KR20140037818A

KR20140037818A - Diketopyrrolopyrrole-type pigment composition for color filters, colored composition for color filters, and color filter

Info

Publication number: KR20140037818A
Application number: KR1020137020929A
Authority: KR
Inventors: 유스케 이이다; 마사유키 후지키; 모토노리 안도우; 유이치 야마모토; 토시오 와쿠; 유타 아베; 히사미쯔 아라카와; 카나에 사사키
Original assignee: 토요잉크Sc홀딩스주식회사; 도요컬러주식회사
Priority date: 2011-01-28
Filing date: 2012-01-27
Publication date: 2014-03-27
Also published as: TWI510561B; KR20180083965A; KR20180135982A; WO2012102399A1; KR101942407B1; CN103339536A; KR101971251B1; TW201233734A; CN103339536B; KR101920285B1

Abstract

In the diketopyrrolopyrrole pigment composition for color filters containing a diketopyrrolopyrrole pigment represented by formula (1) and a diketopyrrolopyrrole pigment represented by formula (A-2), the formula (A-2) Content of the diketopyrrolopyrrole pigment displayed is 1 mass%-15 mass% with respect to the total mass of a diketopyrrolopyrrole pigment, The diketopyrrolopyrrole pigment composition for color filters characterized by the above-mentioned.

Description

DIKETOPYRROLOPYRROLE-TYPE PIGMENT COMPOSITION FOR COLOR FILTERS, COLORED COMPOSITION FOR COLOR FILTERS, AND COLOR FILTER}

This invention relates to the diketopyrrolopyrrole pigment composition for color filters, the coloring composition for color filters, and the color filter formed using this.

A liquid crystal display device is a display device in which a liquid crystal layer sandwiched between two polarizing plates controls the degree of polarization of the light passing through the first polarizing plate and controls the amount of light passing through the second polarizing plate to display the twisted nematic (TN). Type using liquid crystal forms the mainstream. By providing a color filter between the two polarizing plates, color display is possible. Recently, as it is used in televisions, personal computer monitors, and the like, demands for high brightness, high contrast, and high color reproducibility of color filters are increasing.

The color filter is formed by arranging two or more kinds of fine stripe (stripe) shaped filter segments in parallel or intersecting on the surface of a transparent substrate such as glass, or by arranging the fine filter segments in a constant horizontally and vertically arrangement. have. In general, it is often formed of three color filter segments of red, green, and blue, and each of these segments is not only fine, for example, from several microns to several hundred microns, but also arranged in a predetermined arrangement for each color.

In general, in a color liquid crystal display device, a transparent electrode for driving a liquid crystal on a color filter is formed by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a predetermined direction is formed thereon. In order to fully acquire the performance of these transparent electrodes and an oriented film, generally the high temperature process of 200 degreeC or more, Preferably 230 degreeC or more is performed in the manufacturing process of forming a color filter. For this reason, the method called the pigment dispersion method which uses the pigment which is excellent in light resistance and heat resistance as a coloring agent is mainstream in the manufacturing method of a color filter at present.

In the pigment dispersion method, it is common to use, as the colorant, a pigment having excellent light resistance and heat resistance such as diketopyrrolopyrrole pigment, anthraquinone pigment, perylene pigment or disazo pigment as a colorant alone or in combination. .

Among the diketopyrrolopyrrole pigments, CI Pigment Red 254 is a pigment particularly excellent in brightness, but further brightness improvement is desired. In addition, in recent years, there is also a strong demand for high contrast for color filters. For this purpose, it is considered that it is desirable to make the primary particle diameter of diketopyrrolopyrrole pigments as small as possible. However, since the fined diketopyrrolopyrrole pigment has the property of easy crystal growth due to the hydrogen bonding between the molecules, crystallization occurs in the heating step when forming the color filter, foreign matter is generated. There was a problem.

In addition, a diketopyrrolopyrrole pigment can be obtained by the manufacturing method (henceforth a "succinic acid ester synthesis method") disclosed by patent document 1 and patent document 2.

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

Patent Literature 4 describes the use of a mixture of at least two structurally different diketopyrrolopyrrole pigments obtained by a succinic acid ester synthesis method using a nitrile compound having a plurality of specific structural formulas as a raw material for a color filter.

Patent document 5 and patent document 6 use a diketopyrrolopyrrole pigment (mainly CI pigment red 254), the diaryl diketopyrrolopyrrole compound of at least one specific structural formula, and a pigment derivative together, The coloring composition for color filters in which crystal precipitation by the heating process was suppressed is disclosed.

In patent document 7, the coloring composition for color filters using the brominated diketopyrrolopyrrole pigment is disclosed. In addition, Patent Document 8 describes the use of a brominated diketopyrrolopyrrole pigment composition in the color filter.

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

The problem to be solved by the present invention is a diketopyrrolopyrrole pigment composition for color filters, color compositions for color filters, which have good brightness and contrast, and are hard to produce crystallization of diketopyrrolopyrrole pigments even by a heating step. The present invention provides a color filter using the same.

1st Embodiment of this invention is a diketopyrrolopyrrole pigment composition for color filters containing the diketopyrrolopyrrole pigment represented by Formula (1) and the diketopyrrolopyrrole pigment represented by Formula (A-2). WHEREIN: The content of the diketopyrrolopyrrole pigment represented by Formula (A-2) is 1 mass%-15 mass% with respect to the total mass of a diketopyrrolopyrrole pigment, The diketopyrrole for color filters characterized by the above-mentioned. It relates to a pyrrole pigment composition.

[Formula 1]

[In formula (A-2),

A and B are each independently 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 are each independently 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.

However, A and B do not become hydrogen atoms at the same time.]

In the first embodiment, the diketopyrrolopyrrole pigment represented by the formula (A-2) is formula (A-2-1), formula (A-2-2), or formula (A-2- 3) or the diketopyrrolopyrrole pigment composition for color filters described in any one of formula (A-2-4).

(2)

[In formula (A-2-3) and formula (A-2-4),

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

Moreover, 1st Embodiment relates to the diketopyrrolopyrrole pigment composition for the said color filters which further contains CI Pigment Red 254 as a diketopyrrolopyrrole pigment.

Moreover, 1st Embodiment is 85 mass%-99 mass of total content of the diketopyrrolopyrrole pigment and CI pigment red 254 represented by Formula (1) based on the total mass of a diketopyrrolopyrrole pigment. It relates to the diketopyrrolopyrrole pigment composition for the color filter, characterized in that%.

In a first embodiment, the mass ratio of the diketopyrrolopyrrole pigment represented by the formula (1) and the CI Pigment Red 254 is 20:80 to 99: 1, wherein the diketopyrrolopypi for color filters. A roll type pigment composition is related.

Moreover, 1st Embodiment is related with the said diketopyrrolopyrrole pigment composition for color filters which further contains a pigment derivative.

The 2nd embodiment of this invention is the diketopyrrolopyrrole pigment for color filters containing the diketopyrrolopyrrole pigment represented by Formula (1), and the diketopyrrolopyrrole pigment represented by Formula (B-2). The composition WHEREIN: The mass ratio of Formula (1) and Formula (B-2) is 97: 3-85:15, It is related with the diketopyrrolopyrrole pigment composition for color filters.

(3)

In 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 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 are each independently 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.

However, A and B do not become hydrogen atoms at the same time.]

In the second embodiment, the formula (B-2) is a formula (B-2-1), a formula (B-2-2), a formula (B-2-3), or a formula (B-2). -4), formula (B-2-5), formula (B-2-6), or formula (B-2-7), any one of the color filter diketopyrrolopyrrole pigment composition, characterized in that It is about.

[Chemical Formula 4]

[In Formula (B-2-4), Formula (B-2-6), and Formula (B-2-7),

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

Moreover, 2nd Embodiment is related with the said diketopyrrolopyrrole pigment composition for said color filters which further contains a pigment derivative.

A third embodiment of the present invention is a coloring composition containing a colorant, a binder resin, and an organic solvent, wherein the colorant contains the diketopyrrolopyrrole pigment composition of the first embodiment. It relates to a coloring composition.

Moreover, 3rd Embodiment is related with the coloring composition for said color filters which further contains a photopolymerizable monomer and / or a photoinitiator.

A fourth embodiment of the present invention is a coloring composition containing a colorant, a binder resin, and an organic solvent, wherein the colorant contains the diketopyrrolopyrrole pigment composition of the second embodiment. It relates to a coloring composition.

Moreover, 4th Embodiment is related with the coloring composition for said color filters which further contains a photopolymerizable monomer and / or a photoinitiator.

In the fifth embodiment of the present invention, in the color composition for color filters containing a pigment (A), a binder resin (CB), and a solvent, the pigment (A1) represented by formula (1) is a pigment (A1). ), And the binder resin (CB) includes an alkali-soluble photosensitive resin (C-B1).

[Chemical Formula 5]

In the fifth embodiment, the pigment (A) is a diketopyrrolopyrrole pigment, azo pigments, anthraquinone pigments, perylene pigments, quinacridone pigments, benzimidazolone other than the pigment (A1) It relates to the said coloring composition for color filters which further contains at least 1 sort (s) or more selected from the group which consists of a pigment and quinoline pigment.

Further, the fifth embodiment further comprises at least one photopolymerization initiator (CD) selected from the group consisting of acetophenone compounds, phosphine compounds, imidazole compounds and oxime ester compounds. It relates to the coloring composition for the color filter.

In a sixth embodiment of the present invention, in the color composition for color filters containing a pigment (A), a binder resin (DB), and a solvent, the pigment (A1) represented by formula (1) is a pigment (A1). ), And binder resin (DB) contains resin (D-B1) which has structural unit (D-b1) (D-b3), It is related with the coloring composition for color filters characterized by the above-mentioned.

[Chemical Formula 6]

(D-b1) Structural unit having a carboxyl group: 2 to 60 wt%

(D-b2) Structural unit which has an aromatic ring group shown by Formula (D-2) or (D-3): 2-80 weight%

(D-b3) Structural unit which has an aliphatic ring group shown by Formula (D-4) or (D-5): 2-60 weight%

[Formula 7]

[Formula 8]

[In formula (D-2) and (D-3), R is a C1-C20 alkyl group which may have a hydrogen atom or a benzene ring. The dashed portion in formula (D-3) represents a cyclic structure containing one or more saturated or unsaturated heterocycles which may have a substituent adjacent to the benzene ring.]

[Chemical Formula 9]

[Formula 10]

In a sixth embodiment, the pigment (A) is a diketopyrrolopyrrole pigment, azo pigments, anthraquinone pigments, perylene pigments, quinacridone pigments, benzimidazolone other than the pigment (A1) It relates to the said coloring composition for color filters which further contains at least 1 sort (s) or more selected from the group which consists of a pigment and quinoline pigment.

Further, the sixth embodiment further comprises at least one photopolymerization initiator (DD) selected from the group consisting of acetophenone compounds, phosphine compounds, imidazole compounds and oxime ester compounds. It relates to the coloring composition for the color filter.

7th Embodiment of this invention is related with the color filter characterized by including the filter segment formed from the said coloring composition for color filters.

The present disclosure discloses Japanese Patent Application No. 2011-15874, filed Jan. 28, 2011, Japanese Patent Application No. 2011-76928, filed March 31, 2011, and Japanese Patent Application No. 31, 2011. It is related to the subject matter described in the application 2011-76929 and the Japanese patent application 2011-271836 for which it applied to December 13, 2011, These disclosures are integrated here.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described in detail.

