three photographs (three fields of view) capable of identifying primary particles of 100 or more pigments, and measuring the sizes of 100 primary particles from the upper left corner respectively Respectively. Specifically, the minor axis diameter and the major axis diameter of the primary particles of each pigment are measured in units of nm, and the average thereof is taken as the primary particle diameter of the pigment particles. A total of 300 distributions are prepared every 5 nm, (For example, 8 nm in the case of 6 nm or more and 10 nm or less) was approximated as the particle diameter of these particles, and the number average particle diameter was calculated based on the particle diameter and the number of the particles.

&Lt; Process for producing diketopyrrolopyrrole-based pigment composition >

[Example 1]

(Preparation of pigment composition 1 (R-1)

200 parts of tert-amyl alcohol dehydrated by molecular sieves and 140 parts of sodium-tert-amyl alkoxide were added to a stainless steel reaction vessel equipped with a reflux tube and heated to 100 占 폚 with stirring to obtain an alcoholate solution Lt; / RTI &gt; On the other hand, 88 parts of diisopropyl succinate and 153.6 parts of 4-bromobenzonitrile were added to a glass flask and dissolved by heating at 90 占 폚 with stirring to prepare a solution of these mixtures. The heated solution of the mixture was slowly dropped into the above alcoholate solution heated to 100 占 폚 at a constant rate over 2 hours while stirring vigorously. After completion of the dropwise addition, heating and stirring were continued at 90 占 폚 for 2 hours to obtain an alkali metal salt of a diketopyrrolopyrrole compound. Then, 600 parts of methanol, 600 parts of water and 304 parts of acetic acid were added to a reaction vessel equipped with a glass jacket and cooled to -10 占 폚. The cooled mixture was subjected to the addition of a small amount of an alkali metal salt solution of the diketopyrrolopyrrole compound obtained in the previous step in which a common disk having a diameter of 8 cm was rotated at 4000 rpm using a high- Respectively. At this time, while cooling the mixture of methanol, acetic acid and water to keep the temperature at -5 ° C or lower at all times, while adjusting the rate of addition of the alkali metal salt of the diketopyrrolopyrrole compound at 75 ° C, Min. &Lt; / RTI &gt; After addition of the alkali metal salt, red crystals precipitated and a red suspension was formed. Subsequently, the obtained red suspension was washed with an ultrafiltration device at 5 DEG C, and filtered to obtain a red paste. This paste was redispersed in 3500 parts of methanol cooled to 0 DEG C to obtain a suspension having a methanol concentration of about 90% and stirred at 5 DEG C for 3 hours to effect particle sizing and cleaning following the crystal transition. Subsequently, the resulting aqueous diketopyrrolopyrrole compound-based water paste was dried at 80 ° C for 24 hours and pulverized to obtain 150.8 parts of the brominated diketopyrrolopyrrole pigment represented by the formula (1).

Subsequently, 220 parts of tert-amyl alcohol was placed in the reaction vessel 1, and 32 parts of 60% NaH was added while cooling in a water bath, followed by heating and stirring at 90 占 폚. Subsequently, 99 parts of the compound of the following formula (B-16) synthesized by the method of Tetrahedron, 58 (2002) 5547-5565 and 99.2 parts of the benzoic acid of the formula (B-3-1) 60.9 parts of the nitrile compound were dissolved by heating, and this was dropwise added to the reaction vessel 1 over 2 hours. The mixture was allowed to react at 120 DEG C for 10 hours, cooled to 60 DEG C, and then 400 parts of methanol and 50 parts of acetic acid were added, followed by washing with water and methanol to obtain the specific heterodimeropyrrolopyrrole (B- 87.8 parts of pigment B was obtained.

(57)

97.0 parts of the brominated diketopyrrolopyrrole pigment of the formula (1) obtained, 3.0 parts of the specific diketopyrrolopyrrole pigment B of the formula (B-2-1), 1000 parts of sodium chloride and 120 parts of diethylene glycol, Gallon kneader (manufactured by Inoue Manufacturing Co., Ltd.) and kneaded at 60 ° C for 10 hours. Next, the kneaded mixture was charged into hot water and stirred for 1 hour while heating at about 80 DEG C to form a slurry, followed by filtration and washing with water to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 DEG C, Thereby obtaining 96.5 parts of pigment composition 1 (R-1) which is a diketopyrrolopyrrole pigment composition. The average primary particle diameter was 36.8 nm.

[Example 2]

(Production of pigment composition 2 (R-2)

95.0 parts of the brominated diketopyrrolopyrrole pigment of the formula (1) used in the preparation of the pigment composition 1, 5.0 parts of the specific diketopyrrolopyrrole pigment B of the formula (B-2-1), 1000 parts of sodium chloride, and 100 parts of diethylene glycol Were added to a stainless steel first gallon kneader (manufactured by Inoue Manufacturing Co., Ltd.), and kneaded at 60 DEG C for 10 hours. Next, the kneaded mixture was charged into hot water and stirred for 1 hour while heating at about 80 DEG C to form a slurry, followed by filtration and washing with water to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 DEG C, Thereby obtaining 97.2 parts of pigment composition 2 (R-2) which is a diketopyrrolopyrrole pigment composition. The average primary particle diameter was 30.5 nm.

[Example 3]

(Preparation of pigment composition 3 (R-3)

95.0 parts of the brominated diketopyrrolopyrrole pigment of the formula (1) and 5.0 parts of the specific diketopyrrolopyrrole pigment B of the formula (B-2-1) were mixed with 90.0 parts of the brominated diketopyrrolopyrrole pigment of the formula (1) (R-2) was prepared in the same manner as in the production of pigment composition 2 (R-2), except that 10.0 parts of the specific diketopyrrolopyrrole pigment B of Example B-2-1 (R-3). The average primary particle diameter was 26.5 nm.

[Example 4]

(Preparation of pigment composition 4 (R-4)

95.0 parts of the brominated diketopyrrolopyrrole pigment of the formula (1) and 5.0 parts of the specific diketopyrrolopyrrole pigment B of the formula (B-2-1) were mixed with 85.0 parts of the brominated diketopyrrolopyrrole pigment of the formula (1) (R-2) was prepared in the same manner as in the production of pigment composition 2 (R-2) except that the specific diketopyrrolopyrrole pigment B (B-2-1) (R-4). The average primary particle size was 28.5 nm.

[Example 5]

(Preparation of pigment composition 5 (R-5)

The specific heterodimer compound (B-3-1) was obtained in the same manner as in the pigment composition 1 (R-1) except that 60.2 parts of the benzonitrile compound of the formula (B-3-1) was changed to 54.2 parts of the benzonitrile compound of the formula Pyrrole pigment B, 85.2 parts of the specific heterodimeropyrrolopyrrole pigment B represented by the formula (B-2-2) was obtained.

Subsequently, 95.0 parts of the brominated diketopyrrolopyrrole pigment of the formula (1), 5.0 parts of the specific diketopyrrolopyrrole pigment B of the formula (B-2-2), 1000 parts of sodium chloride and 120 parts of diethylene glycol, Gallon kneader (manufactured by Inoue Manufacturing Co., Ltd.) and kneaded at 60 ° C for 10 hours. Next, the kneaded mixture was poured into warm water and stirred for 1 hour while heating at about 80 DEG C to form a slurry, followed by filtration and washing with water to remove sodium chloride and ethylene glycol, followed by drying at 80 DEG C overnight and pulverization Thereby obtaining 96.2 parts of pigment composition 5 (R-5) which is a diketopyrrolopyrrole pigment composition. The average primary particle diameter was 31.6 nm.

[Example 6]

(Preparation of pigment composition 6 (R-6)

First, a specific heterodimer (R-1) was performed in pigment composition 1 (R-1), except that 60.2 parts of the benzonitrile compound of the formula (B-3-1) was changed to 58.2 parts of the benzonitrile compound of the formula Was carried out in the same manner as in the preparation of the tofuropyrrolopyrrole pigment B to obtain 82.2 parts of the specific heterodimeropyrrolopyrrole pigment B represented by the formula (B-2-3).

Subsequently, 95.0 parts of the brominated diketopyrrolopyrrole pigment of the formula (1), 5.0 parts of the specific diketopyrrolopyrrole pigment B of the formula (B-2-3), 1000 parts of sodium chloride and 120 parts of diethylene glycol, Gallon kneader (manufactured by Inoue Manufacturing Co., Ltd.) and kneaded at 60 ° C for 10 hours. Next, the kneaded mixture was charged into hot water and stirred for 1 hour while heating at about 80 DEG C to form a slurry, followed by filtration and washing with water to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 DEG C, Thereby obtaining 95.9 parts of pigment composition 6 (R-6) which is a diketopyrrolopyrrole pigment composition. The average primary particle diameter was 34.6 nm.

[Example 7]

(Preparation of pigment composition 7 (R-7)

1 was prepared in the same manner as in the pigment composition 1 (R-1) except that 60.2 parts of the benzonitrile compound of the formula (B-3-1) was changed to 84.1 parts of the benzonitrile compound of the formula (B- Pyrrole pigment B, to obtain 94.1 parts of a specific heterodimeropyrrolopyrrole pigment B represented by the formula (B-2-4a).

Subsequently, 95.0 parts of the brominated diketopyrrolopyrrole pigment of the formula (1), 5.0 parts of the specific diketopyrrolopyrrole pigment B of the formula (B-2-4a), 1000 parts of sodium chloride and 120 parts of diethylene glycol, Gallon kneader (manufactured by Inoue Manufacturing Co., Ltd.) and kneaded at 60 ° C for 10 hours. Next, the kneaded mixture was charged into hot water and stirred for 1 hour while heating at about 80 DEG C to form a slurry, followed by filtration and washing with water to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 DEG C, Thereby obtaining 97.9 parts of pigment composition 7 (R-7) as a diketopyrrolopyrrole pigment composition. The average primary particle diameter was 28.6 nm.

[Example 8]

(Preparation of pigment composition 8 (R-8)

95.0 parts of the brominated diketopyrrolopyrrole pigment of the formula (1) and 5.0 parts of the specific diketopyrrolopyrrole pigment B of the formula (B-2-4a) were mixed with 85.0 parts of the brominated diketopyrrolopyrrole pigment of the formula (1) (R-7) was prepared in the same manner as in the preparation of the pigment composition 7 (R-7), except that 15.0 parts of the specific diketopyrrolopyrrole pigment B of Example B-2-4a) R-8). The average primary particle diameter was 25.5 nm.

[Example 9]

(Preparation of pigment composition 9 (R-9)

The specific heterodimer compound (B-3-1) was prepared in the same manner as in the pigment composition 1 (R-1) except that 60.2 parts of the benzonitrile compound of the formula (B-3-1) was changed to 71.8 parts of the benzonitrile compound of the formula Pyrrole pigment B to obtain 79.1 parts of the specific diketopyrrolopyrrole pigment B represented by the formula (B-2-4b).

Subsequently, 95.0 parts of the brominated diketopyrrolopyrrole pigment of the formula (1), 5.0 parts of the specific diketopyrrolopyrrole pigment B of the formula (B-2-4b), 1000 parts of sodium chloride and 120 parts of diethylene glycol, Gallon kneader (manufactured by Inoue Manufacturing Co., Ltd.) and kneaded at 60 ° C for 10 hours. Next, the kneaded mixture was charged into hot water and stirred for 1 hour while heating at about 80 DEG C to form a slurry, followed by filtration and washing with water to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 DEG C, Thereby obtaining 96.5 parts of pigment composition 9 (R-9) which is a diketopyrrolopyrrole pigment composition. The average primary particle diameter was 31.1 nm.

[Example 10]

(Preparation of pigment composition 10 (R-10)

(R-1), except that 60.2 parts of the benzonitrile compound of the formula (B-3-1) was changed to 49.7 parts of the benzonitrile compound of the formula (B-3-5) Pyrrole pigment B to obtain 66.9 parts of the specific heterodimethopyrrolopyrrole pigment B represented by the formula (B-2-5).

Subsequently, 95.0 parts of the brominated diketopyrrolopyrrole pigment of the formula (1), 5.0 parts of the specific diketopyrrolopyrrole pigment B of the formula (B-2-5), 1000 parts of sodium chloride and 120 parts of diethylene glycol, Gallon kneader (manufactured by Inoue Manufacturing Co., Ltd.) and kneaded at 60 ° C for 10 hours. Next, the kneaded mixture was charged into hot water and stirred for 1 hour while heating at about 80 DEG C to form a slurry, followed by filtration and washing with water to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 DEG C, Thereby obtaining 97.5 parts of pigment composition 10 (R-10) which is a diketopyrrolopyrrole pigment composition. The average primary particle diameter was 33.1 nm.

[Example 11]

(Preparation of pigment composition 11 (R-11)

(R-1), except that 60.2 parts of the benzonitrile compound of the formula (B-3-1) was changed to 106.9 parts of the benzonitrile compound of the formula (B-3-6b) Pyrrole pigment B, 90.7 parts of the specific diketopyrrolopyrrole pigment B represented by the formula (B-2-6b) was obtained.

Subsequently, 95.0 parts of the brominated diketopyrrolopyrrole pigment of the formula (1), 5.0 parts of the specific diketopyrrolopyrrole pigment B of the formula (B-2-6b), 1000 parts of sodium chloride and 120 parts of diethylene glycol, Gallon kneader (manufactured by Inoue Manufacturing Co., Ltd.) and kneaded at 60 ° C for 10 hours. Next, the kneaded mixture was charged into hot water and stirred for 1 hour while heating at about 80 DEG C to form a slurry, followed by filtration and washing with water to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 DEG C, Thereby obtaining 98.1 parts of pigment composition 11 (R-11), which is a diketopyrrolopyrrole pigment composition. The average primary particle size was 28.9 nm.

[Example 12]

(Preparation of pigment composition 12 (R-12)

The specific heterodimer compound (B) was prepared in the same manner as in the pigment composition 1 (R-1) except that 60.2 parts of the benzonitrile compound of the formula (B-3-1) was changed to 75.6 parts of the benzonitrile compound of the formula Pyrrol pigment B, 100.8 parts of the specific diketopyrrolopyrrole pigment B represented by the formula (B-2-6c) was obtained.

Subsequently, 95.0 parts of the brominated diketopyrrolopyrrole pigment of the formula (1), 5.0 parts of the specific diketopyrrolopyrrole pigment B of the formula (B-2-6c), 1000 parts of sodium chloride and 120 parts of diethylene glycol, Gallon kneader (manufactured by Inoue Manufacturing Co., Ltd.) and kneaded at 60 ° C for 10 hours. Next, the kneaded mixture was charged into hot water and stirred for 1 hour while heating at about 80 DEG C to form a slurry, followed by filtration and washing with water to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 DEG C, Thereby obtaining 97.4 parts of pigment composition 12 (R-12) which is a diketopyrrolopyrrole pigment composition. The average primary particle diameter was 29.8 nm.

[Example 13]

(Preparation of pigment composition 13 (R-13)

(R-1) was prepared in the same manner as in the pigment composition 1 (R-1) except that 60.2 parts of the benzonitrile compound of the formula (B-3-1) was changed to 87.8 parts of the benzonitrile compound of the formula Pyrrole pigment B, 85.2 parts of the specific diketopyrrolopyrrole pigment B represented by the formula (B-2-7) was obtained.

Subsequently, 95.0 parts of the brominated diketopyrrolopyrrole pigment of the formula (1), 5.0 parts of the specific diketopyrrolopyrrole pigment B of the formula (B-2-7), 1000 parts of sodium chloride and 120 parts of diethylene glycol, Gallon kneader (manufactured by Inoue Manufacturing Co., Ltd.) and kneaded at 60 ° C for 10 hours. Next, the kneaded mixture was charged into hot water and stirred for 1 hour while heating at about 80 DEG C to form a slurry, followed by filtration and washing with water to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 DEG C, Thereby obtaining 96.3 parts of pigment composition 13 (R-13) as a diketopyrrolopyrrole pigment composition. The average primary particle diameter was 28.2 nm.

[Example 14]

(Preparation of pigment composition 14 (R-14)

95.0 parts of the brominated diketopyrrolopyrrole pigment of the formula (1) and 5.0 parts of the specific heterodimeropyrrolopyrrole pigment B of the formula (B-2-7) were mixed with 85.0 parts of the brominated diketopyrrolopyrrole pigment of the formula (1) (R-13) was prepared in the same manner as in the preparation of the pigment composition 13 (R-13), except that 15.0 parts of the specific diketopyrrolopyrrole pigment B of Example B-2-7 R-14). The average primary particle diameter was 26.5 nm.

[Example 15]

(Production of pigment composition 15 (R-15)

The specific heterodimer compound (B-3-1) was obtained in the same manner as in the pigment composition 1 (R-1) except that 60.2 parts of the benzonitrile compound of the formula (B-3-1) was changed to 50.0 parts of the benzonitrile compound of the formula Pyrrol pigment B, 64.5 parts of the specific diketopyrrolopyrrole pigment B represented by the formula (B-2-8) was obtained.

Subsequently, 95.0 parts of the brominated diketopyrrolopyrrole pigment of the formula (1), 5.0 parts of the specific diketopyrrolopyrrole B of the formula (B-2-8), 1000 parts of sodium chloride and 120 parts of diethylene glycol, Kneader (manufactured by Inoue Manufacturing Co., Ltd.) and kneaded at 60 占 폚 for 10 hours. Next, the kneaded mixture was charged into hot water and stirred for 1 hour while heating at about 80 DEG C to form a slurry, followed by filtration and washing with water to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 DEG C, Thereby obtaining 97.3 parts of pigment composition 15 (R-15) which is a diketopyrrolopyrrole pigment composition. The average primary particle diameter was 34.2 nm.

[Example 16]

(Preparation of pigment composition 16 (R-16)

200 parts of tert-amyl alcohol dehydrated by molecular sieves and 140 parts of sodium-tert-amyl alkoxide were added to a stainless steel reaction vessel equipped with a reflux tube and heated to 100 占 폚 with stirring to obtain an alcoholate solution Lt; / RTI &gt; On the other hand, 88 parts of diisopropyl succinate, 146.0 parts of 4-bromobenzonitrile and 7.6 parts of benzonitrile compound of the formula (B-3-1) were added to a glass flask and dissolved by heating at 90 캜 with stirring. A solution of the mixture was prepared. The heated solution of the mixture was slowly dropped into the above alcoholate solution heated to 100 占 폚 at a constant rate over 2 hours while stirring vigorously. After completion of the dropwise addition, heating and stirring were continued at 90 占 폚 for 2 hours to obtain an alkali metal salt of a diketopyrrolopyrrole compound. Then, 600 parts of methanol, 600 parts of water and 304 parts of acetic acid were added to a reaction vessel equipped with a glass jacket and cooled to -10 占 폚. The cooled mixture was subjected to the addition of a small amount of an alkali metal salt solution of the diketopyrrolopyrrole compound obtained in the previous step in which a common disk having a diameter of 8 cm was rotated at 4000 rpm using a high- Respectively. At this time, while cooling the mixture of methanol, acetic acid and water to keep the temperature at -5 ° C or lower at all times, while adjusting the rate of addition of the alkali metal salt of the diketopyrrolopyrrole compound at 75 ° C, Min. &Lt; / RTI &gt; After addition of the alkali metal salt, red crystals precipitated and a red suspension was formed. Subsequently, the obtained red suspension was washed with an ultrafiltration device at 5 DEG C, and filtered to obtain a red paste. This paste was redispersed in 3500 parts of methanol cooled to 0 DEG C to obtain a suspension having a methanol concentration of about 90% and stirred at 5 DEG C for 3 hours to effect particle sizing and cleaning following the crystal transition. Subsequently, the obtained aqueous diketopyrrolopyrrole compound-based water paste was filtered with an ultrafilter, and dried at 80 DEG C for 24 hours and pulverized to obtain 145.8 parts of diketopyrrolopyrrole-based pigment composition.

The content of the diketopyrrolopyrrole pigment represented by the formula (1) and the specific diketopyrrolopyrrole pigment B represented by the formula (B-2-1) in the obtained diketopyrrolopyrrole pigment composition was measured by HPLC As a result of quantitative analysis, the mass ratio of the diketopyrrolopyrrole bromide pigment represented by the formula (1) to the specific heterodimeropyrrolopyrrole pigment B represented by the formula (B-2-1) was 94.3: 5.7. The HPLC measurement conditions and the holding time were as follows. The calibration curve required for quantification was obtained by using the diketopyrrolopyrrole bromide pigment of the formula (1) synthesized in the preparation of the pigment composition 1 (R-1) and the specific diketopyrrolopyrrole pigment B of the formula (B-2-1) .

Device; JASCO Corporation 1st Gulliver Series

Detector; UV-970 detector manufactured by JASCO Corporation

column; Symmetry C18 (5 占 퐉, 2.1 mm? 150 mm) manufactured by Waters Corporation,

Liquid phase A; Dimethylformamide / water (1: 1)

Mobile phase B liquid; Dimethylformamide / water (97.5: 2.5)

Gladiant (liquid B); 47% → (15 min) → 47% → (5 min) → 100% → (25 min) → 100%

wavelength; 510 nm

Column temperature; 35 ℃

flux; 0.3 mL / min

Sample injection amount; ₅ μL (dissolved in N-methylpyrrolidone / 28% CH ₃ ONa methanol solution)

The retention time of the formula (1); 11.9 ~ 12.9 min

The retention time of the formula (B-2-1); 13.2 ~ 14.1 min

Subsequently, 100.0 parts of the obtained diketopyrrolopyrrole pigment composition, 1000 parts of sodium chloride and 120 parts of diethylene glycol were put into a stainless steel first gallon kneader (manufactured by Inoue Manufacturing Co., Ltd.) and kneaded at 60 ° C for 10 hours . Next, the kneaded mixture was charged into hot water and stirred for 1 hour while heating at about 80 DEG C to form a slurry, followed by filtration and washing with water to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 DEG C, Thereby obtaining 97.6 parts of pigment composition 16 (R-16) which is a diketopyrrolopyrrole pigment composition. The average primary particle size was 32.2 nm.

[Example 17]

(Preparation of pigment composition 17 (R-17)

200 parts of tert-amyl alcohol dehydrated by molecular sieves and 140 parts of sodium-tert-amyl alkoxide were added to a stainless steel reaction vessel equipped with a reflux tube and heated to 100 占 폚 with stirring to obtain an alcoholate solution Lt; / RTI &gt; On the other hand, 88 parts of diisopropyl succinate, 146.0 parts of 4-bromobenzonitrile and 7.6 parts of benzonitrile compound of the formula (B-3-1) were added to a glass flask and dissolved by heating at 90 캜 with stirring. A solution of the mixture was prepared. The heated solution of the mixture was slowly dropped into the above alcoholate solution heated to 100 占 폚 at a constant rate over 2 hours while stirring vigorously. After completion of the dropwise addition, heating and stirring were continued at 90 占 폚 for 2 hours to obtain an alkali metal salt of a diketopyrrolopyrrole compound. Then, 600 parts of methanol, 600 parts of water and 304 parts of acetic acid were added to a reaction vessel equipped with a glass jacket and cooled to -10 占 폚. The cooled mixture was subjected to the addition of a small amount of an alkali metal salt solution of the diketopyrrolopyrrole compound obtained in the previous step in which a common disk having a diameter of 8 cm was rotated at 4000 rpm using a high- Respectively. At this time, while cooling the mixture of methanol, acetic acid and water to keep the temperature at -5 ° C or lower at all times, while adjusting the rate of addition of the alkali metal salt of the diketopyrrolopyrrole compound at 75 ° C, Min. &Lt; / RTI &gt; After addition of the alkali metal salt, red crystals precipitated and a red suspension was formed. Subsequently, the obtained red suspension was washed with an ultrafiltration device at 5 DEG C, and filtered to obtain a red paste. This paste was redispersed in 3500 parts of methanol cooled to 0 DEG C to obtain a suspension having a methanol concentration of about 90% and stirred at 5 DEG C for 3 hours to effect particle sizing and cleaning following the crystal transition. Subsequently, the mixture was filtered with an ultrafilter to obtain a red paste of a diketopyrrolopyrrole compound. The obtained red paste was re-dispersed in 3000 ml of water, and then a pigment derivative slurry in which 5.5 parts of the benzoisoindole derivative represented by the formula (7-1) was added to 100 parts of water was added with stirring, The mixture was stirred for 1 hour and then washed with water to obtain a water paste of a diketopyrrolopyrrole compound. This water paste was dried at 80 캜 for 24 hours and pulverized to obtain 154.8 parts of diketopyrrolopyrrole pigment composition.

(B-2-1) represented by the formula (B-2-1) and the brominated diketopyrrolopyrrole pigment represented by the formula (1) in the diketopyrrolopyrrole pigment composition were obtained in the same manner as in the production of the pigment composition 16 The content of diketopyrrolopyrrole pigment B was quantitatively analyzed by HPLC to find that the brominated diketopyrrolopyrrole pigment represented by formula (1) and the specific heterodimeric pyrrole represented by formula (B-2-1) The mass ratio of pyrrole pigment B was 94.8: 5.2.

Subsequently, 100.0 parts of the obtained diketopyrrolopyrrole pigment composition, 1000 parts of sodium chloride and 120 parts of diethylene glycol were put into a stainless steel first gallon kneader (manufactured by Inoue Manufacturing Co., Ltd.) and kneaded at 60 ° C for 10 hours . Next, the kneaded mixture was charged into hot water and stirred for 1 hour while heating at about 80 DEG C to form a slurry, followed by filtration and washing with water to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 DEG C, Thereby obtaining 96.6 parts of pigment composition 17 (R-17) which is a diketopyrrolopyrrole pigment composition. The average primary particle diameter was 27.2 nm.

[Example 18]

(Preparation of pigment composition 18 (R-18)

200 parts of tert-amyl alcohol dehydrated by molecular sieves and 140 parts of sodium-tert-amyl alkoxide were added to a stainless steel reaction vessel equipped with a reflux tube and heated to 100 占 폚 with stirring to obtain an alcoholate solution Lt; / RTI &gt; On the other hand, 88 parts of diisopropyl succinate, 146.0 parts of 4-bromobenzonitrile and 7.6 parts of benzonitrile compound of the formula (B-3-1) were added to a glass flask and dissolved by heating at 90 캜 with stirring. A solution of the mixture was prepared. The heated solution of the mixture was slowly dropped into the above alcoholate solution heated to 100 占 폚 at a constant rate over 2 hours while stirring vigorously. After completion of the dropwise addition, heating and stirring were continued at 90 占 폚 for 2 hours to obtain an alkali metal salt of a diketopyrrolopyrrole compound. Then, 600 parts of methanol, 600 parts of water and 304 parts of acetic acid were added to a reaction vessel equipped with a glass jacket and cooled to -10 占 폚. The cooled mixture was subjected to the addition of a small amount of an alkali metal salt solution of the diketopyrrolopyrrole compound obtained in the previous step in which a common disk having a diameter of 8 cm was rotated at 4000 rpm using a high- Respectively. At this time, while cooling the mixture of methanol, acetic acid and water to keep the temperature at -5 ° C or lower at all times, while adjusting the rate of addition of the alkali metal salt of the diketopyrrolopyrrole compound at 75 ° C, Min. &Lt; / RTI &gt; After addition of the alkali metal salt, red crystals precipitated and a red suspension was formed. Subsequently, the obtained red suspension was washed with an ultrafiltration device at 5 DEG C, and filtered to obtain a red paste. This paste was redispersed in 3500 parts of methanol cooled to 0 DEG C to obtain a suspension having a methanol concentration of about 90% and stirred at 5 DEG C for 3 hours to effect particle sizing and cleaning following the crystal transition. Subsequently, the obtained aqueous diketopyrrolopyrrole compound-based water paste was filtered with an ultrafilter, and dried at 80 DEG C for 24 hours and pulverized to obtain 145.8 parts of diketopyrrolopyrrole-based pigment composition.

(B-2-1) represented by the formula (B-2-1) and the brominated diketopyrrolopyrrole pigment represented by the formula (1) in the diketopyrrolopyrrole pigment composition were obtained in the same manner as in the production of the pigment composition 16 The content of diketopyrrolopyrrole pigment B was quantitatively analyzed by HPLC to find that the brominated diketopyrrolopyrrole pigment represented by formula (1) and the specific heterodimeric pyrrole represented by formula (B-2-1) The mass ratio of pyrrole pigment B was 94.5: 5.5.

Subsequently, 85.5 parts of the obtained diketopyrrolopyrrole pigment composition, 4.5 parts of the pigment derivative of the benzoisoindole derivative of the formula (7-1), 1000 parts of sodium chloride and 120 parts of diethylene glycol were added to a stainless steel first gallon kneader Ltd.) and kneaded at 60 占 폚 for 10 hours. Next, the kneaded mixture was charged into hot water and stirred for 1 hour while heating at about 80 DEG C to form a slurry, followed by filtration and washing with water to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 DEG C, Thereby obtaining 95.6 parts of pigment composition 18 (R-18), which is a diketopyrrolopyrrole pigment composition. The average primary particle diameter was 26.2 nm.

[Example 19]

(Preparation of pigment composition 19 (R-19)

200 parts of tert-amyl alcohol dehydrated by molecular sieves and 140 parts of sodium-tert-amyl alkoxide were added to a stainless steel reaction vessel equipped with a reflux tube and heated to 100 占 폚 with stirring to obtain an alcoholate solution Lt; / RTI &gt; On the other hand, 88 parts of diisopropyl succinate, 138.3 parts of 4-bromobenzonitrile and 15.1 parts of benzonitrile compound of the formula (B-3-1) were added to a glass flask and dissolved by heating at 90 캜 with stirring. A solution of the mixture was prepared. The heated solution of the mixture was slowly dropped into the above alcoholate solution heated to 100 占 폚 at a constant rate over 2 hours while stirring vigorously. After completion of the dropwise addition, heating and stirring were continued at 90 占 폚 for 2 hours to obtain an alkali metal salt of a diketopyrrolopyrrole compound. Then, 600 parts of methanol, 600 parts of water and 304 parts of acetic acid were added to a reaction vessel equipped with a glass jacket and cooled to -10 占 폚. The cooled mixture was subjected to the addition of a small amount of an alkali metal salt solution of the diketopyrrolopyrrole compound obtained in the previous step in which a common disk having a diameter of 8 cm was rotated at 4000 rpm using a high- Respectively. At this time, while cooling the mixture of methanol, acetic acid and water to keep the temperature at -5 ° C or lower at all times, while adjusting the rate of addition of the alkali metal salt of the diketopyrrolopyrrole compound at 75 ° C, Min. &Lt; / RTI &gt; After addition of the alkali metal salt, red crystals precipitated and a red suspension was formed. Subsequently, the obtained red suspension was washed with an ultrafiltration device at 5 DEG C, and filtered to obtain a red paste. This paste was redispersed in 3500 parts of methanol cooled to 0 DEG C to obtain a suspension having a methanol concentration of about 90% and stirred at 5 DEG C for 3 hours to effect particle sizing and cleaning following the crystal transition. Subsequently, the obtained aqueous diketopyrrolopyrrole compound-based water paste was filtered with an ultrafilter, and dried at 80 DEG C for 24 hours and pulverized to obtain 145.8 parts of diketopyrrolopyrrole-based pigment composition.