In addition, "CI" mentioned below means color index (CI). In addition, when it represents with "(meth) acrylate", "(meth) acrylic acid", or "(meth) acrylamide", unless otherwise indicated, "acrylate and / or methacrylate", respectively "Acrylic acid and / or methacrylic acid" or "acrylamide and / or methacrylamide" shall be shown.

[ Diketopyrrolopyrrole system Pigment composition]

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

[First Embodiment]

(Diketopyrrolopyrrole Pigment Composition)

1st Embodiment is the diketopyrrolopyrrole pigment for color filters containing the diketopyrrolopyrrole pigment represented by following formula (1), and the specific hetero diketopyrrolopyrrole pigment represented by following formula (A-2). WHEREIN: The content of the specific hetero diketopyrrolopyrrole pigment represented by following formula (A-2) WHEREIN: The diketopyrrole for color filters whose content is 1 mass%-15 mass% based on the total mass of a diketopyrrolopyrrole pigment. It is a pyrrole pigment composition.

As a result of intensive studies, the present inventors have applied a brominated diketopyrrolopyrrole pigment (formula (1)) to a color filter as compared with CI pigment red 254 (chlorinated diketopyrrolopyrrole pigment) that has been conventionally used. We found that the brightness improved. Furthermore, a diketopyrrolopyrrole pigment composition containing a diketopyrrolopyrrole pigment (Formula A-2) (hereinafter referred to as "specific hetero diketopyrrolopyrrole pigment A") introduced with a substituent asymmetrically of a specific structure It was found that a color filter having high contrast as well as high crystallinity and suppressed crystallization by a heating step can be obtained by use of the specific hetero diketopyrrolopyrrole pigment A selected here because the interaction with the resin component is small. In addition, the active surface of the brominated diketopyrrolopyrrole pigment can be efficiently covered, and the thermal aggregation of the pigment by the heating step is suppressed, thereby exhibiting high contrast and crystallization suppression effect in a small amount. Topyrrolopyrrole Pigment A has better color characteristics than the known crystallization inhibitors so far and can be added in less amount. This does not inhibit the excellent brightness improving effect of the brominated diketopyrrolopyrrole pigment Furthermore, since the diketopyrrolopyrrole pigment composition contains a specific hetero diketopyrrolopyrrole pigment A, it is excellent in viscosity stability.

According to the first embodiment, a diketopyrrolopyrrole pigment composition for color filters having good brightness and contrast, not only crystal precipitation of diketopyrrolopyrrole pigments are produced by the heating process but also excellent in viscosity stability. Can provide.

[Formula 11]

[In formula (A-2),

However, A and B do not become hydrogen atoms at the same time.]

The alkyl group having 1 to 12 carbon atoms may be linear or branched, and specifically, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl or hexyl , Heptyl group, octyl group, decyl group, dodecyl group, 1,5-dimethylhexyl group, 1,6-dimethylheptyl group, 2-ethylhexyl group and the like, but are not limited thereto.

Examples of the phenyl group which may have the 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. The phenyl group which has is mentioned. The phenyl group may have one or two or more of these substituents. More specifically, a phenyl group, p-methylphenyl group, 4-tert- butylphenyl group, p-nitrophenyl group, p-methoxyphenyl group, p-chlorophenyl group, 2, 4- dichlorophenyl group, 3-carbamoylphenyl group, etc. are mentioned. It may be, but is not limited to these.

Examples of the aralkyl group which may have the 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. Aralkyl group which has is mentioned. The aralkyl group may have one or two or more of these substituents. More specifically, a benzyl group, 4-methylbenzyl group, 4-tert-butylbenzyl group, 4-methoxybenzyl group, 4-nitrobenzyl group, 2,4-dichlorobenzyl group, etc. are mentioned, It is not limited.

Among the specific hetero diketopyrrolopyrrole pigment A represented by the formula (A-2) used for the pigment composition of the first embodiment, formulas (A-2-1), (A-2-2), and formula ( A-2-3) and formula (A-2-4) are preferable at the point of lightness, contrast, and crystal precipitation inhibiting effect. In addition, R <^6> -R <^8> of Formula (A-2-3) and Formula (A-2-4) has a C4 or more alkyl group or the phenyl group which may have a substituent from the point of contrast and a crystal precipitation suppression effect. desirable. The reason why they are effective in suppressing high contrast and crystallization is due to bulky substituents such as carbonamide groups (carbamoyl groups), phenyl groups and t-butyl groups having an alkyl group having 4 or more carbon atoms. It is considered that aggregation of the pigment is suppressed by the steric hindrance effect. Moreover, since the specific hetero diketopyrrolopyrrole pigment A which has a carboamide group (carbamoyl group), a phenyl group, and a t-butyl group is excellent also in color characteristic, it does not impair the outstanding brightness of the brominated diketopyrrolopyrrole pigment.

[Chemical Formula 12]

[In formula (A-2-3) and formula (A-2-4),

Although the specific example of specific hetero diketopyrrolopyrrole pigment A of Formula (A-2) is given to the following, it is not limited to these.

[Chemical Formula 13]

[Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

The pigment composition is characterized in that the content of the specific hetero diketopyrrolopyrrole 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. . Preferably, it is the range of 3 mass%-10 mass%. When the ratio of the specific hetero diketopyrrolopyrrole pigment A of formula (A-2) exceeds 15 mass%, the crystallization inhibiting effect can be obtained, but the excellent brightness of the brominated diketopyrrolopyrrole pigment of formula (1) is impaired. . On the other hand, when the ratio of specific hetero diketopyrrolopyrrole pigment A of formula (A-2) is less than 1 mass%, the effect of suppressing high contrast and crystallization is not enough. If the crystallization inhibiting effect is not sufficient, light scattering occurs due to the crystalline foreign matter deposited on the surface of the coating film in the heating step, causing a decrease in brightness and contrast ratio. Therefore, by using the diketopyrrolopyrrole pigment composition containing a specific hetero diketopyrrolopyrrole pigment A in the above ratio, it is possible to achieve high brightness and high contrast, and also to determine the diketopyrrolopyrrole pigment by heating process Precipitation can be suppressed. Furthermore, excellent viscosity stability can be obtained.

A pigment composition can use together diketopyrrolopyrrole pigment other than the diketopyrrolopyrrole pigment of Formula (1) and the specific hetero diketopyrrolopyrrole pigment A of Formula (A-2) in the range which does not impair the effect. It may be. Specifically, although diketopyrrolopyrrole pigments, such as CI pigment red 254, 255, 264, 272, CI pigment orange 71, 73, or 81, are not limited to these. As a diketopyrrolopyrrole pigment which can be used together, CI pigment red 254 is preferable. The reason why CI Pigment Red 254 is preferable is normally contained when the specific hetero diketopyrrolopyrrole pigment A of formula (A-2) is manufactured by the succinic acid diester synthesis method, and the diketopyrrolopyrrole pigment of formula (1) This is because it is difficult to affect the excellent brightness of the.

When the pigment composition contains CI Pigment Red 254, the diketopyrrolopyrrole pigment and CI Pigment Red 254 represented by Formula (1) based on the total weight of the diketopyrrolopyrrole pigments (100% by weight). It is preferable that the total content of is 85 mass%-99 mass%. When the total content of the diketopyrrolopyrrole pigment represented by the formula (1) and the CI pigment red 254 is less than 85% by mass, the brightness improvement effect may be reduced, and when more than 99% by mass, the specific hetero dike Since there is little content of topyrrolopyrrole pigment A, contrast ratio and the crystal precipitation suppression effect may not fully be acquired. Moreover, it is preferable that the mass ratio of the diketopyrrolopyrrole pigment represented by Formula (1) and CI pigment red 254 is 20: 80-99: 1. More preferably, it is 50: 50-99: 1. When content of the diketopyrrolopyrrole pigment represented by Formula (1) in the sum total of the diketopyrrolopyrrole pigment represented by Formula (1) and CI pigment red 254 is 20 mass% or more, the brightness improvement effect will increase. Therefore, it is preferable.

Moreover, as a diketopyrrolopyrrole pigment other than the diketopyrrolopyrrole pigment of Formula (1) and the specific hetero diketopyrrolopyrrole pigment A of Formula (A-2), the specific hetero dike of Formula (B-2) mentioned later It is also possible to use topyrrolopyrrole pigments. At this time, it is preferable that the mass ratio of the diketopyrrolopyrrole pigment of Formula (1) and the specific hetero diketopyrrolopyrrole pigment B of Formula (B-2) is 97: 3-85: 15.

(Manufacturing method of diketopyrrolopyrrole pigment)

The diketopyrrolopyrrole pigment represented by Formula (1) can be obtained using the well-known method described in the international publication 2009/144115 pamphlet etc.

In addition, the diketopyrrolopyrrole pigment represented by Formula (1) can be manufactured by the succinic acid diester synthesis method. That is, 2 mol of 4-bromobenzonitrile is carried out with respect to 1 mol of succinic acid diesters in inert organic solvents, such as tert-amyl alcohol, in condensation reaction at 80-110 degreeC high temperature in presence of an alkali metal or alkali metal alkoxide. The alkali metal salt of the diketopyrrolopyrrole compound is produced. Subsequently, the brominated diketopyrrolopyrrole pigment can be obtained by protonating with respect to the alkali metal salt of this diketopyrrolopyrrole compound using water, alcohol, an acid, etc. At this time, the magnitude | size of the primary particle diameter obtained can be controlled according to the kind, ratio, and quantity of temperature, water, alcohol, or acid in protonation. The manufacturing method of the diketopyrrolopyrrole pigment represented by Formula (1) is not limited to this method.

Specific hetero diketopyrrolopyrrole pigment A of formula (A-2) is described, for example, in Synth. Synthesis can be performed using the methods described in Commun., 1988, 18, 1213 and Tetrahedron, 58 (2002) 5547-5565. The manufacturing method of specific hetero diketopyrrolopyrrole pigment A is not limited to this method.

In addition, the specific hetero diketopyrrolopyrrole pigment A of Formula (A-2) can also be synthesize | combined by mixture with CI Pigment Red 254. This can be achieved by using a method of using at least two 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 WO2009 / 081930 pamphlet, a plurality of benzonitrile compounds to be used are selected from 4-chlorobenzonitrile and a benzonitrile compound represented by the following formula (A-3) Certain hetero diketopyrrolopyrrole pigment A of (A-2) can be prepared in a mixture with CI Pigment Red 254.

[Chemical Formula 17]

[In formula (A-3),

However, A and B do not become 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 mix and use the diketopyrrolopyrrole pigment represented by Formula (1) and what manufactured the specific hetero diketopyrrolopyrrole pigment A separately. Moreover, the mixture of specific hetero diketopyrrolopyrrole pigment A and CI pigment red 254 synthesize | combined by the succinic acid diester synthesis method can also be used in mixture with the diketopyrrolopyrrole pigment represented by Formula (1). In these cases, the pigment may be simply mixed before dispersing the pigment in the pigment carrier, or may be ground mixed through a salt milling treatment.

In the pigment composition, the mass ratio of the diketopyrrolopyrrole pigment represented by formula (1) and the specific hetero diketopyrrolopyrrole pigment A and CI Pigment Red 254 of formula (A-2) is TOF-MASS, FD-MASS. Analyzes can be performed using LC-MASS or NMR. Alternatively, as disclosed in Japanese Patent Application Laid-Open No. H08-199085, a solubility obtained by stirring a diketopyrrolopyrrole pigment composition with di-tert-butyldicarbonate and 4-dimethylaminopyridine at room temperature in tetrahydrofuran. After conversion to the diketopyrrolopyrrole compound, the analysis may be performed using NMR, MASS, LC-MASS, or the like. Alternatively, the above analysis may be performed after hydrogen of the NH group of the pyrrolopyrrole ring is substituted with an alkyl group using an alkyl halide or the like and converted into a soluble diketopyrrolopyrrole.