(B-2-1) represented by the formula (B-2-1) and the brominated diketopyrrolopyrrole pigment represented by the formula (1) in the diketopyrrolopyrrole pigment composition were obtained in the same manner as in the production of the pigment composition 16 The content of diketopyrrolopyrrole pigment B was quantitatively analyzed by HPLC to find that the brominated diketopyrrolopyrrole pigment represented by formula (1) and the specific heterodimeric pyrrole represented by formula (B-2-1) The mass ratio of pyrrole pigment B was 88.9: 11.1.

Subsequently, 100.0 parts of the obtained diketopyrrolopyrrole pigment composition, 1000 parts of sodium chloride and 120 parts of diethylene glycol were put into a stainless steel first gallon kneader (manufactured by Inoue Manufacturing Co., Ltd.) and kneaded at 60 ° C for 10 hours . Next, the kneaded mixture was charged into hot water and stirred for 1 hour while heating at about 80 DEG C to form a slurry, followed by filtration and washing with water to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 DEG C, Thereby obtaining 98.1 parts of pigment composition 19 (R-19) which is a diketopyrrolopyrrole pigment composition. The average primary particle diameter was 28.8 nm.

[Referential Example 1]

(Preparation of pigment composition 20 (R-20)

100.0 parts of the brominated diketopyrrolopyrrole pigment of the formula (1), 1000 parts of sodium chloride and 120 parts of diethylene glycol were put into a stainless steel first gallon kneader (manufactured by Inoue Manufacturing Co., Ltd.) and kneaded at 60 DEG C for 10 hours . Next, the kneaded mixture was charged into hot water and stirred for 1 hour while heating at about 80 DEG C to form a slurry, followed by filtration and washing with water to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 DEG C, Thereby obtaining 96.6 parts of pigment composition 20 (R-20), which is a diketopyrrolopyrrole pigment composition. The average primary particle diameter was 38.9 nm.

[Reference Example 2]

(Preparation of pigment composition 21 (R-21)

70.0 parts of the brominated diketopyrrolopyrrole pigment of the formula (1), 30.0 parts of the specific heterodimeropyrrolopyrrole pigment B of the formula (B-2-1), 1000 parts of sodium chloride and 120 parts of diethylene glycol were charged into a stainless steel first gallon kneader Manufactured by Inoue Manufacturing Co., Ltd.) and kneaded at 60 占 폚 for 10 hours. Next, the kneaded mixture was charged into hot water and stirred for 1 hour while heating at about 80 DEG C to form a slurry, followed by filtration and washing with water to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 DEG C, Thereby obtaining 95.8 parts of pigment composition 21 (R-21) which is a diketopyrrolopyrrole pigment composition. The average primary particle diameter was 28.4 nm.

[Referential Example 3]

(Preparation of pigment composition 22 (R-22)

50.0 parts of the diketopyrrolopyrrole bromide pigment of the formula (1), 50.0 parts of the specific diketopyrrolopyrrole pigment B of the formula (B-2-1), 1000 parts of sodium chloride and 120 parts of diethylene glycol were charged into a stainless steel first gallon kneader Manufactured by Inoue Manufacturing Co., Ltd.) and kneaded at 60 占 폚 for 10 hours. Next, the kneaded mixture was charged into hot water and stirred for 1 hour while heating at about 80 DEG C to form a slurry, followed by filtration and washing with water to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 DEG C, Thereby obtaining 94.8 parts of pigment composition 22 (R-22) which is a diketopyrrolopyrrole pigment composition. The average primary particle diameter was 35.4 nm.

[Reference Example 4]

(Preparation of pigment composition 23 (R-23)

80.0 parts of the specific diketopyrrolopyrrole pigment B of the formula (B-2-1), 1000 parts of sodium chloride and 110 parts of diethylene glycol were put into a stainless steel first gallon kneader (manufactured by Inoue Manufacturing Co., Ltd.) Lt; 0 &gt; C for 10 hours. Next, the kneaded mixture was charged into hot water and stirred for 1 hour while heating at about 80 DEG C to form a slurry, followed by filtration and washing with water to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 DEG C, Thereby obtaining 76.8 parts of pigment composition 23 (R-23) which is a diketopyrrolopyrrole-based pigment composition. The average primary particle diameter was 39.4 nm.

[Reference Example 5]

(Preparation of pigment composition 24 (R-24)

70.0 parts of the brominated diketopyrrolopyrrole pigment of the formula (1), 30.0 parts of the specific diketopyrrolopyrrole pigment B of the formula (B-2-4a), 1000 parts of sodium chloride and 120 parts of diethylene glycol were added to a stainless steel first gallon kneader Manufactured by Inoue Manufacturing Co., Ltd.) and kneaded at 60 占 폚 for 10 hours. Next, the kneaded mixture was charged into hot water and stirred for 1 hour while heating at about 80 DEG C to form a slurry, followed by filtration and washing with water to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 DEG C, Thereby obtaining 95.8 parts of pigment composition 24 (R-24) which is a diketopyrrolopyrrole pigment composition. The average primary particle diameter was 27.3 nm.

[Referential Example 6]

(Preparation of pigment composition 25 (R-25)

Commercially available C.I. 100.0 parts of Pigment Red 254 (Irgaphor Red B-CF manufactured by Ciba Specialty Chemicals Inc.), 1000 parts of sodium chloride and 120 parts of diethylene glycol were placed in a stainless steel first gallon kneader (manufactured by Inoue Manufacturing Co., Ltd.) , And kneaded at 60 DEG C for 10 hours. Next, the kneaded mixture was charged into hot water and stirred for 1 hour while heating at about 80 DEG C to form a slurry, followed by filtration and washing with water to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 DEG C, Thereby obtaining 97.8 parts of pigment composition 25 (R-25) which is a diketopyrrolopyrrole pigment composition. The average primary particle size was 36.3 nm.

[Reference Example 7]

(Preparation of pigment composition 26 (R-26)

Commercially available C.I. 90.0 parts of Pigment Red 254 ("Irgaphor Red B-CF" manufactured by Ciba Specialty Chemicals Inc.), 10.0 parts of the specific diketopyrrolopyrrole pigment B of the formula (B-2-1), 1000 parts of sodium chloride and 120 parts of diethylene glycol 120 Were put into a stainless steel first gallon kneader (manufactured by Inoue Manufacturing Co., Ltd.) and kneaded at 60 DEG C for 10 hours. Next, the kneaded mixture was charged into hot water and stirred for 1 hour while heating at about 80 DEG C to form a slurry, followed by filtration and washing with water to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 DEG C, Thereby obtaining 95.8 parts of pigment composition 26 (R-26), which is a diketopyrrolopyrrole pigment composition. The average primary particle diameter was 31.4 nm.

Table B-1 shows the contents of the pigment compositions 1 to 26 (R-1 to 26). &Quot; PR254 &quot; shown in Table B-1 indicates that C.I. Pigment Red 254 &quot;.

[Table B-1]

&Lt; Production method of other pigment >

(Preparation of dianthraquinone-based pigment 1 (PR177-1)

90 parts of a dianthraquinone-based pigment (CI Pigment Red 177), 900 parts of sodium chloride and 110 parts of diethylene glycol were put into a stainless steel first gallon kneader (manufactured by Inoue Manufacturing Co., Ltd.) and kneaded at 60 DEG C for 10 hours . Next, the kneaded mixture was charged into hot water and stirred for 1 hour while heating at about 80 DEG C to form a slurry, followed by filtration and washing with water to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 DEG C, Thereby obtaining 85.0 parts of dianthraquinone-based pigment 1 (PR177-1). The average primary particle diameter was 38.2 nm.

(Production of azo-based pigment 1 (PY150-1)

90 parts of an azo pigment (CI Pigment Yellow 150), 900 parts of sodium chloride and 110 parts of diethylene glycol were placed in a stainless steel first gallon kneader (manufactured by Inoue Manufacturing Co., Ltd.) and kneaded at 60 DEG C for 10 hours. Next, the kneaded mixture was charged into hot water and stirred for 1 hour while heating at about 80 DEG C to form a slurry, followed by filtration and washing with water to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 DEG C, Thereby obtaining 85.0 parts of azo-based pigment 1 (PY150-1). The average primary particle diameter was 26.2 nm.

<Method for producing binder resin solution>

(Preparation of acrylic resin solution 1)

196 parts of cyclohexanone was charged into a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introducing tube, a dropping tube and a stirrer, the temperature was raised to 80 ° C, the inside of the reaction vessel was purged with nitrogen, From the dropping tube, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, 0.1 part of para-cumylphenol ethylene oxide modified acrylate ("Aronix M110" manufactured by Toagosei Co., ), And 1.1 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for another 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 heated and dried at 180 ° C for 20 minutes to measure the non-volatile content. Methoxy propyl acetate was added to the resin solution so as to have a non-volatile content of 20 mass% To prepare Resin Solution 1. The weight average molecular weight (Mw) was 26,000.

(Preparation of acrylic resin solution 2)

207 parts of cyclohexanone was added to a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introducing tube, a dropping tube and a stirrer in a separable four-necked flask, the temperature was raised to 80 DEG C, the inside of the reaction vessel was purged with nitrogen, 20 parts of methacrylic acid, 20 parts of para-cumylphenol ethylene oxide-modified acrylate (Aronix M110, manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate And 1.33 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for another 3 hours to obtain a copolymer resin solution. Next, 2 g of 2-methacryloyloxyethyl isocyanate (Karenz MOI, manufactured by Showa Denko KK) was added to the total amount of the copolymer solution obtained after stopping the nitrogen gas and stirring while injecting dry air for 1 hour, , 0.08 part of dibutyltin laurate, and 26 parts of cyclohexanone was added dropwise at 70 占 폚 over 3 hours. After completion of the dropwise addition, the reaction was continued for another 1 hour to obtain a solution of an acrylic resin. After cooling to room temperature, about 2 parts of the resin solution was sampled and heated and dried at 180 ° C for 20 minutes to measure the nonvolatile content. Cyclohexanone was added to the resin solution so as to have a nonvolatile content of 20 mass% Solution 2 was prepared. The 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 in terms of polystyrene measured by GPC (gel permeation chromatography).

&Lt; Production method of colored composition using diketopyrrolopyrrole-based pigment composition >

[Example 20]

(Preparation of coloring composition 1 (RP-1)) [

The mixture having the following composition was uniformly stirred and dispersed for 8 hours using a PICO MILL (manufactured by ASADA Iron Works Co., Ltd.) using zirconia beads having a diameter of 0.1 mm, To thereby prepare Coloring Composition 1 (RP-1).

Diketopyrrolopyrrole pigment composition 1 (R-1) 11.0 parts

Dye derivative (14-1) 1.0 part

Acrylic resin solution 1 40.0 parts

Propylene glycol monomethyl ether acetate 48.0 parts

[Examples 21 to 38]

(Preparation of colored compositions 2 to 19 (RP-2 to 19)

The colored compositions 2 to 19 (RP-2 to 19) were produced in the same manner as the coloring composition 1 (RP-1) except that the pigment composition 1 (R-1) Respectively.

[Example 39]

(Preparation of coloring composition 20 (RP-20)

The mixture shown below was uniformly stirred and mixed, dispersed with PICO MILL for 8 hours using zirconia beads having a diameter of 0.1 mm, and then filtered with a filter of 5 mu m to obtain Coloring Composition 20 (RP-20) Respectively.

Diketopyrrolopyrrole pigment composition 19 (R-19) 11.0 parts

Dye derivative (6-3) 1.0 part

Resin type dispersant (BYK161 (30% solution) manufactured by BYK-Chemie) 6.0 parts

Acrylic resin solution 1 31.0 parts

Propylene glycol monomethyl ether acetate 51.0 parts

[Example 40]

(Production of coloring composition 21 (RP-21)

The mixture of the following composition was uniformly stirred and dispersed for 8 hours by means of a PICO MILL using zirconia beads having a diameter of 0.1 mm and then filtered through a filter of 5 mu m to obtain Coloring Composition 21 (RP-21) Respectively.

Diketopyrrolopyrrole-based pigment composition 19 (R-19) 12.0 parts

A resinous dispersant ("Ajisper PB821" manufactured by Ajinomoto Fine-Techno Co., Inc.) 3.6 parts

Acrylic resin solution 1 23.0 parts

Propylene glycol monomethyl ether acetate 61.4 parts

[Reference Examples 8 to 14]

(Production of coloring compositions 22 to 28 (RP-22 to 28)

Coloring compositions 22 to 28 (RP-22 to 28) were prepared in the same manner as in Coloring Composition 1 (RP-1) except that Pigment Composition 1 (R-1) was changed to the pigment composition shown in Table B- Respectively.

[Table B-2]

&Lt; Production method of other coloring composition >

(Preparation of coloring composition 29 (RP-29)

The mixture shown below was homogeneously mixed and stirred. The mixture was dispersed for 8 hours by PICO MILL using zirconia beads having a diameter of 0.1 mm, and then filtered through a filter of 5 mu m to obtain Coloring Composition 29 (RP-29) Respectively.

Dianthraquinone-based pigment (PR177-1) 10.8 parts

Dye derivative (8-5) 1.2 part

Acrylic resin solution 1 40.0 parts

Propylene glycol monomethyl ether acetate 48.0 parts

(Preparation of colored composition 30 (YP-30)

The mixture shown below was uniformly mixed and stirred, and dispersed for 8 hours with PICO MILL using zirconia beads having a diameter of 0.1 mm, and then filtered with a filter having a size of 5 mu m to obtain Coloring Composition 30 (YP-30) Respectively.

Azo pigments (PY150-1) 12.0 parts

Resin type dispersant ("BYK6919" (50% solution) manufactured by BYK-Chemie) 6.0 parts

Acrylic resin solution 1 25.0 parts

Propylene glycol monomethyl ether acetate 57.0 parts

&Lt; Method for producing photosensitive coloring composition >

[Example 41]

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

The mixture having the following composition was stirred and mixed so as to be uniform, and then filtered with a filter of 1 mu m to prepare a photosensitive coloring composition 1 (RR-1).