(Pigment derivative)

A pigment derivative can be used for a pigment composition for the purpose of suppressing pigment crystal growth and improving pigment dispersibility. As a pigment derivative used for a pigment composition, a diketopyrrolopyrrole derivative, a benzoisoindole derivative, an anthraquinone derivative, a dianthraquinone derivative, a thiazine indigo derivative, an azo pigment derivative, a quinophthalone derivative, a quinacridone derivative, etc. are mentioned. Can be. Although the pigment derivative represented by following formula (4) is mentioned as a structure of a pigment derivative, It is not limited to these.

P-Lm equation (4)

In formula (4),

P is a diketopyrrolopyrrole residue, a benzoisoindole residue, an anthraquinone residue, a dianthraquinone residue, a thiazine indigo residue, an azo pigment residue, a quinophthalone residue or a quinacridone residue,

m is an integer of 1-4,

Each L independently represents -OH; -SO ₃ H, -COOH, monovalent to trivalent metal salts of these acid groups, alkylammonium salts; Phthalimide methyl group which may have a substituent; It is group represented by following formula (a), (b), (c), (d), (e) or (f),

[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 together May form a heterocycle which may have a substituent, further including nitrogen, oxygen or sulfur atoms, if necessary,

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

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

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

Z is -CONH-, -NHCO-, -SO ₂ NH-, or -NHSO _2- ,

R ²⁵ is a hydrogen atom, -NH ₂ , -NHCOCH ₃ , -NHR ²⁶ , or a substituent represented by formula (c), wherein R ²⁶ is an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a substituent It is a C2-C20 alkenyl group which may have.]

Examples of the monovalent to trivalent metals include sodium, potassium, magnesium, calcium, iron, aluminum, and the like. Moreover, as alkylammonium salt, quaternary alkyl, such as ammonium salt of long-chain monoalkylamine, such as octylamine, laurylamine, or stearylamine, or palmityl trimethylammonium salt, the dilauryl dimethyl ammonium salt, or distearyl dimethyl ammonium salt, etc. Ammonium salt is mentioned.

As a phthalimide methyl group which may have a substituent, an alkyl group which may have a substituent, the alkenyl group which may have a substituent, or the heterocyclic substituent which may have a substituent, a halogen atom, a nitro group, a cyano group, a carbamoyl group , N-substituted carbamoyl group, sulfamoyl group, N-substituted sulfamoyl group, a C1-C20 alkoxyl group, a C1-C20 alkylthio group, and the like, but is not limited thereto.

The dye derivative is sulfonated by heating in sulfuric acid or fuming sulfuric acid, phthalimide methylation reaction for dehydrating and condensation with N-hydroxymethylphthalimide in sulfuric acid, and chlorsulfonated using chlorsulfonic acid and thionyl chloride. Then, it is synthesize | combined by well-known manufacturing methods, such as sulfonamide-ized reaction which makes amine components, such as dimethylaminopropylamine, react.

As an amine component used in order to form the substituent represented by said Formula (a), Formula (b), and Formula (c), for example, dimethylamine, diethylamine, methylethylamine, N, N-ethyl Isopropylamine, N, N-ethylpropylamine, N, N-methylbutylamine, N, N-methylisobutylamine, N, N-butylethylamine, N, N-tert-butylethylamine, diisopropyl Amine, dipropylamine, N, N-sec-butylpropylamine, dibutylamine, di-sec-butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine, diiso Amylamine, dihexylamine, dicyclohexylamine, di (2-ethylhexyl) amine, dioctylamine, N, N-methyloctadecylamine, didecylamine, diallylamine, N, N-ethyl-1, 2-dimethylpropylamine, N, N-methylhexylamine, dioleylamine, distearylamine, N, N-dimethylaminomethylamine, N, N-dimethylaminoethylamine, N, N-dimethylaminoamylamine, N, N-dimethylaminobutylamine, N, N-diethylaminoethyl Amine, N, N-diethylaminopropylamine, N, N-diethylaminohexylamine, N, N-diethylaminobutylamine, N, N-diethylaminopentylamine, N, N-dipropylaminobutyl Amine, N, N-dibutylaminopropylamine, N, N-dibutylaminoethylamine, N, N-dibutylaminobutylamine, N, N-diisobutylaminopentylamine, N, N-methyl-la Urylaminopropylamine, N, N-ethyl-hexylaminoethylamine, N, N-distearylaminoethylamine, N, N-dioleylaminoethylamine, N, N-distearylaminobutylamine, piperi Dean, 2-Pipecoline, 3-Pipecoline, 4-Pipecoline, 2,4-Lupetidine, 2,6-Lupetidine, 3,5-Lupetidine, 3-Piperidinemethanol, Pipeecholine Acid, isonipecotic acid, methyl isonipecoate, ethyl isonipemate, 2-piperidineethanol, pyrrolidine, 3-hydroxypyrrolidine, N-aminoethylpiperidine, N-aminoethyl-4-pipecoline, N-aminoethyl morpholine, N-aminopropyl Piperidine, N-aminopropyl-2-pipecoline, N-aminopropyl-4-pipecoline, N-aminopropylmorpholine, N-methylpiperazine, N-butylpiperazine, N-methylhomopiperazine, 1-cyclopentyl piperazine, 1-amino-4-methyl piperazine, 1-cyclopentyl piperazine, and the like, but are not limited thereto.

In addition, when a substituent is introduce | transduced into an azo dye, an azo dye derivative can also be manufactured by introducing a substituent into a diazo component or a coupling component previously, and performing a coupling reaction after that.

The usage of the dye derivative is not only a method of mixing with the pigment composition when the diketopyrrolopyrrole pigment composition is dispersed in the pigment carrier, but also a method of mixing and mixing in water or an organic solvent at the time of pigment production or adding at the time of salt milling treatment. Can be mentioned. The method of mixing the pigment derivative in water or an organic solvent in the production of the pigment or in the addition of the salt milling treatment expresses the effect of inhibiting the crystal growth of the diketopyrrolopyrrole pigment, but the effect of inhibiting the crystal growth. In order to exert, the dye derivative is required to be efficiently adsorbed on the surface of the diketopyrrolopyrrole pigment, and not to be easily desorbed. Accordingly, the structure of the dye derivative is often considered to partially have a chemical structure similar to the pigment used. For this reason, in the case of producing diketopyrrolopyrrole pigments, in general, pigment derivatives having a diketopyrrolopyrrole structure, thiazine indigo structure, benzoisoindole structure, or quinacridone structure are effective.

Moreover, when using a pigment derivative, it is calculated | required that the color tone of a diketopyrrolopyrrole pigment composition is not reduced as much as possible. From the viewpoint of color, the use of yellow, orange diketopyrrolopyrrole derivatives, benzoisoindole derivatives, thiazineindigo derivatives, azo dye derivatives, or quinophthalone derivatives is preferable.

It is preferable that the compounding quantity of a dye derivative is 0.5-40 mass parts with respect to 100 mass parts of diketopyrrolopyrrole pigment compositions. More preferably, it is the range of 3-35 mass parts with respect to 100 mass parts of diketopyrrolopyrrole pigment compositions. It is because when it is less than 0.5 mass part, the crystal growth inhibitory effect may be inadequate, and when more than 40 mass parts, the favorable color tone of a diketopyrrolopyrrole pigment may be reduced.

Hereinafter, although the specific example of the pigment derivative used for a diketopyrrolopyrrole pigment composition is described, it is not limited to these.

(Specific examples of diketopyrrolopyrrole derivatives)

As a diketopyrrolopyrrole derivative, although the compound represented by following formula (5) or formula (6) can be used specifically, It is not limited to these.

[Chemical Formula 19]

[Chemical Formula 20]

(Specific examples of benzoisoindole derivatives)

As a benzoisoindole derivative, although the compound represented by following formula (7) can be used specifically, it is not limited to these.

[Chemical Formula 21]

(Specific examples of anthraquinone derivatives)

As an anthraquinone derivative, although the compound represented by following formula (8) can be used specifically, it is not limited to these.

[Chemical Formula 22]

(Specific examples of dianthraquinone derivatives)

As a dianthraquinone derivative, although the compound represented by following formula (9) can be used specifically, it is not limited to these.

(23)

(Specific examples of thiazine indigo derivative)

As a thiazine indigo derivative, although the compound represented by following formula (10) can be used specifically, it is not limited to these.

&Lt; EMI ID =

(Specific example of azo dye derivative)

As an azo dye derivative, although the compound represented by following formula (11), formula (12), or formula (13) can be used specifically, It is not limited to these.

(25)

(26)

(27)

(Specific examples of quinophthalone derivatives)

As a quinophthalone derivative, although the compound represented by following formula (14-1)-formula (14-13) can be used specifically, it is not limited to these.

(28)

[Chemical Formula 29]

(30)

(Specific examples of quinacridone derivatives)

As a quinacridone derivative, although the compound represented by following formula (15) can be used specifically, it is not limited to these.

(31)

(Average primary particle size of pigment)

It is preferable that the pigment composition of 1st Embodiment has a very small primary particle diameter, narrow the width of distribution, and has a sharp particle size distribution. It is preferable that the average primary particle diameter (volume average particle diameter) calculated | required by TEM (transmission electron microscope) of the pigment composition of 1st Embodiment is the range of 5-70 nm. When it becomes smaller than 5 nm, dispersion in the organic solvent may become difficult. Moreover, when larger than 70 nm, sufficient contrast ratio may not be obtained. For this reason, the more preferable range is the range of 10-40 nm. In the step of synthesizing and mixing the pigments into a pigment composition, the average primary particle size may be used as it is in the above range. Otherwise, it is preferable to refine and refine the pigments by salt milling or the like. .

(Fineness of pigment)

It is preferable to refine | miniaturize and use the pigment containing the diketopyrrolopyrrole pigment composition of 1st Embodiment, and the salt milling process is preferable as a refinement | miniaturization method.

Salt milling treatment is a mixture of a pigment, a water-soluble inorganic salt and a water-soluble organic solvent using a kneader such as a kneader, a trimix, a two-roll mill, a three-roll mill, a ball mill, an attritor, a sand mill, or the like. After kneading while heating mechanically, it is the process of removing water-soluble inorganic salt and water-soluble organic solvent by water washing. The water-soluble inorganic salt acts as a crushing aid, and it is thought that the pigment is crushed by using the hardness of the inorganic salt at the time of salt milling, thereby forming an active surface and crystal growth. Therefore, during kneading, the crushing and crystal growth of the pigment occur simultaneously, and the primary particle diameter of the pigment obtained according to the kneading conditions is different.

In order to promote crystal growth by heating, it is preferable that heating temperature is 35-150 degreeC. When heating temperature is less than 35 degreeC, crystal growth may not fully generate | occur | produce and the shape of a pigment particle may become near amorphous. On the other hand, when heating temperature exceeds 150 degreeC, crystal growth may advance too much and the primary particle diameter of a pigment may become large. Moreover, it is preferable that the kneading time of a salt milling process is 2 to 24 hours from a viewpoint of the balance of the particle size distribution of the primary particle of the pigment obtained and the cost required for the salt milling process.

By optimizing the conditions at the time of salt milling the pigment, it is possible to obtain a pigment having a very fine primary particle diameter, a narrow distribution width and a sharp particle size distribution.