Coloring composition 1 (RP-1) 38.2 parts

Coloring composition 29 (RP-29) 3.8 parts

Acrylic resin solution 2 13.2 parts

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

Photopolymerization initiator ("Irgacure-907" manufactured by Ciba Japan K.K.) 2.0 parts

(EAB-F manufactured by Hodogaya Chemical Co., Ltd.) 0.4 part

Ethylene glycol monomethyl ether acetate 39.6 parts

[Examples 42 to 61]

(Preparation of Photosensitive Coloring Composition 2 to 21 (RR-2 to 21)

The ratio of the coloring compositions 2 to 21 (RP-2 to 21) and the coloring composition 29 (RP-29) was changed to the coloring compositions 2 to 21 (RP-2 to 21) Sensitive coloring compositions 2 to 21 (RP-2 to 21) were prepared in the same manner as in Example 41, except that the amount of the coloring composition was changed (the proportion was changed within a total amount of 42 parts of the coloring composition). On the other hand, as for the ratio change, the ratio of the coloring compositions 2 to 21 (RP-2 to 21) to the coloring composition 29 (RP-29) so as to match the chromaticity of x = 0.640 and y = Respectively.

[Reference Examples 15 to 18, 20, 21]

(Preparation of photosensitive coloring compositions 22 to 25, 27 and 28 (RR-22 to 25, 27, 28)

The coloring composition 1 (RP-1) was changed to the coloring compositions 22 to 25, 27 and 28 (RP-22 to 25, 27 and 28), and the coloring compositions 22 to 25, 27 and 28 27, 28) and the coloring composition 29 (RP-29) were changed (the ratio was changed within 42 parts of the total amount of the coloring composition), the photosensitive coloring compositions 22 to 25, 27, 28 (RR-22 to 25, 27, 28). On the other hand, regarding the ratio change, the coloring compositions 22 to 25, 27 and 28 (RP-22 to 25, 27 and 28) and the coloring composition 29 (RP-29) was changed.

[Reference Example 19]

(Preparation of photosensitive coloring composition 26 (RR-26)

(RP-26) was used instead of the coloring composition 1 (RP-1), the coloring composition 29 (RP-29) was changed to the coloring composition 30 A photosensitive coloring composition 26 (RR-26) was prepared in the same manner as in Example 41 except that the ratio of the coloring composition 30 (YP-30) was changed (proportion was changed within 42 parts of the total amount of the coloring composition) . On the other hand, as for the ratio change, the ratio of the coloring composition 26 (RP-26) to the coloring composition 30 (YP-30) was changed so as to match the chromaticity of x = 0.640 and y = 0.328 in the C light source during coating film evaluation.

&Lt; Preparation and evaluation of coating film using photosensitive coloring composition >

The color characteristics, contrast ratio, and heat precipitation of the red coating formed using the obtained photosensitive coloring compositions (RR-1 to RR-28) were evaluated by the following methods. Table B-3 shows the kind of the colored composition in the photosensitive coloring composition and the evaluation result.

(Evaluation of Color Characteristics of Coating Film)

A photosensitive coloring composition was applied on a glass substrate having a thickness of 100 mm x 100 mm and a thickness of 0.7 mm so that x = 0.640 and y = 0.328 in the C light source, and after drying, Ultraviolet rays were irradiated. Then, the red coating film was obtained by heating at 230 占 폚 for 60 minutes. Then, the brightness (Y) of the obtained coating film was measured with a brown spectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.). On the other hand, the chromaticity was also measured with a brown spectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.).

(Evaluation of contrast ratio of coating film)

A method of measuring the contrast ratio of the coating film will be described. Light emitted from a backlight unit for a liquid crystal display passes through a polarizing plate, is polarized, passes through a dried coating film of a colored composition applied on a glass substrate, and reaches a polarizing plate. When the polarizing planes of the polarizing plate and the polarizing plate are parallel, the light transmits through the polarizing plate, but when the plane of polarization is straight, the light is blocked by the polarizing plate. However, when light polarized by the polarizing plate passes through the dried coating film of the coloring composition, scattering by the pigment particles occurs, and when a part of the polarizing plane is shifted, the amount of light transmitted through the polarizing plate is reduced when the polarizing plate is parallel, A part of light is transmitted through the polarizing plate. The transmitted light was measured with the brightness on the polarizing plate, and the ratio between the brightness when the polarizing plate was parallel and the brightness when the polarizing plate was parallel (orthogonal) (contrast ratio) was calculated.

(Contrast ratio) = (luminance in parallel) / (luminance in direct)

Therefore, when scattering is caused by the pigment in the coating film, the luminance at the time of paralleling decreases and the luminance at the time of directing increases, so that the contrast ratio is lowered.

On the other hand, a color intensity meter ("BM-5A" manufactured by Topcon Corporation) was used as the luminance meter and a polarizing plate ("NPF-G1220DUN" manufactured by Nitto Denko Corporation) was used as the polarizer. On the other hand, at the time of measurement, a black mask having a hole of 1 cm in length and 1 cm was attached to the measurement portion in order to shield unnecessary light. In addition, a red coating film obtained by the same method as in color characteristic evaluation was used for the contrast ratio measurement.

(Evaluation of crystal precipitation on the coating film surface)

A photosensitive coloring composition was applied on a glass substrate of 100 mm x 100 mm and a thickness of 0.7 mm to a thickness of x = 0.640 in a C light source, dried and irradiated with ultraviolet rays at 300 mJ / cm 2 using an ultra high pressure mercury lamp . Subsequent to the heat treatment at 230 캜 for 60 minutes, the heat treatment at 240 캜 for 60 minutes was repeated twice. After the heat treatment, the surface of the coated film of the substrate was observed with an optical microscope, and the presence or absence of crystal precipitation was judged according to the following criteria.

⊚: After the heat treatment at 230 占 폚 for 60 minutes, additionally, after the heat treatment at 240 占 폚 for 60 minutes and additionally at 240 占 폚 for 60 minutes,

?: After the heat treatment at 230 占 폚 for 60 minutes, no further precipitation was observed in the heat treatment at 240 占 폚 for 60 minutes (the second time, the crystal was precipitated in the heat treatment for 60 minutes at 240 占 폚)

DELTA: no crystal precipitation after the heat treatment at 230 DEG C for 60 minutes, but further crystallization by heat treatment at 240 DEG C for 60 minutes

×: Crystalline precipitation after heat treatment at 230 ° C. for 60 minutes

[Table B-3]

From the results in Table B-3, it can be seen that, in the color filter formation, the diketopyrrolopyrrole pigment containing a specific diketopyrrolopyrrole pigment B and the specific diketopyrrolopyrrole pigment B in a specific ratio (mass ratio 97: 3 to 85: 15) It has been found that the embodiment using the pigment composition has not only excellent brightness but also high contrast and can suppress crystal precipitation of the diketopyrrolopyrrole pigment by the heating process.

In the comparison between Example 43 and Reference Example 21, the photosensitive coloring composition using a diketopyrrolopyrrole pigment composition containing a diketopyrrolopyrrole bromide pigment and a specific heterodimeropyrrolopyrrole pigment B was prepared by the same method as that of the conventional C.I. Pigment Red 254, and had no problems in crystal precipitation. Further, it was found that the diketopyrrolopyrrole bromide pigment not containing the specific heterodimeropyrrolopyrrole pigment B of Reference Example 15 had a high brightness but a low contrast, and crystal precipitation was not inhibited. From the results of Example 42, Examples 45 to 47 and Examples 49 to 53, it was also confirmed that the effect of using the specific diketopyrrolopyrrole pigment B was dependent on the kind thereof.

In Examples 41 to 44 and Reference Examples 15 to 18, although the brightness decreases as the content of the specific diketopyrrole pigment in the formula (B-2-1) increases, the effect of inhibiting the precipitation of crystals tends to increase . Further, there is an optimum point for contrast, and it has been found that if the content ratio of a specific heterodimeric pigment is controlled, a balance of lightness and contrast can be obtained.

The pigment compositions prepared by the co-synthesis of succinic acid diester, the diketopyrrolopyrrole bromide pigment and the specific diketopyrrolopyrrole pigment B were separately synthesized in Examples 42 and 56, and mixed in a salt milling process to prepare It was found that the same effect was obtained in one pigment composition. The same effect was also confirmed in the comparison between Example 43 and Example 59.

In Examples 56 to 58, it has been found that the dye derivative treatment is effective for achieving high contrast and inhibiting crystal precipitation.

&Lt; Fabrication of color filter &

A green photosensitive coloring composition and a blue photosensitive coloring composition used in the production of a color filter were produced. On the other hand, for the red color, the photosensitive coloring composition 16 (RR-16) of this Example B was used.

(Preparation of green coloring composition 1 (GP-1)

A green coloring composition 1 (GP-1) was obtained by filtering the mixture with a filter of 5 mu m after 8 hours of dispersion with a PICO MILL using zirconia beads having a diameter of 0.1 mm, Respectively.

Green pigment (CI Pigment Green 36) 6.8 parts

Yellow pigment (CI Pigment Yellow 150) 5.2 parts

1.0 part of a resinous dispersant ("EFKA4300" manufactured by Ciba Japan K.K.)

Acrylic resin solution 1 35.0 parts

Propylene glycol monomethyl ether acetate 52.0 parts

(Preparation of green photosensitive coloring composition 1 (GR-1)

The mixture having the following composition was stirred and mixed so as to be uniform, and then filtered with a filter of 1 탆 to prepare a green photosensitive coloring composition 1 (GR-1).

Green coloring composition 1 (GP-1) 42.0 parts

Acrylic resin solution 2 13.2 parts

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

Photopolymerization initiator ("Irgacure-907" manufactured by Ciba Japan K.K.) 2.0 parts

(EAB-F manufactured by Hodogaya Chemical Co., Ltd.) 0.4 part

Ethylene glycol monomethyl ether acetate 39.6 parts

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

The mixture of the following composition was uniformly stirred and dispersed for 8 hours by means of a PICO MILL using zirconia beads having a diameter of 0.1 mm and then filtered with a filter of 5 mu m to obtain a blue colored composition 1 (BP-1) Respectively.

Blue pigment (CI Pigment Blue 15: 6) 7.2 parts

Purple pigment (CI Pigment Violet 23) 4.8 parts

1.0 part of a resinous dispersant ("EFKA4300" manufactured by Ciba Japan K.K.)

Acrylic resin solution 1 35.0 parts

Propylene glycol monomethyl ether acetate 52.0 parts

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

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

Blue coloring composition 1 (BP-1) 34.0 parts

Acrylic resin solution 2 15.2 parts

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

Photopolymerization initiator ("Irgacure-907" manufactured by Ciba Japan K.K.) 2.0 parts

(EAB-F manufactured by Hodogaya Chemical Co., Ltd.) 0.4 part

Ethylene glycol monomethyl ether acetate 45.1 parts

A black matrix was patterned on a glass substrate, and the photosensitive coloring composition 16 (RR-16) was coated on the substrate with a spin coater to a thickness of x = 0.640 and y = 0.328 to form a colored film. This coating film was irradiated with ultraviolet rays of 300 mJ / cm &lt; 2 &gt; through a photomask using an ultra-high pressure mercury lamp. Subsequently, an unexposed portion was removed by spray development using an alkali developing solution comprising an aqueous solution of sodium carbonate of 0.2 wt%, followed by washing with ion-exchanged water. The substrate was heated at 230 ° C for 20 minutes to form a red filter segment. X = 0.150 and y = 0.060 were obtained by using the blue photosensitive coloring composition 1 (BR-1) at a film thickness of x = 0.300 and y = , And a green filter segment and a blue filter segment were formed to obtain a color filter.

By using the photosensitive coloring composition 16 (RR-16), it was possible to produce a color filter having high definition and high contrast, and free from crystal precipitation in the heating process.

[Example C]

In Example C, "part" and "%" mean "part by weight" and "% by weight", respectively. The specific surface area of the pigment, the primary particle diameter of the pigment, the weight average molecular weight (Mw) of the resin, the acid value of the resin and the contrast ratio (CR) of the coating film are measured as follows.

(Specific surface area of pigment)

The specific surface area of the pigment particles was determined by the BET method by nitrogen adsorption. On the other hand, an automatic vapor adsorption amount measuring device ("BELSORP 18" manufactured by BEL Japan, Inc.) was used for measurement.

(Average primary particle diameter of pigment)

The average primary particle diameter of the pigment was measured by a method of directly measuring the primary particle size from an electron microscope photograph. Specifically, the minor axis diameter and the major axis diameter of primary particles of each pigment were measured, and the average was determined as the particle diameter of the pigment particles. Subsequently, the volume (weight) of each particle was determined with respect to 100 or more pigment particles to approximate the cubic of the obtained particle diameter, and the volume average particle diameter was determined as the average primary particle diameter. On the other hand, the transmission electron microscope (TEM) was used.

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

(Mw) in terms of polystyrene measured using GPC (Tosoh Corporation, HLC-8120GPC) equipped with an RI detector using a TSKgel column (manufactured by Tosoh Corporation) and THF as a developing solvent.

(Acid value of resin)

(COM-555) manufactured by Hiranuma Sangyo Co., Ltd. (hereinafter referred to as &quot; COM-555 &quot;) was prepared by adding 80 ml of acetone and 10 ml of water to 0.5-1 g of the resin solution, Ltd.), and the acid value of the resin solution was measured. The acid value per solid fraction of the resin was calculated from the acid value of the resin solution and the solid content concentration of the resin solution.

(Contrast ratio of coating film)

Light emitted from a backlight unit for a liquid crystal display passes through a polarizing plate, is polarized, passes through a dried coating film of a colored composition applied on a glass substrate, and reaches a polarizing plate. When the polarizing planes of the polarizing plate and the polarizing plate are parallel, the light transmits through the polarizing plate, but when the plane of polarization is straight, the light is blocked by the polarizing plate. However, when light polarized by the polarizing plate passes through the dried coating film of the coloring composition, scattering by the pigment particles occurs, and when a part of the polarizing plane is shifted, the amount of light transmitted through the polarizing plate is reduced when the polarizing plate is parallel, A part of light is transmitted through the polarizing plate. The transmitted light was measured with the brightness on the polarizing plate, and the brightness when the polarizing plate was parallel and the ratio between the brightness when the polarizing plate was parallel (contrast ratio) were calculated.

(Contrast ratio) = (luminance in parallel) / (luminance in direct)

On the other hand, a color intensity meter ("BM-5A" manufactured by Topcon Corporation) was used as the luminance meter and a polarizing plate ("NPF-G1220DUN" manufactured by Nitto Denko Corporation) was used as the polarizer. On the other hand, at the time of measurement, a black mask having a hole of 1 cm in length and 1 cm was attached to the measurement portion in order to shield unnecessary light.

Prior to the examples, a description will be given of the solution of the binder resin (B) used in the examples and the reference examples, the pigment (A1) shown in the formula (1), the finely divided pigment, and the method of producing the pigment dispersion.

&Lt; Process for producing binder resin (B) solution >

[Alkali-soluble photosensitive resin (B1-1)]

A separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introducing tube, a dropping tube and a stirrer was charged with 370 parts of cyclohexanone, and the temperature was raised to 80 ° C. After the inside of the flask was replaced with nitrogen, 18 parts of cumyl phenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2,2'-azo And 2.0 parts of bisisobutyronitrile was added dropwise over 2 hours. After dropwise addition, the mixture was reacted again at 100 DEG C for 3 hours, and then 1.0 part of azobisisobutyronitrile was dissolved in 50 parts of cyclohexanone, and the reaction was further continued at 100 DEG C for 1 hour. Next, 0.5 part of trisdimethylaminophenol and 0.1 part of hydroquinone were added to 9.3 parts of acrylic acid (equivalents of glycidyl group) and 0.1 part of hydroquinone in the vessel, and the reaction was continued at 120 占 폚 for 6 hours to obtain a solid content of 0.5 , The reaction was terminated to obtain a solution of an acrylic resin. Subsequently, 19.5 parts of the tetrahydrophthalic anhydride (equivalent weight of the produced hydroxyl group) and 0.5 part of triethylamine were added and reacted at 120 ° C for 3.5 hours to obtain a solution of the acrylic resin.