Moreover, although sodium chloride, barium chloride, potassium chloride, sodium sulfate, etc. can be used as a water-soluble inorganic salt used for a salt milling process, it is preferable to use sodium chloride (salt) from a viewpoint of price. It is preferable to use 50-2000 mass parts with respect to 100 mass parts of pigments from both surfaces of a processing efficiency and a production efficiency, and, as for a water-soluble inorganic salt, it is most preferable to use 300-1200 mass parts.

In addition, the water-soluble organic solvent has a function of wetting the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it is dissolved (mixed) in water and does not substantially dissolve the inorganic salt used. However, since a temperature rises at the time of salt milling and a solvent becomes easy to evaporate, the high boiling point solvent of 120 degreeC or more of boiling point is preferable from a safety viewpoint.

For example, there can be mentioned 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl Diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, diethylene glycol monomethyl ether, Monoethyl ether, and liquid polypropylene glycol. It is preferable to use 5-1000 mass parts with respect to 100 mass parts of pigments, and, as for a water-soluble organic solvent, it is most preferable to use 50-500 mass parts.

In the salt milling process, a dye derivative may be used in combination to improve the kneading efficiency, and is very effective for miniaturizing and sizing the pigment. In miniaturization of a diketopyrrolopyrrole pigment composition, it is preferable to use the pigment derivative, but is not limited thereto. It is preferable that the usage-amount of a dye derivative does not affect color tone, ie, it is the range of 0.5-40 mass parts with respect to 100 mass parts of pigments.

In addition, when performing a salt milling process, you may add resin as needed. The type of 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. It is preferable that resin used is solid at room temperature, and is water-insoluble, and it is more preferable that it is partially soluble in the said organic solvent. It is preferable that the usage-amount of resin is the range of 5-200 mass parts with respect to 100 mass parts of pigments.

Second Embodiment

(Diketopyrrolopyrrole Pigment Composition)

2nd Embodiment is the diketopyrrolopyrrole pigment composition for color filters containing the brominated diketopyrrolopyrrole pigment of following formula (1), and the specific hetero diketopyrrolopyrrole pigment of following formula (B-2). It is a diketopyrrolopyrrole pigment composition for color filters whose mass ratio of following formula (1) and following formula (B-2) is 97: 3-85:15.

As a result of intensive studies, the present inventors applied a brominated diketopyrrolopyrrole pigment (formula (1)) to a color filter in place of the CI pigment red 254 (chlorinated diketopyrrolopyrrole pigment) that has been conventionally used. Was found to improve. And a diketopyrrolopyrrole pigment (formula (B-2)) having a substituent introduced asymmetrically with this brominated diketopyrrolopyrrole pigment (hereinafter referred to as `` specific hetero diketopyrrolopyrrole pigment B '') in a specific ratio. By using a pigment composition, it discovered that the color filter which crystallization by the heating process was suppressed while being high brightness and high contrast was obtained.

According to the second embodiment, it is possible to provide a pigment composition for color filters, in which crystal precipitation of diketopyrrolopyrrole pigments does not occur even by a heating step with high brightness and high contrast.

(32)

In 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 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 ,

However, A and B do not become hydrogen atoms at the same time.]

Although the specific example of specific hetero diketopyrrolopyrrole pigment B of Formula (B-2) is given to the following, it is not limited to these.

(33)

(34)

(35)

(36)

In formula (B-2) used for a pigment composition, a formula (B-2-1), a formula (B-2-2), a formula (B-2-4a), a formula (B-2-6b), a formula (B-2-7) and the like are preferred from the viewpoint of color, contrast and crystallization inhibiting effect.

The ratio of Formula (1) and Formula (B-2) in a pigment composition is the range of 97: 3-85:15 by mass ratio. If the ratio of the formula (B-2) exceeds 15% by mass, the crystallization inhibiting effect can be obtained, but the excellent color tone of the formula (1) is impaired. This is because the brominated diketopyrrolopyrrole pigment of formula (1) is excellent in color tone than the specific hetero diketopyrrolopyrrole pigment B of formula (B-2). On the other hand, when the ratio of the formula (B-2) is less than 3% by mass, the effect of suppressing high contrast and crystallization is not sufficient. If the crystallization inhibiting effect is not sufficient, light scattering occurs due to the crystalline foreign matter deposited on the surface of the coating film in the heating step, causing 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 the heating step.

A pigment composition may use together diketopyrrolopyrrole pigments other than the diketopyrrolopyrrole pigment of Formula (1) and the specific hetero diketopyrrolopyrrole pigment B of Formula (B-2) in the range which does not impair the effect. It may be.

Moreover, as a diketopyrrolopyrrole pigment other than the diketopyrrolopyrrole pigment of Formula (1) and the specific hetero diketopyrrolopyrrole pigment B of Formula (B-2), the specific hetero dike of Formula (A-2) mentioned above It is also possible to use topyrrolopyrrole pigments. At this time, it is preferable that content of the specific hetero diketopyrrolopyrrole pigment represented by Formula (A-2) is 1 mass%-15 mass% based on the total mass of a diketopyrrolopyrrole pigment.

(Manufacturing method of diketopyrrolopyrrole pigment)

The brominated diketopyrrolopyrrole pigment of formula (1) can be manufactured by the method similar to the method in 1st embodiment.

Specific hetero diketopyrrolopyrrole pigment B of formula (B-2) is described, for example, in Synth. Synthesis can be performed using the methods described in Commun., 1988, 18, 1213 and Tetrahedron, 58 (2002) 5547-5565. The manufacturing method of specific hetero diketopyrrolopyrrole pigment B is not limited to this method.

In addition, the brominated diketopyrrolopyrrole pigment of formula (1) and the specific hetero diketopyrrolopyrrole pigment B of formula (B-2) may be prepared simultaneously as a fine pigment composition. This can be achieved by using a method of using at least two structurally different benzonitrile compounds in the succinic acid diester synthesis method (hereinafter, referred to as "succinic acid diester co-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 benzonitrile compounds represented by the following formula (B-3). The diketopyrrolopyrrole pigment composition of the second embodiment can be produced.

[Formula 37]

[In formula (B-3),

However, A and B do not become 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).

Although the specific example of the benzonitrile compound of said Formula (B-3) which can be used for a 2nd embodiment is given to the following, it is not limited to these.

(38)

Although the pigment composition may mix the brominated diketopyrrolopyrrole pigment and the thing which manufactured specific hetero diketopyrrolopyrrole pigment B separately, it is preferable to manufacture a pigment composition simultaneously by the succinic acid diester co-synthesis method from the ease of manufacture. . In the case of using separately prepared ones, the two kinds of pigments may be simply mixed before dispersing, or may be ground mixed through a salt milling treatment.

When producing the pigment composition of the brominated diketopyrrolopyrrole pigment of formula (1) and the specific hetero diketopyrrolopyrrole pigment B of formula (B-2) by the succinic acid diester co-synthesis method, with respect to 1 mol of succinic acid diesters, 2 mol of a mixture of 4-bromobenzonitrile and the benzonitrile compound of formula (B-3) is reacted. At this time, the 4-bromobenzonitrile and the formula (B-3) of the formula (1) and formula (B-2) in the resulting diketopyrrolopyrrole pigment composition is 97: 3 to 85:15 It is preferable to adjust the mixing ratio (molar ratio) of the benzonitrile compound. Since the reactivity varies depending on the kind of benzonitrile compound of formula (B-3), the mixing ratio (molar ratio) of 4-bromobenzonitrile and formula (B-3) changes. In order to make the mass ratio of a diketopyrrolopyrrole pigment composition into a desired range, the mixing ratio (molar ratio) of 4-bromobenzonitrile and a formula (B-3) becomes about 80: 20-98: 2. In the succinic acid diester co-synthesis method, a diketopyrrolopyrrole pigment (that is, a diketopyrrolopyrrole pigment containing no bromine atom) in which the benzonitrile compound of formula (B-3) is reacted with 2 mol of 1 mole of succinic acid diester. Is produced, but there is little effect since it is extremely small.

In the succinic acid diester co-synthesis method, the reaction ratio of the succinic acid diester and the benzonitrile compound is based on 2 moles of the benzonitrile compound per 1 mole of the succinic acid diester, but the amount of the succinic acid diester is 25 moles with respect to the benzonitrile compound. Overuse to about% is effective for improving a yield.

In the pigment composition prepared by the diester succinic acid synthesis method, the mass ratio of the brominated diketopyrrolopyrrole pigment and the specific hetero diketopyrrolopyrrole pigment B can be analyzed in the same manner as in the method for analyzing the mass ratio in the first embodiment. have.

(Pigment derivative)

A pigment derivative can be used for the pigment composition of a 2nd embodiment for the purpose of suppressing pigment crystal growth and improving pigment dispersibility. As an example of a pigment derivative, the pigment derivative similar to the pigment derivative of 1st Embodiment is mentioned. The preferred amount of dye derivative is also the same as in the first embodiment.

(Average primary particle size of pigment)

It is preferable that the diketopyrrolopyrrole pigment composition of the second embodiment has a very fine primary particle diameter, a narrow distribution width, and a sharp particle size distribution. It is preferable that the average primary particle diameter (number average particle diameter) calculated | required by the TEM (transmission electron microscope) of the diketopyrrolopyrrole pigment composition of 2nd Embodiment is a range of 5-70 nm. When it becomes smaller than 5 nm, dispersion in the organic solvent may become difficult. Moreover, when larger than 70 nm, sufficient contrast ratio may not be obtained. For this reason, the more preferable range is the range of 10-40 nm. In the step of preparing the diketopyrrolopyrrole pigment composition by the above-described synthesis method, if the average primary particle size is in the above range, may be used as it is, otherwise, the fineness and sizing of the pigment by salt milling or the like It is preferable.

(Fineness of pigment)

It is preferable to refine | miniaturize and use the pigment containing the diketopyrrolopyrrole pigment composition of 2nd Embodiment, and the salt milling process is preferable as a refinement | miniaturization method. 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 color filters which is embodiment of this invention is demonstrated.

Third Embodiment

(Color composition for color filters)

The coloring composition for color filters of a 3rd embodiment contains the diketopyrrolopyrrole pigment composition of a 1st embodiment. The diketopyrrolopyrrole pigment composition of the first embodiment can be used as a coloring composition by using in combination with a binder resin and an organic solvent. Moreover, coloring agents other than the diketopyrrolopyrrole pigment composition of 1st Embodiment can also be used together. For example, it is also possible to use the diketopyrrolopyrrole pigment composition of the second embodiment.

(Other colorant)

The coloring composition of a 3rd embodiment can independently or two or more pigments or dyes other than the diketopyrrolopyrrole pigment composition of a 1st embodiment in the range which does not impair the effect, for preparation of chromaticity, etc. It can also be used in combination.

When using coloring agents other than a diketopyrrolopyrrole pigment composition together, it is a thing of 30 mass%-100 mass% of the diketopyrrolopyrrole pigment composition of 1st Embodiment in a coloring agent whole quantity (100 mass%). desirable. More preferably, it is the range of 50 mass%-100 mass%. When the diketopyrrolopyrrole pigment composition of the first embodiment is less than 30% by mass, the excellent effect of brightness may not be sufficiently exhibited.

(Binder resin)

As binder resin contained in a coloring composition, a conventionally well-known thermoplastic resin and thermosetting resin are mentioned. Moreover, as binder resin, it is also possible to use binder resin (CB) containing alkali-soluble photosensitive resin (C-B1) in 5th Embodiment, and the structural unit (D-b1) in 6th Embodiment. It is also possible to use binder resin (DB) containing resin (D-B1) having (D-b3).

As the thermoplastic resin, for example, acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane-based resin, Polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, cellulose, polyethylene (HDPE, LDPE), polybutadiene, polyimide resin, etc. are mentioned.