After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 占 폚 for 20 minutes to measure the nonvolatile content. PGMEA was added to the resin solution so that the nonvolatile fraction was 20% by weight to obtain an alkali- (B1-1) solution. The weight average molecular weight (Mw) was 19,000.

[Acrylic resin solution 1]

370 parts of cyclohexanone was added to the reaction vessel, and 20.0 parts of methacrylic acid, 10.0 parts of methyl methacrylate, 55.0 parts of n-butyl methacrylate, and 20.0 parts of 2- A mixture of 15.0 parts of hydroxyethyl methacrylate and 4.0 parts of 2,2'-azobisisobutyronitrile was added dropwise over 1 hour to carry out a polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 80 DEG C for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added and the reaction was continued at 80 DEG C for 1 hour to obtain an acrylic resin solution .

After cooling to room temperature, about 2 g of the acrylic resin solution was sampled and heated and dried at 180 캜 for 20 minutes to measure the nonvolatile content. Cyclohexanone was added to the acrylic resin solution so as to have a nonvolatile content of 20% by weight Acrylic resin solution 1 was obtained. The weight average molecular weight (Mw) was 40,000.

&Lt; Process for producing pigment (A1) shown in formula (1) >

First, 200 parts of tert-amyl alcohol dehydrated by molecular sieve and 140 parts of sodium-tert-amyl alkoxide were added to a stainless steel reaction vessel equipped with a reflux tube under nitrogen atmosphere, and the mixture was heated to 100 占 폚 with stirring to obtain an alcoholate Solution. On the other hand, 88 parts of diisopropyl succinate and 153.6 parts of 4-bromobenzonitrile were added to a glass flask and dissolved by heating at 90 占 폚 with stirring to prepare a solution of these mixtures. The heated solution of the mixture was slowly dropped into the above alcoholate solution heated to 100 占 폚 at a constant rate over 2 hours while stirring vigorously. After completion of the dropwise addition, heating and stirring were continued at 90 占 폚 for 2 hours to obtain an alkali metal salt of a diketopyrrolopyrrole compound. Then, 600 parts of methanol, 600 parts of water and 304 parts of acetic acid were added to a reaction vessel equipped with a glass jacket and cooled to -10 占 폚. The cooled mixture was subjected to the addition of a small amount of an alkali metal salt solution of the diketopyrrolopyrrole compound obtained in the previous step in which a common disk having a diameter of 8 cm was rotated at 4000 rpm using a high- Respectively. At this time, while cooling the mixture of methanol, acetic acid and water to keep the temperature at -5 ° C or lower at all times, while adjusting the rate of addition of the alkali metal salt of the diketopyrrolopyrrole compound at 75 ° C, Min. &Lt; / RTI &gt; After addition of the alkali metal salt, red crystals precipitated and a red suspension was formed. Subsequently, the obtained red suspension was washed with an ultrafiltration device at 5 DEG C, and filtered to obtain a red paste. This paste was redispersed in 3500 parts of methanol cooled to 0 DEG C to obtain a suspension having a methanol concentration of about 90% and stirred at 5 DEG C for 3 hours to effect particle sizing and cleaning following the crystal transition. Subsequently, the obtained aqueous diketopyrrolopyrrole compound-based water paste was dried at 80 DEG C for 24 hours and pulverized to obtain pigment (A1) bromide diketopyrrolopyrrole pigment 1 represented by the formula (1) 150.8 parts.

[Brominated diketopyrrolopyrrole pigment (A1-1)]

100.0 parts of bromo diketopyrrolopyrrole pigment 1, 1000 parts of sodium chloride and 120 parts of diethylene glycol were put into a stainless steel first gallon kneader (manufactured by Inoue Manufacturing Co., Ltd.) and kneaded at 60 DEG C for 2 hours. Next, the kneaded mixture was charged into hot water and stirred for 1 hour while heating at about 80 DEG C to form a slurry, followed by filtration and washing with water to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 DEG C, Thereby obtaining 96.5 parts of the brominated diketopyrrolopyrrole pigment (A1-1) represented by the formula (1). The average primary particle diameter was 65 nm and the specific surface area was 30 m ² / g.

[Brominated diketopyrrolopyrrole pigment (A1-2)]

100.0 parts of brominated diketopyrrolopyrrole pigment 1, 1000 parts of sodium chloride and 120 parts of diethylene glycol were put into a stainless steel first gallon kneader (manufactured by Inoue Manufacturing Co., Ltd.) and kneaded at 60 DEG C for 4 hours. Next, the kneaded mixture was charged into hot water and stirred for 1 hour while heating at about 80 DEG C to form a slurry, followed by filtration and washing with water to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 DEG C, Thereby obtaining 96.6 parts of a diketopyrrolopyrrole bromide pigment (A1-2). The average primary particle diameter was 55 nm and the specific surface area was 45 m ² / g.

[Brominated diketopyrrolopyrrole pigment (A1-3)]

100.0 parts of bromo diketopyrrolopyrrole pigment 1, 1000 parts of sodium chloride and 120 parts of diethylene glycol were put into a stainless steel first gallon kneader (manufactured by Inoue Manufacturing Co., Ltd.) and kneaded at 60 DEG C for 8 hours. Next, the kneaded mixture was charged into hot water and stirred for 1 hour while heating at about 80 DEG C to form a slurry, followed by filtration and washing with water to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 DEG C, Thereby obtaining 96.5 parts of a diketopyrrolopyrrole bromide pigment (A1-3). The average primary particle diameter was 38 nm and the specific surface area was 80 m ² / g.

[Brominated diketopyrrolopyrrole pigment (A1-4)]

100.0 parts of bromo diketopyrrolopyrrole pigment 1, 1000 parts of sodium chloride and 120 parts of diethylene glycol were put into a stainless steel first gallon kneader (manufactured by Inoue Manufacturing Co., Ltd.) and kneaded at 60 DEG C for 12 hours. Next, the kneaded mixture was charged into hot water and stirred for 1 hour while heating at about 80 DEG C to form a slurry, followed by filtration and washing with water to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 DEG C, Thereby obtaining 96.2 parts of a diketopyrrolopyrrole bromide pigment (A1-4). The average primary particle diameter was 30 nm and the specific surface area was 120 m ² / g.

[Brominated diketopyrrolopyrrole pigment (A1-5)]

100.0 parts of bromo diketopyrrolopyrrole pigment 1, 1000 parts of sodium chloride and 120 parts of diethylene glycol were put into a stainless steel first gallon kneader (manufactured by Inoue Manufacturing Co., Ltd.) and kneaded at 60 DEG C for 24 hours. Next, the kneaded mixture was charged into hot water and stirred for 1 hour while heating at about 80 DEG C to form a slurry, followed by filtration and washing with water to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 DEG C, Thereby obtaining 96.2 parts of a diketopyrrolopyrrole bromide pigment (A1-5). The average primary particle diameter was 19 nm, and the specific surface area was 180 m ² / g.

[Brominated diketopyrrolopyrrole pigment (A1-6)]

100.0 parts of bromo diketopyrrolopyrrole pigment 1, 1000 parts of sodium chloride and 120 parts of diethylene glycol were put into a stainless steel first gallon kneader (manufactured by Inoue Manufacturing Co., Ltd.) and kneaded at 60 DEG C for 48 hours. Next, the kneaded mixture was charged into hot water and stirred for 1 hour while heating at about 80 DEG C to form a slurry, followed by filtration and washing with water to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 DEG C, Thereby obtaining 96.2 parts of a diketopyrrolopyrrole bromide pigment (A1-6). The average primary particle diameter was 9 nm and the specific surface area was 270 m ² / g.

The contents of the produced brominated diketopyrrolopyrrole pigments (A1-1 to A6) are shown in Table C-1.

[Table C-1]

&Lt; Production method of pigment dispersion >

[Pigment dispersion (P-1)]

The mixture having the following composition was homogeneously stirred and dispersed for 5 hours using an Eiger mill ("mini model M-250 MKII" manufactured by Eiger Japan Co., Ltd.) using zirconia beads having a diameter of 1 mm, Mu] m filter to obtain a red pigment dispersion (P-1).

8.78 parts of brominated diketopyrrolopyrrole pigment (A1-1)

Acidic resin type pigment dispersant 1.74 parts

(BYK-111 manufactured by BYK Chemie Japan K.K.)

Diketopyrrolopyrrole-based pigment derivative 2.05 parts

(58)

Derivative 1

Acrylic resin solution 1 5.83 parts

81.60 parts of cyclohexanone

[Pigment dispersion (P-2)]

A red pigment dispersion (P-1) was obtained in the same manner as in the red pigment dispersion (P-1), except that the brominated diketopyrrolopyrrole pigment (A1-1) was changed to the diketopyrrolopyrrole bromide pigment (A1-2) 2).

[Pigment dispersion (P-3)]

A red pigment dispersion (P-1) was obtained in the same manner as in the red pigment dispersion (P-1), except that the brominated diketopyrrolopyrrole pigment (A1-1) was changed to the diketopyrrolopyrrole bromide pigment (A1-3) 3).

[Pigment dispersion (P-4)]

A red pigment dispersion (P-1) was obtained in the same manner as in the red pigment dispersion (P-1) except that the brominated diketopyrrolopyrrole pigment (A1-1) was changed to the diketopyrrolopyrrole bromide pigment (A1-4) R4).

[Pigment dispersion (P-5)]

(P-5) was obtained in the same manner as in the case of the red pigment dispersion (P-1) except that the brominated diketopyrrolopyrrole pigment (A1-1) was changed to the diketopyrrolopyrrole bromide pigment (A1-5) ).

[Pigment dispersion (P-6)]

A red pigment dispersion (P-1) was obtained in the same manner as in the red pigment dispersion (P-1), except that the brominated diketopyrrolopyrrole pigment (A1-1) was changed to the diketopyrrolopyrrole bromide pigment (A1-6) 6).

[Pigment dispersion (P-7)]

Except that the red pigment dispersion (P) was obtained except that the brominated diketopyrrolopyrrole pigment (A1-1) was changed to a chlorinated diketopyrrolopyrrole pigment (CI Pigment Red 254; Ciba Japan KK "Irgaphor Red B- -1), a red pigment dispersion (P-7) was obtained.

[Pigment dispersion (P-8)]

The mixture having the following composition was homogeneously stirred and dispersed for 5 hours using an Eiger mill ("mini model M-250 MKII" manufactured by Eiger Japan Co., Ltd.) using zirconia beads having a diameter of 1 mm, Mu] m filter to obtain a pigment dispersion (P-8).

6.82 parts of a diketopyrrolopyrrole bromide pigment (A1-3)

Anthraquinone-based pigment (CI Pigment Red 177) 1.08 part

("Cromophtal Red A2B" manufactured by Ciba Japan K.K.)

Nickel azo pigment pigments (CI Pigment Yellow 150) 0.88 parts

(Lanxess Corporation &quot; E4GN &quot;)

Acidic resin type pigment dispersant 1.74 parts

("Solsperse 21000" manufactured by The Lubrizol Corporation)

Pigment Derivative 1 2.05 parts

[Chemical Formula 59]

Derivative 1

Acrylic resin solution 1 5.83 parts

81.60 parts of cyclohexanone

[Pigment dispersion (P-9 to 20)]

(P-9 to P-20) were obtained in the same manner as in the pigment dispersion (P-8), except that the kind and amount of the pigment, pigment derivative and resin type pigment dispersant shown in Table C- &Lt; / RTI &gt;

[Table C-2]

Abbreviations in Table C-2 are as follows.

<Pigment>

PR254; Diketopyrrolopyrrole pigments C.I. Pigment Red 254

"Irgaphor Red B-CF" manufactured by Ciba Japan K.K.

PO71; Diketopyrrolopyrrole pigments C.I. Pigment Orange 71

Ciba Japan K.K. "Irgazin DPP orange 398"

PR242; Azo pigments C.I. Pigment Red 242

Clariant (Japan) K.K. &quot; Novoperm &quot;

PR179; Perylene pigments C.I. Pigment Red 179

Dainippon Ink and Chemicals, Inc. &quot; FastogenSuper Maroon PSK &quot;

PR122; Quinacridone pigments C.I. Pigment Red 122

Clariant (Japan) K.K. "Hostaperm"

PY 180; Benzimidazolone pigments C.I. Pigment Yellow 180

Clariant (Japan) K.K. &quot; PV Fast Yellow HG

PY138; Quinoline pigments C.I. Pigment Yellow 180

"Paliotol Yellow K0960-HD" manufactured by BASF Corporation

<Pigment Derivative>

(60)

Derivative 2

(61)

Derivative 3

(62)

Derivative 4

[Example 1]

(Red coloring composition (DR-1))

The mixture of the following composition was uniformly stirred and then filtered through a filter of 5 탆 to obtain a red coloring composition (DR-1).

Red pigment dispersion (P-1) 40.5 parts

Alkali-soluble photosensitive resin (B1-1) 8.6 parts

Cyclohexanone 50.9 parts

[Examples 2 to 6 and Reference Example 1]

(Red coloring compositions (DR-2-7))

(DR-2 to 7) were obtained in the same manner as in the red coloring composition (DR-1) except that the red pigment dispersion (P-1) was changed to the red pigment dispersion shown in Table C- ).

[Reference Example 2]

(Red coloring composition (DR-8))

A red coloring composition (DR-8) was obtained in the same manner as in the red coloring composition (DR-1) except that the alkali-soluble photosensitive resin (B1-1) was changed to the acrylic resin solution 1.

[Evaluation of red coloring composition]

The color characteristics, contrast ratio (CR) and crystal precipitation of the coating film surface of the obtained red coloring composition were evaluated by the following methods. The results are shown in Table C-3.

(Color characteristic, contrast ratio (CR) evaluation)

The obtained red coloring composition was coated on a glass substrate having a thickness of 100 mm x 100 mm and a thickness of 0.7 mm at a film thickness of x = 0.644 and y = 0.340 (+/- 0.001) Dried for 20 minutes in a hot air oven, and then heated again at 230 DEG C for 60 minutes to obtain a red coating film. Then, the brightness (Y) and the contrast ratio (CR) of the obtained coated substrate were measured.

On the other hand, the chromaticity and brightness (Y) were measured with a brown spectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.).

(Evaluation of crystal precipitation on the coating film surface)

The substrate obtained in the evaluation of color characteristics and contrast ratio (CR) was again subjected to heat treatment at 240 캜 for 60 minutes twice. After the heat treatment, the coating film surface of the coated substrate was observed with an optical microscope, and the presence or absence of crystal precipitation was judged according to the following criteria. In the evaluation results,? And? Are good because there is no crystal precipitation,? Is a level at which there is crystal precipitation but no problem in use, and X is a state that can not be used due to crystal precipitation.

⊚: After the heat treatment at 230 占 폚 for 60 minutes, additionally, after the heat treatment at 240 占 폚 for 60 minutes and additionally at 240 占 폚 for 60 minutes,

?: No crystal precipitation after heat treatment at 230 占 폚 for 60 minutes and additionally at 240 占 폚 for 60 minutes (crystal precipitation in second heat treatment at 240 占 폚 for 60 minutes)

DELTA: no crystal precipitation after the heat treatment at 230 DEG C for 60 minutes, but further crystallization by heat treatment at 240 DEG C for 60 minutes

×: Crystalline precipitation after heat treatment at 230 ° C. for 60 minutes

[Table C-3]

The coloring composition for a color filter comprising the pigment (A1) and the alkali-soluble photosensitive resin (B1) shown in the formula (1) all have high brightness and a high contrast ratio and can be subjected to crystallization of a diketopyrrolopyrrole pigment Good results were obtained.

[Examples 7 to 41, Reference Examples 3 to 5]

(Photosensitive coloring composition)

Each material was mixed and stirred with the composition and mixing amount shown in Tables C-4 to 9, and the mixture was filtered with a 1 탆 filter to obtain a photosensitive coloring composition.

[Table C-4]

[Table C-5]

[Table C-6]

[Table C-7]

[Table C-8]

[Table C-9]

Abbreviations in Tables C-4 to 9 are shown below.

&Lt; Photopolymerization initiator (D) >

Photopolymerization initiator D1: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-

(Irgacure 907, manufactured by Ciba Japan K.K.)

Photopolymerization initiator D2: 2- (Dimethylamino) -2 - [(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl]

(Irgacure 379 made by Ciba Japan K.K.)

Photopolymerization initiator D3: Ethan-1-one, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-

(Irgacure OXE02 made by Ciba Japan K.K.)

Photopolymerization initiator D4: 2,2'-bis (o-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-

("Biimidazole" manufactured by Kurogane Kasei Co., Ltd.)

Photopolymerization initiator D5: 2,4,6-Trimethylbenzoyl-diphenyl-phosphine oxide

("Lucirin TPO" manufactured by BASF Corporation)

<Increase / decrease>

Sensitizer E1: 2,4-diethylthioxanthone

(Kayacure DETX-S made by Nippon Kayaku Co., Ltd.)

Sensitizer E2: 4,4'-bis (diethylamino) benzophenone

("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.)

&Lt; Photopolymerizable compound >

Photopolymerizable compound: dipentaerythritol hexaacrylate

(Aronix M-402 manufactured by Toagosei Co., Ltd.)

<Multifunctional Thiol>

Polyfunctional thiol F1: trimethylol ethane tris (3-mercaptobutyrate)

(Showa Denko K.K. &quot; TEMB &quot;)

Polyfunctional thiol F2: trimethylolpropane tri (3-mercaptobutyrate)

(Showa Denko K.K. &quot; TPMB &quot;)

Polyfunctional thiol F3: pentaerythritol tetrakis (3-mercaptopropionate)

("PEMP" manufactured by Sakai Chemical Industry Co., Ltd.)

<Ultraviolet absorber>

Ultraviolet absorber G1: 2- [4 - [(2-hydroxy-3- (dodecyl and tridecyl) oxypropyl) oxy] -2- hydroxyphenyl] ) -1,3,5-triazine

("TINUVIN 400" manufactured by Ciba Japan K.K.)

Ultraviolet absorber G2: 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-

("TINUVIN 900" manufactured by Ciba Japan K.K.)

<Polymerization inhibitor>

Polymerization inhibitor H1: N-Nitrosophenylhydroxylamine aluminum salt

("Q-1301" manufactured by Wako Pure Chemical Industries, Ltd.)

Polymerization inhibitor H2: methyl hydroquinone

("MH" manufactured by Seiko Chemical Co., Ltd.)

<Storage Stabilizer>

Storage stabilizer J1: 2,6-bis (1,1-dimethylethyl) -4-methylphenol

("BHT" manufactured by Honshu Chemical Industry Co., Ltd.)

Storage stabilizer J2: Triphenylphosphine

("TPP" manufactured by Hokko Chemical Industry Co., Ltd.)

<Solvent>

Organic solvent: cyclohexanone

[Evaluation of Photosensitive Coloring Composition]

The color characteristics, contrast ratio (CR), crystallization of the surface of the coating film, sensitivity, linearity, pattern shape, resolution, developing resistance, drug resistance and aging stability were evaluated for the obtained photosensitive coloring composition by the following methods. The results are shown in Table C-10. In the evaluation results of the respective evaluations,? Is a very good level,? Is a good level,? Is a level that does not interfere with use, and X is a level that is not preferable for use.

(Color characteristic, contrast ratio (CR) evaluation)

The resulting photosensitive coloring composition was coated on a glass substrate having a thickness of 100 mm x 100 mm and a thickness of 0.7 mm at a film thickness of x = 0.640 and y = 0.328 in a C light source after the post-treatment and dried in a hot air oven at 70 DEG C for 20 minutes Thereafter, ultraviolet exposure was carried out using an ultra-high pressure mercury lamp at an integrated light quantity of 150 mJ, followed by heating at 230 DEG C for 1 hour and cooling to obtain a red coating film. Then, the brightness (Y) and the contrast ratio (CR) of the obtained coated substrate were measured.

On the other hand, the chromaticity and brightness (Y) were measured with a brown spectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.).

(Evaluation of crystal precipitation on the coating film surface)

The substrate obtained in the evaluation of color characteristics and contrast ratio (CR) was heated again at 260 DEG C for 1 hour and then cooled. After the heat treatment, the coating film surface of the coated substrate was observed with an optical microscope, and the presence or absence of crystal precipitation was judged according to the following criteria. In the evaluation results,? Is very good without crystal precipitation,? Is a good level although there is little crystal precipitation,? Is a level at which there is crystal precipitation but no problem in use, and X is a state that can not be used due to crystal precipitation .

&Amp; cir &amp;: 0 number of determinations

○: Number of determinations is 1 or more and less than 10

DELTA: Number of determinations: 10 or more and less than 100

X: More than 100 crystals

(Sensitivity, linearity, pattern shape, resolution, development tolerance, drug resistance evaluation)

The obtained photosensitive coloring composition was coated on a glass substrate having a thickness of 100 mm x 100 mm and a thickness of 0.7 mm and then heated in a clean oven at 70 DEG C for 20 minutes to remove the solvent to obtain a coating film having a thickness of about 2 mu m. Subsequently, the substrate was cooled to room temperature, and ultraviolet rays were exposed through a photomask having a stripe pattern with a width of 100 mu m (pitch: 200 mu m) and a width of 25 mu m (pitch: 50 mu m) using an ultra-high pressure mercury lamp. Thereafter, the substrate was spray-developed with an aqueous solution of sodium carbonate at 23 캜, washed with air, dried in air, and heated at 230 캜 for 330 minutes in a clean oven. The spraying was carried out for the coating film in each photosensitive coloring composition in the shortest possible time for forming a pattern without development residue, and this was regarded as an appropriate developing time.

The film thickness of the coating film was measured using Dektak 3030 (manufactured by Japan Vacuum Technology Co., Ltd. (currently ULVAC, Inc.)).

(Sensitivity evaluation)

The pattern film thickness in the 100 mu m photomask portion of the filter segment formed by the above method was measured and the minimum exposure amount which was 90% or more with respect to the film thickness after coating was evaluated. The smaller the minimum amount of exposure, the higher the sensitivity and the better the photosensitive coloring composition. The rank of evaluation is as follows.

?: Less than 50 mJ / cm 2

?: 50 mJ / cm2 or more and less than 100 mJ / cm2

×: 100 mJ / cm 2 or more

(Linearity evaluation)

The pattern on the 100 mu m photomask portion of the filter segment formed by the above method was observed using an optical microscope and then evaluated. The rank of evaluation is as follows.

○: Good linearity

Δ: Partial linearity defect

×: poor linearity

(Pattern shape evaluation)

The section of the pattern in the 100 mu m photomask portion of the filter segment formed by the above method was observed using an electron microscope and then evaluated. The pattern section has a favorable net taper. The rank of evaluation is as follows.

○: The section has a net taper shape

X: Inverse tapered shape

(Evaluation of Resolution)

The pattern in the 25 mu m photomask portion of the filter segment formed by the above method was observed using an optical microscope and then evaluated. The rank of evaluation is as follows. The defective resolution means that adjacent stripe patterns are connected or defects occur.

◎: Good resolution and linearity

○: Slightly inferior in linearity but good in resolution

△: Partially poor resolution

X: poor resolution

(Evaluation of Phenol resistance)

At the time of spray development, the pattern thickness of a 100 μm photomask portion of the filter segment formed by development at twice the appropriate time was measured and compared with the pattern film thickness formed by development at the optimum development time. The rank of evaluation is as follows.

⊚: difference in film thickness within 20%

?: Thickness difference greater than 20%, within 40%

B: Difference in film thickness is greater than 40%

×: Defects or peeling (peeling) occurred due to double development

(Drug resistance evaluation)

The filter segments formed by the above method were immersed in N-methylpyrrolidone solution for 30 minutes, washed with ion-exchanged water, air-dried, observed with an optical microscope for a pattern in a 100 mu m photomask portion, and then evaluated. The rank of evaluation is as follows.

◎: Good appearance without change in color

○: Some wrinkles and the like were observed,

?: Slight discoloration (discoloration) occurred

X: peeling or discoloration occurred

(Evaluation of stability with time of coloring composition)

The viscosity of the obtained photosensitive coloring composition was measured at the initial stage and at room temperature for one month, and the degree of viscosity increase with respect to the initial viscosity was calculated and evaluated. The rank of evaluation is as follows.

(Initial Viscosity) - (Initial Viscosity) x 100 (%) (Initial Viscosity)

⊚: The viscosity increase ratio is 5% or less and good

○: The viscosity increase ratio is greater than 5% and less than 10%

X: The viscosity increase rate is larger than 10%

[Table C-10]

As shown in Table C-10, the coloring composition for a color filter containing the pigment (A1) and the photosensitive resin (B1) shown in the formula (1) gave a high evaluation result in all evaluations.

(Production of color filter)

4.54 parts of the total of the pigment and the pigment derivative in the photosensitive coloring composition (RR-1) was used. Pigment Green 58 / C.I. Pigment Yellow 150 = 2.72 parts / 1.82 part, and in the case of the blue photosensitive coloring composition, C.I. Pigment Blue 15: 6 / CI. A pigment dispersion was prepared in the same manner as in the preparation of the pigment dispersion (P-3), except that the pigment dispersion (P-3) was replaced with 3.63 parts of Pigment Violet 23/0.91 parts and further the pigment dispersion of the photosensitive coloring composition (RR- To obtain a green photosensitive coloring composition for a color filter and a blue photosensitive coloring composition for a color filter.

A photosensitive coloring composition (RR-1) was coated on a glass substrate of 100 mm x 100 mm with a die coater to a thickness of about 2 mu m and dried in an oven at 70 DEG C for 20 minutes by removing the solvent. Then, stripe pattern exposure was performed by ultraviolet rays using an exposure apparatus. The exposure dose was 100 mJ / cm 2. Then, the unexposed portions were removed by developing with a developer composed of an aqueous solution of sodium carbonate and then washed with ion-exchanged water. The substrate was heated at 230 占 폚 for 30 minutes to form a red filter segment having a line width of about 50 占 퐉. Then, in the same manner, a green filter segment was formed next to the red filter segment using a green photosensitive coloring composition, and then a blue filter segment was formed using a blue photosensitive coloring composition to form three filter segments on the same glass substrate Lt; / RTI &gt;

By using the coloring composition for a color filter as described above, it is possible to produce a fixed color filter having a red filter segment having excellent color characteristics in a wide chromaticity range and having good heat resistance.

[Example D]

In Example D, "part" and "%" indicate "part by weight" and "% by weight", respectively. The specific surface area of the pigment, the primary particle diameter of the pigment, the weight average molecular weight (Mw) of the resin, the acid value of the resin and the contrast ratio (CR) of the coating film are measured as follows.

(Specific surface area of pigment)

The specific surface area of the pigment particles was determined by the BET method by nitrogen adsorption. On the other hand, an automatic vapor adsorption amount measuring device ("BELSORP 18" manufactured by BEL Japan, Inc.) was used for measurement.

(Average primary particle diameter of pigment)

The average primary particle diameter of the pigment was measured by a method of directly measuring the primary particle size from an electron microscope photograph. Specifically, the minor axis diameter and the major axis diameter of primary particles of each pigment were measured, and the average was determined as the particle diameter of the pigment particles. Subsequently, the volume (weight) of each particle was determined with respect to 100 or more pigment particles to approximate the cubic of the obtained particle diameter, and the volume average particle diameter was determined as the average primary particle diameter. On the other hand, the transmission electron microscope (TEM) was used.

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

(Mw) in terms of polystyrene measured using GPC (Tosoh Corporation, HLC-8120GPC) equipped with an RI detector using a TSKgel column (manufactured by Tosoh Corporation) and THF as a developing solvent.

(Acid value of resin)

("COM-555" manufactured by Hiranuma Sangyo Co., Ltd. (Japan)) was added to 0.5 to 1 g of the resin solution by adding 80 ml of acetone and 10 ml of water and the mixture was uniformly dissolved with stirring and a KOH aqueous solution of 0.1 mol / Ltd.), and the acid value of the resin solution was measured. The acid value per solid fraction of the resin was calculated from the acid value of the resin solution and the solid content concentration of the resin solution.

(Contrast ratio of coating film)

Light emitted from a backlight unit for a liquid crystal display passes through a polarizing plate, is polarized, passes through a dried coating film of a colored composition applied on a glass substrate, and reaches a polarizing plate. When the polarizing planes of the polarizing plate and the polarizing plate are parallel, the light transmits through the polarizing plate, but when the plane of polarization is straight, the light is blocked by the polarizing plate. However, when light polarized by the polarizing plate passes through the dried coating film of the coloring composition, scattering by the pigment particles occurs, and when a part of the polarizing plane is shifted, the amount of light transmitted through the polarizing plate is reduced when the polarizing plate is parallel, A part of light is transmitted through the polarizing plate. The transmitted light was measured with the brightness on the polarizing plate, and the brightness when the polarizing plate was parallel and the ratio between the brightness when the polarizing plate was parallel (contrast ratio) were calculated.

(Contrast ratio) = (luminance in parallel) / (luminance in direct)

On the other hand, a color intensity meter ("BM-5A" manufactured by Topcon Corporation) was used as the luminance meter and a polarizing plate ("NPF-G1220DUN" manufactured by Nitto Denko Corporation) was used as the polarizer. On the other hand, at the time of measurement, a black mask having a hole of 1 cm in length and 1 cm was attached to the measurement portion in order to shield unnecessary light.

Prior to the examples, a description will be given of the solution of the binder resin (B) used in the examples and the reference examples, the pigment (A1) shown in the formula (1), the finely divided pigment, and the method of producing the pigment dispersion.

&Lt; Process for producing binder resin (B) solution >

[Resin solution (B1-1)]

(Step 1: Polymerization of resin main chain)

100 parts of propylene glycol monomethyl ether acetate (PGMAC) was charged into a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introducing tube and a stirrer, and heated to 120 DEG C while introducing nitrogen gas into the container. At the same temperature, a mixture of 16.2 parts of styrene, 35.5 parts of glycidyl methacrylate, 41.0 parts of dicyclopentyl methacrylate, and 1.0 part of azobisisobutyronitrile as a catalyst required for the synthesis of the precursor in this step was mixed with 2.5 parts of 2.5 Over a period of time to carry out a polymerization reaction.