When using as a coloring composition for color filters, it is preferable that spectral transmittance | permeability is 80% or more, More preferably, it is 95% or more resin in 400-700 nm total wavelength area | regions which are visible light regions. In addition, when using in the form of alkali developing type colored resist, it is preferable to use alkali-soluble vinyl resin which copolymerized the acidic group containing ethylenically unsaturated monomer. In addition, in order to further improve photosensitivity, an energy ray curable resin having an ethylenically unsaturated active double bond may be used.

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

As an energy-beam curable resin which has an ethylenically unsaturated active double bond, (meth) acrylic compound and cinnamic acid which have reactive substituents, such as an isocyanate group, an aldehyde group, and an epoxy group, are made to react with the polymer which has reactive substituents, such as a hydroxyl group, a carboxyl group, and an amino group, Resin which introduce | transduced photocrosslinkable groups, such as a (meth) acryloyl group and a styryl group, into the said polymer is used. Furthermore, the polymer containing acid anhydrides, such as a styrene-maleic anhydride copolymer and an alpha-olefin-maleic anhydride copolymer, is half-esterified by the (meth) acryl compound which has a hydroxyl group, such as hydroxyalkyl (meth) acrylate. It is also used.

As a thermoplastic resin, what has both alkali-soluble ability and energy-beam hardening performance is also suitable as the photosensitive coloring composition for color filters.

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

Or cyclohexyl maleimide, phenyl maleimide, methyl maleimide, ethyl maleimide, 1,2-bismaleimide ethane, 1,6-bismaleimide hexane, 3-maleimide propionic acid, 6,7-methylenedioxy -4-methyl-3-maleimidecoumarin, 4,4'-bismaleimidediphenylmethane, bis (3-ethyl-5-methyl-4-maleimidephenyl) methane, N, N'-1,3- Phenylenedimaleimide, N, N'-1,4-phenylenedimaleimide, N- (1-pyrenyl) maleimide, N- (2,4,6-trichlorophenyl) maleimide, N- (4 -Aminophenyl) maleimide, N- (4-nitrophenyl) maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidebenzoate , N-succinimidyl-3-maleimide propionate, N-succinimidyl-4-maleimidebutyrate, N-succinimidyl-6-maleimidehexanoate, N- [4- (2-benzo N-substituted males such as imidazolyl) phenyl] maleimide and 9-maleimideacridine Imides can be mentioned.

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

In order for the mass average molecular weight (Mw) of binder resin to disperse | distribute a coloring agent preferably, the range of 5,000-80,000 is preferable, More preferably, it is the range of 7,000-50,000. Moreover, the range of 2,500-40,000 is preferable, and, as for number average molecular weight (Mn), it is preferable that the value of Mw / Mn is 10 or less.

Here, the mass average molecular weight (Mw) and the number average molecular weight (Mn) are the gel permeation chromatography "HLC-8120GPC" manufactured by Tosoh Corporation, in which four separation columns are connected in series, and as a filler, Tosoh Corporation in this order. It is polystyrene conversion molecular weight measured using tetrahydrofuran as a mobile phase using "TSK-GEL SUPER H5000", "H4000", "H3000", and "H2000".

In the case of using the binder resin as the color composition for color filters, it is necessary to consider the balance between the carboxyl group acting as the pigment sorbent and the alkali soluble group during development, the aliphatic group serving as the affinity group for the pigment carrier and the solvent, and the aromatic group. It is preferable. It is preferable to use resin of acid value 20-300 mgKOH / g from a pigment dispersibility, developability, and also a viewpoint of durability. If the acid value is less than 20 mgKOH / g, the solubility in a developing solution is low, and it may be difficult to form a fine pattern. When it exceeds 300 mgKOH / g, a fine pattern may not remain at the time of image development.

Binder resin can be used in the quantity of 20-500 mass parts with respect to 100 mass parts of coloring agents. When less than 20 mass parts, film-forming property and various tolerance may become inadequate, and when more than 500 mass parts, pigment density | concentration is low and color characteristics may not be expressed.

(Organic solvent)

The coloring composition contains an organic solvent in order to make it easy to disperse | distribute a coloring agent in a coloring agent carrier, and to apply | coat so that a dry film thickness may be set to 0.2-5 micrometers on board | substrates, such as a glass substrate, and to form a filter segment. The organic solvent is selected in consideration of the solubility of each component of the coloring composition and further safety in addition to having good applicability of the coloring composition.

It is preferable to use the organic solvent in the quantity of 500-4000 mass parts with respect to 100 mass parts of coloring agents from the point which can adjust the coloring composition to appropriate viscosity and can form the filter segment of the target uniform film thickness.

(Production method of coloring composition)

The coloring composition comprises a kneader, a two roll mill, a three roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, and an annular bead mill in the colorant carrier comprising the diketopyrrolopyrrole pigment composition comprising the binder resin and the organic solvent. It can be produced by finely dispersing using a variety of dispersing means such as, or attritor. In addition, the coloring composition may disperse | distribute a diketopyrrolopyrrole pigment composition, another coloring agent, etc. simultaneously to a coloring agent carrier, and may mix separately what disperse | distributed to a coloring material carrier.

(Dispersion aid)

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

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

(Optional component)

The coloring composition may further contain, for example, the following components in addition to the dispersion aid as an optional component. The specific example of an arbitrary component is as mentioned later.

(Photopolymerizable monomer and / or photopolymerization initiator)

A coloring composition can add a photopolymerizable monomer and / or a photoinitiator further, and can be used as a photosensitive coloring composition.

Although the photopolymerizable monomer used for the photosensitive coloring composition contains the monomer or oligomer which hardens | cures by an ultraviolet-ray, a heat, etc. and produces a transparent resin, these can be used individually or in mixture of 2 or more types.

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

In the photosensitive coloring composition, when the composition is cured by ultraviolet irradiation and a filter segment is formed by the photolithography method, a photopolymerization initiator can be added to prepare a solvent developing type or an alkali developing type colored resist material. .

It is preferable that it is 2-200 mass parts with respect to 100 mass parts of coloring agents in the photosensitive coloring composition, and, as for a photoinitiator, it is more preferable that it is 3-150 mass parts from a viewpoint of photocurability and developability.

(Sensitizer)

A photosensitive coloring composition can be made to contain a sensitizer.

It is preferable that it is 3-60 mass parts with respect to 100 mass parts of photoinitiators contained in the photosensitive coloring composition, and, as for the compounding quantity at the time of using a sensitizer, it is more preferable that it is 5-50 mass parts from a viewpoint of photocurability and developability.

(Polyfunctional thiol)

The photosensitive coloring composition may contain a polyfunctional thiol which acts as a chain transfer agent. It is preferable that a polyfunctional thiol is a compound which has 2 or more of thiol groups.

The content of the polyfunctional thiol is preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass, based on the mass of the total solids of the photosensitive coloring composition (100% by mass). When content of polyfunctional thiol is less than 0.1 mass%, the effect of adding polyfunctional thiol may not fully be acquired, and when it exceeds 30 mass%, a sensitivity may be too high and the resolution may fall rather.

(Antioxidant)

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

When content of antioxidant is 0.5-5.0 mass% on the basis of 100 mass% of solid content mass of a coloring composition, since brightness and a sensitivity are favorable, it is more preferable.

(Amine compound)

An coloring compound can be made to contain the amine compound which has a function which reduces the dissolved oxygen.

(Leveling agent)

It is preferable to add a leveling agent to the coloring composition in order to improve the leveling property of the composition on the transparent substrate. It is preferable to normally use 0.003-0.5 mass% of content of a leveling agent on the basis of 100 mass% of the total mass of a coloring composition.

(Curing agent, curing accelerator)

The coloring composition may contain the hardening | curing agent, a hardening accelerator, etc. as needed in order to assist hardening of a thermosetting resin. As content of the said hardening accelerator, 0.01-15 mass parts is preferable with respect to 100 mass parts of thermosetting resins.

(Other additives)

The coloring composition may contain a storage stabilizer in order to stabilize the viscosity over time. Moreover, in order to improve adhesiveness with a transparent substrate, adhesive improving agents, such as a silane coupling agent, can also be contained.

A storage stabilizer can be used in the quantity of 0.1-10 mass% with respect to the whole amount of a coloring agent as a reference | standard (100 mass%).

The adhesion improving agent 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 coloring agent in the coloring composition (100% by mass).

Furthermore, in addition to the above arbitrary components, it is also possible to contain any of the arbitrary components mentioned later.

(Removal of coarse particles)

The coloring composition may contain coarse particles of 5 μm or more, preferably 1 μm or more of coarse particles, more preferably 0.5 μm or more of coarse particles and mixed dust through means such as centrifugation, sintering or filtration with a membrane filter. It is preferable to perform the removal. Thus, it is preferable that a coloring composition does not contain particle | grains 0.5 micrometer or more substantially. More preferably, it is 0.3 micrometer or less.

Fourth Embodiment

(Color composition for color filters)

The coloring composition for color filters of 4th Embodiment contains the diketopyrrolopyrrole pigment composition of 2nd Embodiment. The diketopyrrolopyrrole 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. Moreover, coloring agents other than the diketopyrrolopyrrole pigment composition of 2nd Embodiment can also be used together. For example, it is also possible to use the diketopyrrolopyrrole pigment composition of the first embodiment.

(Other colorant)

A coloring composition can also use together single or 2 types or more of pigments or dyes other than the diketopyrrolopyrrole pigment composition of 2nd Embodiment in the range which does not inhibit the effect, for preparation of chromaticity, etc.

When using a coloring agent other than a diketopyrrolopyrrole pigment composition together, it is a thing of 40 mass%-100 mass% in the diketopyrrolopyrrole pigment composition of 2nd Embodiment in a coloring agent whole quantity (100 mass%). desirable. More preferably, it is the range of 60 mass%-100 mass%. When the diketopyrrolopyrrole pigment composition of the second embodiment is 40% by mass or less, the excellent effects of brightness and contrast ratio may not be sufficiently exhibited.

(Binder resin)

As binder resin contained in a coloring composition, a conventionally well-known thermoplastic resin and thermosetting resin are mentioned. As an example of binder resin, the binder resin similar to the binder resin in 3rd Embodiment is mentioned. The preferred amount of binder resin is also the same as in the third embodiment.

(Organic solvent)

The coloring composition contains an organic solvent in order to make it easy to disperse | distribute a coloring agent in a coloring agent carrier, and to apply | coat so that a dry film thickness may be set to 0.2-5 micrometers on board | substrates, such as a glass substrate, and to form a filter segment. The organic solvent can be selected similarly to the selection method in the third embodiment. The preferred amount of organic solvent is also the same as in the third embodiment.

(Production method of coloring composition)

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

(Optional component)

In the coloring composition of 4th Embodiment, arbitrary components, such as a dispersing aid, a photopolymerizable monomer, and / or a photoinitiator, a sensitizer, a polyfunctional thiol, antioxidant, an amine compound, a leveling agent, a hardening | curing agent, a hardening accelerator, another additive, etc. It can be contained. As a specific example of these arbitrary components, it is the same as that of 3rd embodiment. In addition, preferable examples, preferable usage amounts, etc. are the same as that of 3rd embodiment.

(Removal of coarse particles)

It is preferable that the coloring composition of 4th Embodiment removes coarse particle similarly to the coloring composition of 3rd Embodiment.