(Step 2: Polymerization to epoxy group)

Next, the inside of the flask was purged with air, and 17.0 parts of acrylic acid and 0.3 part of trisdimethylaminomethylphenol and 0.3 part of hydroquinone as a catalyst required for polymerization of the precursor in this step were added and reacted at 120 DEG C for 5 hours, A resin solution having an average molecular weight of about 12,000 (measured by GPC) was obtained. Since the added acrylic acid is ester-bonded to the epoxy group terminal of the glycidyl methacrylate constituent unit, the carboxyl group is not produced in the resin structure.

(Step 3: Polymerization to hydroxyl group)

Further, 30.4 parts of tetrahydrophthalic anhydride and 0.5 part of triethylamine as a catalyst required for the polymerization of the precursor in this step were added, and the reaction was carried out at 120 ° C for 4 hours. In the tetrahydrophthalic anhydride phthalic acid added, one of the two carboxyl groups formed by cleavage (cleavage) of the carboxylic anhydride moiety is esterified to the hydroxyl group in the resin structure and the other carboxy terminal is produced.

(Step 4: adjustment of non-volatile content)

Propylene glycol monomethyl ether acetate was added so that the non-volatile content became 40% to obtain a resin solution (B1-1).

The weight ratio of the constituent units in the resin solution (B1-1) is selected from the group consisting of tetrahydrophthalic anhydride as the constituent unit (D-b1); 21.7% by weight, styrene as the constituent unit (D-b2); 11.6% by weight, dicyclopentanyl methacrylate as the constituent unit (D-b3); 29.3% by weight, the sum of glycidyl methacrylate and acrylic acid ester-bonded at the glycidyl terminal thereof as other structural units; 37.4% by weight.

[Resin solution (B1-2)]

Synthesis reaction was carried out in the same manner as in the resin solution (B1-1) except that dicyclopentanyl methacrylate in the resin solution (B1-1) was changed to dicyclopentenyl methacrylate to obtain a resin solution (B1-2 ).

[Resin solution (B1-3)]

Synthesis reaction was carried out in the same manner as in the resin solution (B1-1) except that dicyclopentanyl methacrylate in the resin solution (B1-1) was changed to dicyclopentenyloxyethyl methacrylate to obtain a resin solution (B1 -3) was prepared.

[Resin solution (B1-4)]

A separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introducing tube, a dropping tube and a stirrer was charged with 370 parts of PGMEA, and the temperature was raised to 80 ° C. After the inside of the flask was replaced with nitrogen, 18 parts of ethylene oxide-modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate and 2,2'- And 2.0 parts of butyronitrile was added dropwise over 2 hours. After dropwise addition, the mixture was reacted again at 100 DEG C for 3 hours, and then 1.0 part of azobisisobutyronitrile was dissolved in 50 parts of cyclohexanone, and the reaction was further continued at 100 DEG C for 1 hour. Subsequently, 0.5 part of trisdimethylaminophenol and 0.1 part of hydroquinone were added to 9.3 parts of acrylic acid (equivalents of epoxy group) in the vessel, and the reaction was continued at 120 DEG C for 6 hours to obtain a copolymer having a solid content of 0.5 The reaction was terminated to obtain a solution of an acrylic resin. Subsequently, 19.5 parts of the tetrahydrophthalic anhydride (equivalent weight of the produced hydroxyl group) and 0.5 part of triethylamine were added and reacted at 120 ° C for 3.5 hours to obtain a solution of the acrylic resin.

After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 캜 for 20 minutes to measure the nonvolatile content. PGMEA was added to the resin solution so that the nonvolatile content became 20% by weight to obtain an acrylic resin solution B1 -4) was prepared. The weight average molecular weight (Mw) was 19,000.

[Resin solutions (B1-5 to 15) and (B2-1 to 4)]

The resin solutions (B1-5) to (B1-15) and (B2-1) to (B2-5) were prepared in the same manner as the resin solution (B1-1).

That is, in the production process of the resin solution (B1-1), the precursors corresponding to the constituent units (D-b1) to (D-b3) and other constituent units were substituted in accordance with Table D-1. In the case of a resin solution in which no GMA-AA or GMA-MAA is present in the table, all the precursors are mixed and only steps 1 and 4 of the preparation are carried out. If GMA-AA or GMA-MAA is present in the table and THPA is present, GMA-AA or GMA-MAA among GMA, the constituent units (D-b2) Step 1 of the preparation was carried out by mixing the precursors except for the epoxy equivalents of GMA and AA or MAA as precursors and then step 2 of the preparation was carried out and THPA was again added as a precursor to prepare step 3 and 4 . When GMA-AA or GMA-MAA is present in the table and THPA is not present, first, GMA-AA or GMA-MAA among the GMA, the constituent units (D-b1) Step 1 of the preparation is carried out by mixing the precursors except for the epoxy equivalents of GMA AA or MAA as precursors, followed by step 2 of the preparation and then step 4. The number of catalysts required for each step is proportional to the total number of precursors mixed in each step.

Table D-1 shows the composition and weight ratios of the obtained resin solutions (B1-1 to 15) and resin solutions (B2-1 to 4). The brackets indicate the weight ratio (weight%) of the constituent units in the resin solid content.

[Table D-1]

Explanation of the abbreviations of the precursors and constituent units of the constituent units in Table D-1

MAA: methacrylic acid

THPA: tetrahydrophthalic anhydride (4-cyclohexene-1,2-dicarboxylic anhydride

BzMA: Benzyl methacrylate

St: Styrene

M110: Paracumylphenol ethylene oxide modified acrylate

DCPMA: dicyclopentanyl methacrylate

GMA: glycidyl methacrylate

GMA-AA: a constituent unit in which acrylic acid is bonded to GMA by addition reaction

GMA-MAA: a constituent unit in which GMA is bound by methacrylic acid addition reaction

BMA: n-butyl methacrylate

[Preparation of resin solution (B2-5)] [

370 parts of cyclohexanone was added to the reaction vessel, and 20.0 parts of methacrylic acid, 10.0 parts of methyl methacrylate, 55.0 parts of n-butyl methacrylate, and 20.0 parts of 2- A mixture of 15.0 parts of hydroxyethyl methacrylate and 4.0 parts of 2,2'-azobisisobutyronitrile was added dropwise over 1 hour to carry out a polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 80 DEG C for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added and the reaction was continued at 80 DEG C for 1 hour to obtain an acrylic resin solution .

After cooling to room temperature, about 2 g of the acrylic resin solution was sampled and heated and dried at 180 캜 for 20 minutes to measure the nonvolatile content. Cyclohexanone was added to the acrylic resin solution so as to have a nonvolatile content of 20% by weight To prepare a resin solution (B2-5). The weight average molecular weight (Mw) was 40,000.

&Lt; Process for producing pigment (A1) shown in formula (1) >

[Brominated diketopyrrolopyrrole pigment (A1-1)]

200 parts of tert-amyl alcohol dehydrated by molecular sieves and 140 parts of sodium-tert-amyl alkoxide were added to a stainless steel reaction vessel equipped with a reflux tube and heated to 100 占 폚 with stirring to obtain an alcoholate solution Lt; / RTI &gt; On the other hand, 88 parts of diisopropyl succinate and 153.6 parts of 4-bromobenzonitrile were added to a glass flask and dissolved by heating at 90 DEG C with stirring to prepare a solution of these mixtures. The heated solution of the mixture was slowly added dropwise at a constant rate over 2 hours while stirring vigorously in the alcoholate solution heated to 100 占 폚. After completion of the dropwise addition, heating and stirring were continued at 90 占 폚 for 2 hours to obtain an alkali metal salt of a diketopyrrolopyrrole compound. Then, 600 parts of methanol, 600 parts of water and 304 parts of acetic acid were added to a reaction vessel equipped with a glass jacket and cooled to -10 占 폚. The cooled mixture was subjected to the addition of a small amount of an alkali metal salt solution of the diketopyrrolopyrrole compound obtained in the previous step in which a common disk having a diameter of 8 cm was rotated at 4000 rpm using a high- Respectively. At this time, while cooling the mixture of methanol, acetic acid and water to keep the temperature at -5 ° C or lower at all times, while adjusting the rate of addition of the alkali metal salt of the diketopyrrolopyrrole compound at 75 ° C, Min. &Lt; / RTI &gt; After addition of the alkali metal salt, red crystals precipitated and a red suspension was formed. Subsequently, the obtained red suspension was washed with an ultrafiltration device at 5 DEG C, and filtered to obtain a red paste. This paste was redispersed in 3500 parts of methanol cooled to 0 DEG C to obtain a suspension having a methanol concentration of about 90% and stirred at 5 DEG C for 3 hours to effect particle sizing and cleaning following the crystal transition. Subsequently, the obtained aqueous diketopyrrolopyrrole compound-based water paste was dried at 80 DEG C for 24 hours and pulverized to obtain a pigment (A1) having a brominated diketopyrrolopyrrole pigment represented by the formula (1) Min.

100.0 parts of the obtained diketopyrrolopyrrole bromide pigment, 1000 parts of sodium chloride and 120 parts of diethylene glycol were put into a stainless steel first gallon kneader (manufactured by Inoue Manufacturing Co., Ltd.) and kneaded at 60 DEG C for 8 hours. Next, the kneaded mixture was poured into hot water and stirred for 1 hour while heating at about 80 DEG C to form a slurry, followed by filtration and washing with water to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 DEG C, Thereby obtaining 96.5 parts of the brominated diketopyrrolopyrrole pigment (A1-1) represented by the formula (1). The average primary particle diameter was 38 nm and the specific surface area was 80 m ² / g.

&Lt; Production method of pigment dispersion >

[Pigment dispersion (P-1)]

The mixture having the following composition was homogeneously stirred and dispersed for 5 hours using an Eiger mill ("mini model M-250 MKII" manufactured by Eiger Japan Co., Ltd.) using zirconia beads having a diameter of 1 mm, Mu] m filter to obtain a pigment dispersion (P-1).

8.78 parts of brominated diketopyrrolopyrrole pigment (A1-1)

Acidic resin type pigment dispersant 1.74 parts

(BYK-111 manufactured by BYK Chemie Japan K.K.)

Pigment Derivative 1 2.05 parts

(63)

Derivative 1

Resin solution (B2-5) 5.83 parts

81.60 parts of cyclohexanone

[Pigment dispersion (P-2)]

Except that the pigment dispersion (P-1) was obtained except that the brominated diketopyrrolopyrrole pigment (A1-1) was changed to a chlorinated diketopyrrolopyrrole pigment (CI Pigment Red 254; Ciba Japan KK "Irgaphor Red B- 1), a pigment dispersion (P-2) was obtained.

[Pigment dispersion (P-3)]

The mixture having the following composition was homogeneously stirred and dispersed for 5 hours using an Eiger mill ("mini model M-250 MKII" manufactured by Eiger Japan Co., Ltd.) using zirconia beads having a diameter of 1 mm, Mu] m filter to obtain a pigment dispersion (P-3).

6.82 parts of brominated diketopyrrolopyrrole pigment (A1-1)

Anthraquinone-based pigment (CI Pigment Red 177) 1.08 part

("Cromophtal Red A2B" manufactured by Ciba Japan K.K.)

Nickel azo pigment pigments (CI Pigment Yellow 150) 0.88 parts

(Lanxess Corporation &quot; E4GN &quot;)

Acidic resin type pigment dispersant 1.74 parts

(Solsperse 21000 from The Lubrizol Corporation &quot;).

Pigment Derivative 1 2.05 parts

&Lt; EMI ID =

Derivative 1

Resin solution (B2-5) 5.83 parts

81.60 parts of cyclohexanone

[Pigment dispersion (P-4 to 10)]

(P-4 to P-11) were obtained in the same manner as in the pigment dispersion (P-3), except that the kind and amount of the pigment, pigment derivative and resin type pigment dispersant shown in Table D- &Lt; / RTI &gt;

[Table D-2]

Abbreviations in Table D-2 are shown below.

<Pigment>

PR254; Diketopyrrolopyrrole pigments C.I. Pigment Red 254

"Irgaphor Red B-CF" manufactured by Ciba Japan K.K.

PO71; Diketopyrrolopyrrole pigments C.I. Pigment Orange 71

Ciba Japan K.K. "Irgazin DPP orange 398"

PR242; Azo pigments C.I. Pigment Red 242

Clariant (Japan) K.K. &quot; Novoperm &quot;

PR179; Perylene pigments C.I. Pigment Red 179

Dainippon Ink and Chemicals, Inc. &quot; FastogenSuper Maroon PSK &quot;

PR122; Quinacridone pigments C.I. Pigment Red 122

Clariant (Japan) K.K. "Hostaperm"

PY 180; Benzimidazolone pigments C.I. Pigment Yellow 180

Clariant (Japan) K.K. &quot; PV Fast Yellow HG

PY138; Quinoline pigments C.I. Pigment Yellow 180

"Paliotol Yellow K0960-HD" manufactured by BASF Corporation

<Pigment Derivative>

(65)

Derivative 2

(66)

Derivative 3

(67)

Derivative 4

[Example 1]

(Red coloring composition (DR-1))

The mixture of the following composition was uniformly stirred and then filtered through a filter of 5 탆 to obtain a red coloring composition (DR-1).

Red pigment dispersion (P-R1) 40.5 parts

Resin solution (B1-1) 8.6 parts

Cyclohexanone 50.9 parts

[Examples 2 to 6 and Reference Example 1]

(Red coloring compositions (DR-2-7))

Red coloring compositions DR-2 to 7 were obtained in the same manner as in the red coloring composition (DR-1) except that the resin solution (B1-1) was changed to the resin solution shown in Table D-2 .

[Reference Example 2]

(Red coloring composition (DR-8))

A red coloring composition (DR-8) was obtained in the same manner as in the red coloring composition (DR-1) except that the red pigment dispersion (P-R1) was changed to the red pigment dispersion (P-R2) .

[Evaluation of red coloring composition]

The color characteristics, contrast ratio (CR) and crystal precipitation of the coating film surface of the obtained red coloring composition were evaluated by the following methods. The results are shown in Table D-3.

(Color characteristic, contrast ratio (CR) evaluation)

The obtained red coloring composition was coated on a glass substrate having a thickness of 100 mm x 100 mm and a thickness of 0.7 mm at a film thickness of x = 0.644 and y = 0.340 (+/- 0.001) in a C light source, , And then heated again at 230 캜 for 60 minutes to obtain a red coating film. Then, the brightness (Y) and the contrast ratio (CR) of the obtained coated substrate were measured.

On the other hand, the chromaticity and brightness (Y) were measured with a brown spectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.).

(Evaluation of crystal precipitation on the coating film surface)

The substrate obtained in the evaluation of color characteristics and contrast ratio (CR) was again subjected to heat treatment at 240 캜 for 60 minutes twice. After the heat treatment, the coating film surface of the coated substrate was observed with an optical microscope, and the presence or absence of crystal precipitation was judged according to the following criteria. In the evaluation results,? And? Are good because there is no crystal precipitation,? Is a level at which there is crystal precipitation but no problem in use, and X is a state that can not be used due to crystal precipitation.