[Fifth Embodiment]

(Color composition for color filters)

The coloring composition for color filters of 5th Embodiment contains the pigment (A), binder resin (CB), and a solvent, and the pigment (A) contains the pigment (A1) shown by Formula (1), , Binder resin (CB) contains alkali-soluble photosensitive resin (C-B1). The coloring composition for color filters of 5th Embodiment can be used as a photosensitive coloring composition.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching, the present inventors substituted brominated diketopyrrolopyrrole pigment (formula (1)) and alkali-soluble photosensitive resin instead of the CI pigment red 254 (chlorinated diketopyrrolopyrrole pigment) used conventionally. By using a coloring composition, it was discovered that the color filter which has a high definition, high contrast ratio, and the high definition filter segment in which crystal precipitation was suppressed by the heating process is obtained.

According to the fifth embodiment, the crystallization of the diketopyrrolopyrrole pigments does not occur even in the high brightness and high contrast ratio, but also in the heating process, and the performance necessary for forming good filter segments such as sensitivity and linearity is achieved. The coloring composition for color filters excellent in the balance can be provided.

(Pigment (A))

Pigment (A) contains the pigment (A1) shown by Formula (1).

Pigment (A1)

[Chemical Formula 39]

The brominated diketopyrrolopyrrole pigment which is the pigment (A1) shown by Formula (1) can be manufactured by the method similar to the method in 1st Embodiment. By using the pigment (A1) shown in Formula (1), it can be set as the red coloring composition of high brightness and high contrast ratio compared with the former.

In addition, as the pigment (A), it is also possible to use the diketopyrrolopyrrole pigment composition in the first embodiment, it is also possible to use the diketopyrrolopyrrole pigment composition in the second embodiment.

`` Other pigments ''

The coloring composition may use together pigments other than pigment (A1), and, as such a pigment, organic or inorganic pigment can be used individually or in combination of 2 or more types. Among the pigments, pigments having high color development and high heat resistance are preferable, and organic pigments are usually used.

As an organic pigment which can be used, For example, diketopyrrolopyrrole pigments other than pigment (A1); Azo pigments, such as azo, disazo, and polyazo; Phthalocyanine-based pigments such as copper phthalocyanine, halogenated copper phthalocyanine and metal-free phthalocyanine; Anthraquinone pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavantron, anthrone, indanthrone, pyrantrone, and viorantrone; Quinacridone pigments; Dioxazine pigments; Perinone pigments; Perylene pigments; Thioindigo pigments; Isoindolin-based pigments; Isoindolinone pigments; Quinophthalone pigments; Threne pigments; Metal complex pigments; and the like.

Among these pigments, diketopyrrolopyrrole pigments other than the pigment (A1), azo pigments, anthraquinone pigments, perylene pigments, quinacridone pigments, benzimidazolone pigments and quinoline pigments selected from the group consisting of It is preferable to include at least 1 type or more which becomes. Like pigment (A1), these are easy to adjust color by adjustment of the compounding ratio which is a red pigment, and since these are excellent in light resistance and heat resistance, they are preferable.

In addition, the inorganic pigments include barium sulfate, zinc oxide, lead sulfate, yellow lead, zinc sulfur, bengal (red iron oxide (III)), cadmium red, ultramarine blue, royal blue, and oxidized. And metal oxide powders such as chromium green, cobalt green, umber, titanium black, synthetic iron black, titanium oxide and iron tetraoxide, metal sulfide powder and metal powder. Inorganic pigments are used in combination with organic pigments in order to ensure good applicability, sensitivity, developability and the like while balancing saturation and lightness.

When using together with a red pigment and a yellow pigment, content of the pigment (A1) represented by Formula (1) is 40-100 weight% in 100 weight% of total of pigment (A), Preferably it is 50-100 weight% More preferably, it is 60-100 weight%. The range of this content is preferable at the point which can fully express the color characteristic of the pigment (A1) represented by Formula (1).

Content of a preferable pigment (A) component is 10 weight% or more from a viewpoint of obtaining sufficient color reproducibility among 100 weight% of all the non volatile components of a coloring composition, More preferably, it is 15 weight% or more, Most preferably, 20 By weight or more. Moreover, since the stability of a coloring composition improves, content of a preferable pigment (A) component is 90 weight% or less, More preferably, it is 80 weight% or less, Most preferably, it is 70 weight% or less.

The photosensitive coloring composition may further contain a dye within the range of not lowering the heat resistance for coloring.

<< pigment refinement >>

It is preferable to refine | miniaturize and use pigment (A1) and other pigments.

It is preferable that the primary particle diameter of the refined pigment | dye is 20 nm or more from the point which the dispersion | distribution to a coloring agent support is favorable. Moreover, it is preferable that it is 100 nm or less from the point which can form the filter segment with high contrast ratio. Especially preferable range is the range of 25-85 nm.

In addition, the primary particle diameter of a pigment can be performed by the method of directly measuring the magnitude | size of a primary particle from the electron microscope photograph by a TEM (transmission electron microscope) of a pigment. Specifically, the short axis diameter and long axis diameter of the primary particles of each pigment are measured, and the average is made the particle diameter of the pigment particle. Next, with respect to 100 or more pigment particles, the average volume of each particle is approximated to the cube of the particle size obtained, and the length of one side of the cube having the average volume is made the average primary particle size.

Moreover, it is preferable that the specific surface area by the BET method of these refinement | miniaturization pigments is 60m <^2> / g-130m <^2> / g. When the specific surface area of the pigment (A) is smaller than the lower limit, the luminance and contrast ratio of the color filter may be lowered. When the specific surface area is larger than the upper limit, pigment dispersion may be difficult to maintain stability as the coloring composition and to secure fluidity. As a result, there exists a tendency for the characteristic of the brightness | luminance and contrast ratio of a color filter to fall.

As a means of controlling the specific surface area of the pigment, a method of mechanically pulverizing the pigment to control the specific surface area (called a grinding method), or a solution dissolved in a good solvent is added to a poor solvent to obtain a desired ratio. The method of depositing the pigment of surface area (called a precipitation method), and the method of manufacturing the pigment of a desired specific surface area at the time of synthesis | combination (called a synthetic precipitation method), etc. are mentioned. According to the synthesis | combining method, chemical property, etc. of the pigment to be used, an appropriate method can be selected and performed about each pigment. As a control method of the specific surface area of the pigment contained in a coloring composition, one of the said methods can also be used.

It is preferable to refine | miniaturize the pigment used for 5th Embodiment through the salt milling process also in the grinding | polishing method, and, by using such a pigment, a filter segment with a higher contrast ratio can be formed. Salt milling process can be performed similarly to the method in the said diketopyrrolopyrrole pigment composition.

(Binder Resin (C-B))

Binder resin (CB) disperse | distributes pigment (A) and contains alkali-soluble photosensitive resin (C-B1).

<< alkali-soluble photosensitive resin (C-B1) >>

As alkali-soluble photosensitive resin (C-B1), resin which introduce | transduced ethylenically unsaturated double bond by the method of (Ci) and (C-ii) shown below, for example is mentioned.

As a method (Ci), the carboxyl group of the unsaturated monobasic acid which has an ethylenically unsaturated double bond is added to the side chain epoxy group of the copolymer obtained by copolymerizing the ethylenically unsaturated monomer which has an epoxy group, and another 1 or more types of monomers, for example. There is a method of reacting the resulting hydroxyl group with the polybasic acid anhydride, introducing an ethylenically unsaturated double bond to give a function of the photosensitive resin, and introducing a carboxyl group having an alkali-soluble function.

As an ethylenically unsaturated monomer which has an epoxy group, glycidyl (meth) acrylate, methylglycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, 3, 4- epoxy, for example Butyl (meth) acrylate and 3, 4- epoxycyclohexyl (meth) acrylate are mentioned, These may be used independently or may use two or more types together. From the viewpoint of reactivity with unsaturated monobasic acid of the next step, glycidyl (meth) acrylate is preferred.

As unsaturated monobasic acid, (meth) acrylic acid, crotonic acid, o-, m-, p-vinyl benzoic acid, the (alpha) position haloalkyl, alkoxyl, halogen, nitro, cyano of (meth) acrylic acid Monocarboxylic acids, such as a substituent, etc. are mentioned, These may be used independently or may use two or more types together.

Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride and maleic anhydride. These may be used alone or in combination of two or more kinds. If necessary, such as increasing the number of carboxyl groups, hydrolyzing the remaining anhydride groups using tricarboxylic anhydrides such as trimellitic anhydride, tetracarboxylic dianhydrides such as pyromellitic dianhydride, etc. It is possible. In addition, when polybasic acid anhydride is used, tetrahydrophthalic anhydride or maleic anhydride having an ethylenically unsaturated double bond 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 the side chain carboxyl group of the copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group with at least one other monomer. There is a method of introducing an ethylenically unsaturated double bond and a carboxyl group.

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

As an ethylenically unsaturated monomer which has a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acryl And hydroxyalkyl (meth) acrylates such as acrylate, glycerol (meth) acrylate, or cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. It does not matter. Furthermore, polyether mono (meth) acrylate which addition-polymerized ethylene oxide, propylene oxide, and / or butylene oxide to the said hydroxyalkyl (meth) acrylate, (poly) (gamma) -valerolactone, (poly (poly) ester mono (meth) acrylate which added) (epsilon) -caprolactone and / or (poly) 12-hydroxystearic acid, etc. can also be used. 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferable from a viewpoint of coating film foreign material suppression.

Examples of the ethylenically unsaturated monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis [(meth) acryloyloxy] ethyl isocyanate, and the like, but are not limited thereto. You may use together 2 or more types.

As alkali-soluble photosensitive resin (C-B1), it contains carboxyl groups, such as unsaturated monocarboxylic acid, such as (meth) acrylic acid, crotonic acid, or (alpha)-chloroacrylic acid, or unsaturated dicarboxylic acid, such as maleic acid or fumaric acid, Moreover, resin obtained using the monomer which has an ethylenically unsaturated double bond is mentioned. As another ethylenically unsaturated monomer which is a precursor of alkali-soluble photosensitive resin (C-B1), methyl (meth) methacrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) Acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl acrylate, neopentyl (Meth) acrylate, t-pentyl (meth) acrylate, 1-methylbutyl (meth) acrylate, hexyl (meth) acrylate, hepta (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) acrylate, allyl (meth) Acrylate, or oleyl (meta) 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. Among these, methyl (meth) acryl methacrylate or ethyl (meth) acrylate is preferable from a viewpoint of pigment dispersibility.

The weight average molecular weight (Mw) of alkali-soluble photosensitive resin (C-B1) has a preferable range of 5,000-100,000, More preferably, it is the range of 5,000-80,000, More preferably, it is the range of 5,000-30,000. Moreover, the range of 5,000-50,000 is preferable, and, as for number average molecular weight (Mn), it is preferable that the value of Mw / Mn is 10 or less. When the weight average molecular weight (Mw) of alkali-soluble photosensitive resin (C-B1) exceeds 100,000, interaction between resin will become strong and the viscosity of the coloring composition for color filters will become high, and handling may become difficult. Moreover, when weight average molecular weight (Mw) is less than 5,000, adhesiveness with respect to board | substrates, such as developability and glass, may fall.

It is preferable that the acid value of alkali-soluble photosensitive resin (C-B1) is 20-300 KOH-mg / g from a viewpoint of the dispersibility, permeability, developability, and tolerance of a pigment. If the acid value is less than 20 KOH-mg / g, the solubility in a developing solution is low, and it may be difficult to form a fine pattern. When it exceeds 300 KOH-mg / g, a fine pattern may not remain.

As for content of alkali-soluble photosensitive resin (C-B1), 10-100 weight% is preferable in 100 weight% of total of binder resin (CB), 20-100 weight% is more preferable, More preferably, it is 40- 100% by weight. When content of alkali-soluble photosensitive resin (C-B1) in binder resin (CB) is 10 weight% or more, since the effect of the high brightness and a high contrast ratio of a coloring composition is easy to be acquired, it is preferable.

`` Other resins ''

Binder resin (CB) may also contain other resin other than alkali-soluble photosensitive resin (C-B1). The other resin is preferably a resin having a transmittance of 80% or more and more preferably 95% or more in the entire wavelength region of 400 to 700 nm which is the visible light region. For example, a thermoplastic resin, a thermosetting resin, etc. can be used individually or in mixture of 2 or more types can be used.

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, and polyester resin. , Acrylic resins, alkyd resins, polystyrenes, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene, polybutadiene, polyimide resins, and the like. Moreover, as a thermosetting resin, an epoxy resin, benzoguanamine resin, rosin modified maleic acid resin, rosin modified fumaric acid resin, melamine resin, urea resin, a phenol resin etc. are mentioned, for example.

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

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

Binder resin (CB) is 20-400 weight part with respect to 100 weight part of pigments (A) in a coloring composition, Preferably it can use in the quantity of 50-250 weight part.

(solvent)

A solvent is used in order to make it easy to form a filter segment by disperse | distributing a pigment (A) fully in binder resin (CB) and apply | coating a coloring composition to substrates, such as a glass substrate, so that a dry film thickness may be set to 0.2-5 micrometers. do. As a solvent, an organic solvent is preferable.

Use of content of a solvent in the quantity of 800-4000 weight part with respect to 100 weight part of pigments (A) adjusts a coloring composition to appropriate viscosity, and can form the filter segment of the uniform film thickness made into the objective. Preferred at

(Production method of photosensitive coloring composition)

The photosensitive coloring composition is a pigment (A) in a dye carrier and a solvent such as binder resin (CB), preferably with a pigment dispersant, various dispersions such as three roll mill, two roll mill, sand mill, kneader, attritor, etc. It is finely dispersed using means to produce a pigment dispersion, which is a photopolymerization initiator (CD), a binder resin (CB), a photopolymerizable compound, optionally a sensitizer (CE), a polyfunctional thiol, and an ultraviolet ray. An absorbent, a polymerization inhibitor, a storage stabilizer, and other components can be prepared by mixing and stirring. Moreover, the coloring composition containing 2 or more types of pigments mixes what disperse | distributed finely each pigment dispersion in a pigment carrier and / or a solvent separately, and also mixes and stirs a photoinitiator (CD), a photopolymerizable compound, etc. It can be prepared by.

Pigment Dispersant (C-C)

When disperse | distributing a pigment (A) in binder resin (CB) and / or a solvent, pigment dispersing agents (CC), such as a resin type pigment dispersing agent, a pigment derivative, and surfactant, can be contained suitably. Since the pigment dispersant (CC) is excellent in dispersing the pigment and has a great effect of preventing the reaggregation of the pigment after dispersion, the pigment dispersant (CC) is used to disperse the pigment in the binder resin (CB) and / or the solvent. When the coloring composition which consists of is used, the color filter excellent in transparency is obtained.

It is preferable that especially a coloring composition contains an acidic resin pigment dispersant from a viewpoint of stability of a coloring composition. By using together an acidic resin pigment dispersant and a basic pigment derivative, it is preferable because not only the fluidity | liquidity and stability of a coloring composition but the filter segment excellent in high brightness and high contrast ratio is obtained.

The pigment dispersant (CC) can be used in an amount of 0.1 to 40 parts by weight, preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the pigment (A).

<< resin type pigment dispersant, surfactant >>

Examples of the resinous pigment dispersant and the surfactant are described later.

<< pigment derivative >>

As a pigment derivative, the compound which introduced the phthalimide methyl group which may have a basic substituent, an acidic substituent, or a substituent to organic pigment, anthraquinone, acridon, or triazine is mentioned. The structure is a compound represented by following formula (50), for example, and a pigment derivative is especially preferable.

P-Lm equation (50)

[In formula (50),

P: organic pigment residue, anthraquinone residue, acridon residue or triazine residue

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

m is an integer of 1 to 4]

Examples of the dye derivatives include Japanese Patent Laid-Open No. S63-305173, Japanese Patent Laid-Open No. S57-15620, Japanese Patent Laid-Open No. S59-40172, Japanese Patent Laid-Open No. S63-17102, or Japanese Patent Publication H5- What is described in 9469 etc. can be used, These can be used individually or in mixture of 2 or more types.

In formula (50), the following can be mentioned as an organic pigment which comprises the organic pigment residue of P.

As an organic pigment which comprises the organic pigment residue of P, it is a diketopyrrolopyrrole pigment, for example; Azo pigments, such as azo, disazo, and polyazo; Phthalocyanine-based pigments such as copper phthalocyanine, halogenated copper phthalocyanine, zinc phthalocyanine, halogenated zinc phthalocyanine and metal phthalocyanine; Anthraquinone pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavantron, ananthrone, indanthrone, pyrantrone, and bioanthrone; Quinacridone pigments; Dioxazine pigments; Perinone pigments; Perylene pigments; Thioindigo pigments; Isoindolin-based pigments; Isoindolinone pigments; Threne pigments; Quinophthalone pigments; Dioxazine pigments; Metal complex pigments; and the like.

Especially, the pigment derivative which has a basic substituent whose L in Formula (50) is a basic substituent can be used preferably. Since the pigment derivative which has a basic substituent is included, even if it is a pigment which is difficult to disperse without the pigment derivative which has a basic substituent, since it can be set as the pigment composition excellent in dispersibility, fluidity | liquidity, and storage stability, it is preferable. The synergistic effect of an acidic resin type dispersant and a pigment derivative having a basic substituent can effectively disperse the pigment, thereby making it 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)

In formulas (51) to (53),

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, a C1-C36 alkyl group which may have a substituent, a C2-C36 alkenyl group 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 are added together; Is a heterocyclic ring which may have a substituent containing nitrogen, oxygen, or sulfur atom,

R ⁵² , R ⁵³ , R ⁵⁴ and R ⁵⁵ may each independently have 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, or a substituent It is 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, or an alkenyl group having 2 to 20 carbon atoms which may have a substituent,

R ⁵⁷ is a substituent represented by Formula (51) or a substituent represented by Formula (52),

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

As an amine component used in order to form the substituent represented by Formula (51)-(53), the same amine component as the amine component in 1st Embodiment is mentioned.

The pigment derivative which has a basic substituent can be synthesize | combined by various synthetic routes. For example, after introducing a substituent represented by formulas (54) to (57) into an organic pigment, the amine component, which forms a substituent represented by formulas (51) to (53) by reacting with the substituent, for example For example, N, N-dimethylaminopropylamine, N-methylpiperazine, diethylamine, or 4- [4-hydroxy-6- [3- (dibutylamino) propylamino] -1,3,5- It is obtained by making triazin-2-ylamino] aniline etc. react.

Formula (54): -SO ₂ Cl

Formula (55): -COCl

Formula (56): -CH ₂ NHCOCH ₂ Cl

Formula (57): -CH ₂ Cl

At the time of reaction of the substituent of Formula (54)-(56) with the said amine component, one part of the substituent of Formula (54)-(57) may be hydrolyzed and the thing by which chlorine was substituted by the hydroxyl group may be mixed. In this case, although Formula (54) and Formula (55) become a sulfonic acid group and a carboxylic acid group, respectively, all of them may be in the state of a free acid, and may also be a monovalent trivalent metal or a salt with the said monoamine. have.

When the organic pigment is an azo pigment, the azo pigment derivative is prepared by introducing a substituent represented by the formulas (51) to (53) into the diazo component or the coupling component in advance and then performing a coupling reaction. It can also manufacture.

Triazine derivatives having a basic substituent can be synthesized by various synthetic routes. For example, the amine component which uses cyanuric chloride as a starting material and forms the substituent represented by Formula (51)-(53) in at least 1 chlorine of cyanuric chloride, for example, N, N-dimethylamino It is obtained by reacting propylamine or N-methylpiperazine or the like followed by reacting the remaining chlorine of cyanuric chloride with various amines or alcohols.

(Optional component)

The coloring composition of 5th Embodiment may contain the following components further as an optional component other than a pigment dispersant, for example. The specific example of an arbitrary component is as mentioned later.

(Photoinitiator (C-D))

In order to harden this composition by ultraviolet irradiation and to form a filter segment by the photolithographic method, a photoinitiator (C-D) can be added to the photosensitive coloring composition and it can be prepared in the form of alkali developing photosensitive coloring composition.

It is preferable that it is 5-200 weight part with respect to 100 weight part of pigments (A), and, as for content of a photoinitiator (CD), it is more preferable that it is 10-150 weight part from a viewpoint of photocurability and developability.

(Sensitizer)

A photosensitive coloring composition can be made to contain a sensitizer.

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

(Photopolymerizable compound)

The photosensitive coloring composition may contain a photopolymerizable compound. The photopolymerizable compound includes a monomer or oligomer that is cured by ultraviolet rays, heat, or the like to generate a resin.

It is preferable that it is 10-300 weight part with respect to 100 weight part of pigments (A), and, as for content of a photopolymerizable monomer (CC), it is more preferable that it is 10-200 weight part from a 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. By using the polyfunctional thiol together with the above-described photopolymerization initiator (CD), in the radical polymerization process after light irradiation, it acts as a chain transfer agent and generates thiyl radicals which are difficult to be inhibited by oxygen polymerization. The obtained photosensitive coloring composition becomes high sensitivity. In particular, the polyfunctional aliphatic thiol which SH group couple | bonded with aliphatic groups, such as methylene and ethylene group, is preferable.

As for content of a polyfunctional thiol, 0.05-100 weight part is preferable with respect to 100 weight part of pigments (A), More preferably, it is 1.0-50.0 weight part. By using 0.05 weight part or more of polyfunctional thiols, better image development tolerance can be acquired. In the case of using a monofunctional thiol having one thiol (SH) group, such improvement in development resistance is not obtained.

(Ultraviolet absorber)

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

Content of a ultraviolet absorber is 0.01-20 weight part with respect to 100 weight part of pigments (A), Preferably it can use in the quantity of 0.05-10 weight part. By using 0.01 weight part or more of ultraviolet absorbers, a 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 a pattern can be controlled.

Content of a polymerization inhibitor is 0.01-20 weight part with respect to 100 weight part of pigments (A), Preferably it can use in the quantity of 0.05-10 weight part. By using 0.01 weight part or more of polymerization inhibitors, a better resolution can be obtained.

(Storage stabilizer)

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

Content of a storage stabilizer is 0.01-20 weight part with respect to 100 weight part of pigments (A), Preferably it can use in the quantity of 0.05-10 weight part. By using 0.01 weight part or more of a storage stabilizer, time-lapse stability of a coloring composition improves.

(Other additives)

In order to improve adhesiveness with a transparent substrate, the photosensitive coloring composition can be made to contain adhesion promoters, such as a silane coupling agent, or an amine compound which has a function which reduces the dissolved oxygen.

An adhesion improving agent can be used in 0.01-10 weight part with respect to 100 weight part of pigments (A), Preferably it is the quantity of 0.05-5 weight part.

(Removal of coarse particles)

It is preferable that the coloring composition of 5th Embodiment removes coarse particle similarly to the coloring composition of 3rd Embodiment.

[Sixth Embodiment]

In the coloring composition for color filters of a 6th embodiment, in the coloring composition for color filters containing a pigment (A), binder resin (DB), and a solvent, the pigment (A) is shown by Formula (1). A pigment (A1) is included and binder resin (DB) contains resin (D-B1) which has the following structural units (D-b1)-(D-b3). The coloring composition for color filters of 6th Embodiment can be used as a photosensitive coloring composition.