⊚: After the heat treatment at 230 占 폚 for 60 minutes, additionally, after the heat treatment at 240 占 폚 for 60 minutes and additionally at 240 占 폚 for 60 minutes,

?: After the heat treatment at 230 占 폚 for 60 minutes, no further precipitation was observed in the heat treatment at 240 占 폚 for 60 minutes (the second time, the crystal was precipitated in the heat treatment for 60 minutes at 240 占 폚)

DELTA: no crystal precipitation after the heat treatment at 230 DEG C for 60 minutes, but further crystallization by heat treatment at 240 DEG C for 60 minutes

×: Crystalline precipitation after heat treatment at 230 ° C. for 60 minutes

[Table D-3]

The coloring composition for a color filter comprising the pigment (A1) represented by the formula (1) and the resin (D-B1) having the constitutional units (D-b1) to (D-b3) has high brightness and high contrast ratio , And a good result was obtained that the crystallization of the diketopyrrolopyrrole pigment was not caused even by the heating process.

[Examples 7 to 31, Reference Examples 3 to 9]

(Photosensitive coloring composition (RR-1 to 32))

Each of the materials was mixed and stirred at the compositions and mixing ratios shown in Tables D-4 to 10, and the mixture was filtered with a filter of 1 mu m to obtain photosensitive coloring compositions (RR-1 to 32).

[Table D-4]

[Table D-5]

[Table D-6]

[Table D-7]

[Table D-8]

[Table D-9]

[Table D-10]

Abbreviations in Tables D-4 to 10 are shown below.

&Lt; Photopolymerization initiator (D) >

Photopolymerization initiator D1: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-

(Irgacure 907, manufactured by Ciba Japan K.K.)

Photopolymerization initiator D2: 2- (Dimethylamino) -2 - [(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl]

(Irgacure 379 made by Ciba Japan K.K.)

Photopolymerization initiator D3: 2,4,6-Trimethylbenzoyl-diphenyl-phosphine oxide

("Lucirin TPO" manufactured by BASF Corporation)

Photopolymerization initiator D4: 2,2'-bis (o-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-

("Biimidazole" manufactured by Kurogane Kasei Co., Ltd.)

Photopolymerization initiator D5: p-Dimethylaminoacetophenone

("DMA" manufactured by DAIKI FINECHEMICAL Co., Ltd.)

Photopolymerization initiator D6: ethan-1-one, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-

(Irgacure OXE02 made by Ciba Japan K.K.)

<Increase / decrease>

Sensitizer E1: 2,4-diethylthioxanthone

(Kayacure DETX-S made by Nippon Kayaku Co., Ltd.)

Sensitizer E2: 4,4'-bis (diethylamino) benzophenone

("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.)

&Lt; Photopolymerizable compound >

Photopolymerizable compound C1: dipentaerythritol hexaacrylate

(Aronix M-402 manufactured by Toagosei Co., Ltd.)

<Multifunctional Thiol>

Polyfunctional thiol F1: trimethylol ethane tris (3-mercaptobutyrate)

(Showa Denko K.K. &quot; TEMB &quot;)

Polyfunctional thiol F2: trimethylolpropane tri (3-mercaptobutyrate)

(Showa Denko K.K. &quot; TPMB &quot;)

Polyfunctional thiol F3: pentaerythritol tetrakis (3-mercaptopropionate)

("PEMP" manufactured by Sakai Chemical Industry Co., Ltd.)

<Ultraviolet absorber>

Ultraviolet absorber G1: 2- [4 - [(2-hydroxy-3- (dodecyl and tridecyl) oxypropyl) oxy] -2- hydroxyphenyl] ) -1,3,5-triazine

("TINUVIN 400" manufactured by Ciba Japan K.K.)

Ultraviolet absorber G2: 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-

("TINUVIN 900" manufactured by Ciba Japan K.K.)

<Storage Stabilizer>

Storage stabilizer J1: 2,6-bis (1,1-dimethylethyl) -4-methylphenol

("BHT" manufactured by Honshu Chemical Industry Co., Ltd.)

Storage stabilizer J2: Triphenylphosphine

("TPP" manufactured by Hokko Chemical Industry Co., Ltd.)

<Solvent>

PGMAC: Propylene glycol monomethyl ether acetate

[Evaluation of Photosensitive Coloring Composition]

The color characteristics, the contrast ratio (CR), the crystallization of the surface of the coating film, the sensitivity, the linearity, the pattern shape, the resolution, the development resistance, the chemical resistance and the aging stability were measured for the obtained photosensitive coloring compositions (RR-1-32) Respectively. The results are shown in Table D-11. In the evaluation results of the respective evaluations,? Is a very good level,? Is a good level,? Is a level that does not interfere with use, and X is a level that is not preferable for use.

(Color characteristic, contrast ratio (CR) evaluation)

The resulting photosensitive coloring composition was coated on a glass substrate having a thickness of 100 mm x 100 mm and a thickness of 0.7 mm to a thickness of x = 0.640 and y = 0.328 after post-treatment in a C light source and dried in a hot air oven at 70 DEG C for 20 minutes Subsequently, ultraviolet exposure was carried out using an ultra-high pressure mercury lamp at an integrated light quantity of 150 mJ, followed by heating at 230 DEG C for 1 hour and cooling. Thus, a red coating film was obtained. Then, the brightness (Y) and the contrast ratio (CR) of the obtained coated substrate were measured.

On the other hand, the chromaticity and brightness (Y) were measured with a brown spectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.).

(Evaluation of crystal precipitation on the coating film surface)

The substrate obtained in the evaluation of color characteristics and contrast ratio (CR) was heated again at 260 DEG C for 1 hour and then cooled. After the heat treatment, the coating film surface of the coated substrate was observed with an optical microscope, and the presence or absence of crystal precipitation was judged according to the following criteria. In the evaluation result,? Is very good because there is no crystal precipitation,? Means that there is a slight degree of crystal precipitation but a good level,? Indicates a level of crystal precipitation but no problem in use, and X means a state that can not be used due to crystal precipitation .

&Amp; cir &amp;: 0 number of determinations

○: Number of determinations is 1 or more and less than 10

DELTA: Number of determinations: 10 or more and less than 100

X: More than 100 crystals

(Sensitivity, linearity, pattern shape, resolution, development tolerance, drug resistance evaluation)

The obtained photosensitive coloring composition was coated on a glass substrate having a thickness of 100 mm x 100 mm and a thickness of 0.7 mm and then heated in a clean oven at 70 DEG C for 20 minutes to remove the solvent to obtain a coating film having a thickness of about 2 mu m. Subsequently, the substrate was cooled to room temperature, and ultraviolet rays were exposed through a photomask having a stripe pattern with a width of 100 mu m (pitch: 200 mu m) and a width of 25 mu m (pitch: 50 mu m) using an ultra-high pressure mercury lamp. Thereafter, the substrate was spray-developed with an aqueous solution of sodium carbonate at 23 캜, washed and air-dried with ion-exchanged water, and heated in a clean oven at 230 캜 for 330 minutes. The spraying was carried out for the coating film in each photosensitive coloring composition in the shortest possible time for forming a pattern without development residue, and this was regarded as an appropriate developing time.

The film thickness of the coating film was measured using Dektak 3030 (manufactured by Japan Vacuum Technology Co., Ltd.).

(Sensitivity evaluation)

The pattern film thickness in the 100 mu m photomask portion of the filter segment formed by the above method was measured and the minimum exposure amount which was 90% or more with respect to the film thickness after coating was evaluated. The smaller the minimum amount of exposure, the higher the sensitivity and the better the photosensitive coloring composition. The rank of evaluation is as follows.

?: Less than 50 mJ / cm 2

?: 50 mJ / cm2 or more and less than 100 mJ / cm2

×: 100 mJ / cm 2 or more

(Linearity evaluation)

The pattern on the 100 mu m photomask portion of the filter segment formed by the above method was observed using an optical microscope and then evaluated. The rank of evaluation is as follows.

○: Good linearity

Δ: Partial linearity defect

×: poor linearity

(Pattern shape evaluation)

The section of the pattern in the 100 mu m photomask portion of the filter segment formed by the above method was observed using an electron microscope and then evaluated. The pattern section has a favorable net taper. The rank of evaluation is as follows.

○: The section has a net taper shape

X: Inverse tapered shape

(Evaluation of Resolution)

The pattern in the 25 mu m photomask portion of the filter segment formed by the above method was observed using an optical microscope and then evaluated. The rank of evaluation is as follows. The defective resolution means that adjacent stripe patterns are connected or defects occur. The rank of evaluation is as follows.

◎: Good resolution and linearity

○: Slightly inferior in linearity but good in resolution

△: Partially poor resolution

X: poor resolution

(Evaluation of Phenol resistance)

At the time of spray development, the pattern thickness of a 100 μm photomask portion of the filter segment formed by development at twice the appropriate time was measured and compared with the pattern film thickness formed by development at the optimum development time. The rank of evaluation is as follows.

⊚: difference in film thickness within 20%

?: Thickness difference greater than 20%, within 40%

B: Difference in film thickness is greater than 40%

X: Defect or peeling occurred due to double development

(Drug resistance evaluation)

The filter segments formed by the above method were immersed in N-methylpyrrolidone solution for 30 minutes, washed with ion-exchanged water, air-dried, observed with an optical microscope for a pattern in a 100 mu m photomask portion, and then evaluated. The rank of evaluation is as follows.

◎: Good appearance without change in color

○: Wrinkles and the like are generated in a part, but color is good without change

B: slight discoloration occurred

X: peeling or discoloration occurred

(Evaluation of stability with time of coloring composition)

The viscosity of the obtained photosensitive coloring composition was measured at the initial stage and at room temperature for one month, and the degree of viscosity increase with respect to the initial viscosity was calculated and evaluated. The rank of evaluation is as follows.

(Initial Viscosity) - (Initial Viscosity) x 100 (%) (Initial Viscosity)

⊚: The viscosity increase ratio is 5% or less and good

○: The viscosity increase ratio is greater than 5% and less than 10%

X: The viscosity increase rate is larger than 10%

[Table D-11]

As shown in Table D-11, the coloring composition for a color filter comprising the pigment (A1) represented by the formula (1) and the resin (D-B1) having the constituent units (D-b1) , And high evaluation results were obtained in all evaluations.

That is, in the composition containing a large amount of the structural unit (D-b1) of the resin (D-B1) in combination with the pigment (A1), the improvement of the contrast and the stabilization of the temporal stability In the composition containing a large amount of the constituent unit (D-b3), the effect of suppressing the crystallization of the pigment in the heating step and the effect of suppressing resolution tend to be confirmed However, if all the constituent units satisfy the specific content ratio, a photosensitive coloring composition having a high performance can be obtained. By providing an appropriate unit ratio, a high-performance and well-balanced color filter segment can be obtained.

Furthermore, when the photopolymerization initiator (D) is a combination of an acetophenone compound, a phosphine compound, an imidazole compound or an oxime ester compound, sensitivity, linearity and resolution are better.

Among them, the photopolymerization initiator (D) is preferably at least one selected from the group consisting of ethan-1-one, 1- [9-ethyl-6- (2-methylbenzoyl) -9H- In the coloring composition, the development resistance was further improved.

Further, the photosensitive coloring composition containing the polyfunctional thiol was more excellent in developing resistance.

Further, in the photosensitive coloring composition further comprising the ultraviolet absorber, the resolution was better.

In addition, the photosensitive coloring composition further comprising a storage stabilizer had better stability over time.

On the other hand, in the photosensitive coloring compositions of Reference Examples 3 to 9, neither lightness nor contrast ratio was low, and neither the crystallization of the pigment in the heating step nor the evaluation of the filter segment including sensitivity and the like could be obtained.

(Production of color filter)

The total amount of the pigment and the pigment derivative in the photosensitive coloring composition (RR-1) (4.39 parts), and the green photosensitive coloring composition, C.I. Pigment Green 58 / C.I. Pigment Yellow 150 = 2.63 parts / 1.76 parts, and in the case of the blue photosensitive coloring composition, C.I. Pigment Blue 15: 6 / CI. (P-3) was prepared in the same manner as in the pigment dispersion (P-3) except that the pigment dispersion was replaced with Pigment Violet 23 = 3.51 part / 0.88 part. Further, the pigment dispersion of the photosensitive coloring composition (RR- To obtain a green photosensitive coloring composition for a color filter and a blue photosensitive coloring composition for a color filter.

A photosensitive coloring composition (RR-1) was coated on a glass substrate of 100 mm x 100 mm with a die coater to a thickness of about 2 mu m and dried in an oven at 70 DEG C for 20 minutes by removing the solvent. Then, stripe pattern exposure was performed by ultraviolet rays using an exposure apparatus. The exposure dose was 100 mJ / cm 2. Then, the unexposed portions were removed by developing with a developer composed of an aqueous solution of sodium carbonate and then washed with ion-exchanged water. The substrate was heated at 230 占 폚 for 30 minutes to form a red filter segment having a line width of about 50 占 퐉. Then, in the same manner, a green filter segment was formed next to the red filter segment using a green photosensitive coloring composition, and then a blue filter segment was formed using a blue photosensitive coloring composition to form three filter segments on the same glass substrate Lt; / RTI &gt;

By using the above coloring composition for a color filter, it is possible to produce a fixed three color filter having a red filter segment having excellent color characteristics in a wide chromaticity range and having good heat resistance.

Industrial availability

According to the embodiment of the present invention, it is possible to provide a pigment composition for a color filter, a coloring composition and a color filter using the pigment composition, wherein the crystallization of the diketopyrrolopyrrole-based pigment is less likely to occur even by a heating process, .

Claims (3)

In a coloring composition for a color filter comprising a pigment (A), a binder resin (CB) and a solvent,
Wherein the pigment (A) is at least one selected from the group consisting of a diketopyrrolopyrrole pigment, an azo pigment, an anthraquinone pigment, a perylene pigment, a quinacridone pigment, a benzimidazole pigment other than the pigment (A1) At least one member selected from the group consisting of azo pigments, azo pigments, azo pigments,
The content of the pigment (A1) in the total of 100% by weight of the pigment (A) is 40 to 83.6% by weight,
Wherein the binder resin (CB) comprises an alkali-soluble photosensitive resin (C-B1)
The alkali-soluble photosensitive resin (C-B1)
An addition reaction of a carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond with a side chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group with at least one other monomer, A resin obtained by reacting a polybasic acid anhydride and introducing an ethylenically unsaturated double bond and a carboxyl group,
An ethylenically unsaturated monomer having an epoxy group is additionally reacted with a part of side chain carboxyl groups of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group and at least one other monomer to obtain a resin having an ethylenically unsaturated double bond and a carboxyl group introduced therein , And
Reacting an isocyanate group of an ethylenically unsaturated monomer having an isocyanate group with a branched chain hydroxyl group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a hydroxyl group with a monomer having an unsaturated monobasic acid having another carboxyl group and another monomer to obtain an ethylenically unsaturated The resin having a double bond and a carboxyl group introduced therein
And at least one member selected from the group consisting of a colorant and a colorant.

The method according to claim 1,
At least one photopolymerization initiator selected from the group consisting of an acetophenone-based compound, a phosphine-based compound, an imidazole-based compound and an oxime ester-based compound.
A color filter comprising a filter segment formed from the coloring composition for a color filter according to claim 1.