MEANS TO SOLVE THE PROBLEM As a result of earnest research, the present inventors used the coloring composition containing the brominated diketopyrrolopyrrole pigment and the binder resin which has a specific structure instead of the CI pigment red 254 (chlorinated diketopyrrolopyrrole pigment) used conventionally. By doing so, it was found that a color filter having a high definition, high contrast and high definition filter segment in which crystal precipitation was suppressed by the heating step was obtained.

According to the sixth embodiment, the crystallization of the diketopyrrolopyrrole pigments does not occur in the high brightness and high contrast ratio and also in the heating step, and when used as a photosensitive coloring composition, the sensitivity and linearity are good. The coloring composition for color filters which is excellent in the balance of the performance required when forming a filter segment can be provided.

(Pigment (A))

Pigment (A) is a pigment similar to pigment (A) in 5th Embodiment, and can be obtained by the method similar to the manufacturing method in 5th Embodiment.

By using in combination the pigment (A1) and resin (D-B1) shown by Formula (1), it can be set as the red coloring composition of high brightness and a high contrast ratio conventionally.

Similarly to the coloring composition of the fifth embodiment, the coloring composition of the sixth embodiment can also use other pigments together with the pigment (A1), and furthermore, the pigment (A1) and the other pigments can be used by miniaturization. desirable.

(Binder Resin (D-B))

<< resin (D-B1) >>

Binder resin (D-B) contained in the coloring composition for color filters is characterized by including resin (D-B1) which has the following structural units (D-b1)-(D-b3).

(D-b1) Structural unit having a carboxyl group: 2 to 60 wt%

(43)

(44)

[Chemical Formula 45]

(46)

Below, the structural unit D-b1, the structural unit D-b2, and the structural unit D-b3 are demonstrated in order. In this embodiment, the content weight% of each structural unit is the weight% of the precursor which brings each structural unit to resin (D-b1).

The structural unit (D-b1) has a carboxyl group and functions as an alkali-soluble site | part at the time of image development. Based on the weight of all the structural units of binder resin (D-B1), structural unit (D-b1) is 2-60 weight% from a viewpoint of developability and dispersion stability. If it is less than 2 weight%, the removal property of the unexposed part by alkaline developing solution will become inadequate, and dispersion stability will worsen. Moreover, when it exceeds 60 weight%, the dissolution rate with respect to alkaline developing solution will accelerate and it will melt | dissolve to an exposure part.

As a precursor of the structural unit (D-b1) which has a carboxyl group, Carboxyl groups, such as unsaturated monocarboxylic acid, such as (meth) acrylic acid, crotonic acid, or (alpha)-chloroacrylic acid, or unsaturated dicarboxylic acid, such as maleic acid or fumaric acid, are mentioned. The compound etc. which have ethylenically unsaturated double bond are mentioned, containing. Moreover, what half-esterified the anhydride of unsaturated dicarboxylic acid, such as maleic anhydride, with the (meth) acryl compound which has hydroxyl groups, such as hydroxyalkyl (meth) acrylate, can also be used. Among these, (meth) acrylic acid is more preferable from a viewpoint of polymerizability (easiness of control, such as molecular weight), and methacrylic acid is the most preferable especially. This can be used individually or in combination of 2 or more types.

Even if it is the precursor containing a carboxyl group in a raw material stage, when a carboxyl group turns into ester bond etc. in the process of forming binder resin (DB), it does not correspond to a structural unit (D-b1).

Structural unit (D-b2) has a cyclic structure by the aromatic ring group shown by Formula (D-2) or (D-3), and functions as an affinity site with respect to the pigment composition which consists of a pigment or a pigment, a dispersing agent, etc. . Based on the weight of all the structural units of binder resin (DB), structural unit (D-b2) is 20 to 80 weight% from a viewpoint of developability and the quality of a filter segment. If it is less than 20% by weight, there is a lack of affinity for a pigment or a pigment composition composed of a pigment and a dispersant, so that a high-quality color filter is not obtained or the resistance of the filter segment is deteriorated. If it exceeds, the dissolution rate with respect to alkaline developing solution will become slow, a developing time will be long and productivity of a color filter will deteriorate.

The bromine atom contained in the structure of the pigment (A1) shown in Formula (1) has a higher polarization rate than the chlorine atom. Accordingly, the structural unit (D-b2) containing an aromatic ring group can be expected that the π-electron system exhibits stronger interaction such as affinity than that of the chlorinated diketopyrrolopyrrole pigment (CI Pigment Red 254). have.

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(48)

As a precursor of a structural unit (D-b2), styrene, (alpha) -methylstyrene, divinylbenzene, indene, acetyl naphthene, benzyl acrylate, benzyl methacrylate, bisphenol A diglycidyl ether di (meth) acryl The monomer oligomers, such as the rate and the (meth) acrylic acid ester of methylolated melamine, or the ethylenically unsaturated monomer shown by Formula (D-6), etc. are mentioned.

(49)

[In formula (D-6), R <^1> is a hydrogen atom or a methyl group, R <^2> is a C2 or 3 alkylene group, R <^3> is a C1-C20 alkyl group which may have a benzene ring. , n is an integer of 1 to 15.]

As an ethylenically unsaturated monomer shown by Formula (D-6), it is, for example,

New Frontier CEA manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. [EO modified cresol acrylate, R ¹ : hydrogen atom, R ² : ethylene group, R ³ : methyl group, n = 1 or 2,], NP-2 [ n-nonylphenoxypolyethylene glycol acrylate, R ¹ : hydrogen atom, R ² : ethylene group, R ³ : n-nonyl group, n = 2], N-177E [n-nonylphenoxypolyethylene glycol acrylate, R ¹ : hydrogen atom, R ² : ethylene group, R ³ : n-nonyl group, n = 16-17], or PHE [phenoxyethylacrylate, R ¹ : hydrogen atom, R ² : ethylene group, R ³ : Hydrogen atom, n = 1],

Daicel Corporation claim, IRR169 [ethoxylated phenyl acrylate (EO 1mol), R ^1: a hydrogen atom, R ^2: an ethylene group, R ^3: a hydrogen atom, n = 1], or Ebecryl 110 [ethoxylated phenyl acrylate (EO 2 mol), R ¹ : hydrogen atom, R ² : ethylene group, R ³ : 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 Phenol EO-modified (n ≒ 4) acrylate, R ¹ : hydrogen atom, R ² : ethylene group, R ³ : hydrogen atom, n ≒ 4], M-110 [paracuylphenol EO-modified (n ≒ 1) acrylate , R ¹ : hydrogen atom, R ² : ethylene group, R ³ : paracumyl, n'1], M-111 [n-nonylphenol EO-modified (n'1) acrylate, R ¹ : hydrogen atom, R ² : Ethylene group, R ³ : n-nonyl group, n ≒ 1], M-113 [n-nonylphenol EO-modified (n ≒ 4) acrylate, R ¹ : hydrogen atom, R ² : ethylene group, R ³ : n-nonyl group, n'4] or M-117 [n-nonylphenol PO-modified (n'2.5) acrylate, R ¹ : hydrogen atom, R ² : propylene group, R ³ : n-nonyl group, n 2.5],

Kyoeisha Chemical Co. Light acrylate PO-A [phenoxyethyl acrylate, R ¹ : hydrogen atom, R ² : ethylene group, R ³ : hydrogen atom, n = 1], P-200A [phenoxy polyethylene Glycol acrylate, R ¹ : hydrogen atom, R ² : ethylene group, R ³ : hydrogen atom, n ≒ 2], NP-4EA [nonylphenol EO adduct acrylate, R ¹ : hydrogen atom, R ² : 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-nonyl group, n ' 8] or light ester PO [phenoxyethyl methacrylate, R ¹ : methyl group, R ² : propylene group, R ³ : hydrogen atom, n = 1],

NOM Corporation Blemmer ANE-300 [nonylphenoxypolyethylene glycol acrylate, R ¹ : hydrogen atom, R ² : ethylene group, R ³ : n-nonyl group, n '5], ANP-300 [nonylphenoxypolypropylene Glycol acrylate, R ¹ : hydrogen atom, R ² : propylene group, R ³ : n-nonyl group, n ≒ 5], 43ANEP-500 [nonylphenoxy-polyethyleneglycol-polypropyleneglycol-acrylate, R ¹ : Hydrogen atom, R ² : ethylene group and propylene group, R ³ : n-nonyl group, n ≒ 5 + 5], 70ANEP-550 [nonylphenoxy-polyethylene glycol-polypropylene glycol-acrylate, R ¹ : hydrogen atom , R ² : ethylene group and propylene group, R ³ : n-nonyl group, n ≒ 9 + 3], 75ANEP-600 [nonylphenoxy-polyethylene glycol-polypropylene glycol-acrylate, R ¹ : 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 Acrylate, R ¹ : methyl group, R ² : ethylene group, R ³ : hydrogen atom, n = 1], PAE-100 [phenoxypolyethylene glycol methacrylate, R ¹ : methyl group, R ² : 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 : hydrogen atom, n ' 6 + 6],

NK ESTER AMP-10G manufactured by Shin Nakamura Chemical Co., Ltd. (phenoxyethylene glycol acrylate (EO 1mol), R ¹ : hydrogen atom, R ² : ethylene group, R ³ : hydrogen atom, n = 1), 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 (EO 6mol) ), R ¹ : hydrogen atom, R ² : ethylene group, R ³ : hydrogen atom, n ≒ 6], PHE-1G [phenoxyethylene glycol methacrylate (EO 1mol), R ¹ : methyl group, R ² : 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) manufactured by Osaka Organic Chemical Industry Co., Ltd., or

SR-339A [2-phenoxyethylene glycol acrylate, R ¹ : hydrogen atom, R ² : ethylene group, R ³ : hydrogen atom, n = 1] manufactured by Nippon Kayaku Co., Ltd., or SR-504 (ethoxy Shioned nonylphenol acrylate, R <^1> : hydrogen atom, R <^2> : ethylene group, R < ³ : n-nonyl group] etc. are mentioned, It is not limited to these and can also use together two or more types.

In the ethylenically unsaturated monomer represented by Formula (D-6), although carbon number of the alkyl group of R <^3> is 1-20, More preferably, it is 1-10. The alkyl group includes not only linear alkyl groups but also branched alkyl groups and alkyl groups having a benzene ring as a substituent. When the alkyl group of R ³ has 1 to 10 carbon atoms, the alkyl group is impeded to inhibit the access between the resins and promotes adsorption / orientation to the pigment of the resin. The adsorption / orientation of the benzene ring pigments also tends to interfere. This tendency becomes remarkable as the carbon chain length of the alkyl group of R ³ becomes long, but when carbon number exceeds 20, the adsorption / orientation of a benzene ring will fall extremely. As an alkyl group which has a benzene ring represented by R <^3> , a benzyl group, 2-phenyl (iso) propyl group, etc. are mentioned. As one side chain benzene ring is increased, solvent affinity and pigment orientation are further improved, and not only dispersibility but also developability are improved.

In the ethylenically unsaturated monomer represented by Formula (D-6), n has an integer of 1-15. When n exceeds 15, since hydrophilicity increases and the effect of solvation becomes small, the viscosity of vinyl resin becomes high and the viscosity of the coloring composition using this also increases, and it may affect fluidity. From a viewpoint of solvation, 1-4 are especially preferable.

As a precursor of a structural unit (D-b2), styrene, (alpha) -methylstyrene, benzyl acrylate, benzyl methacrylate, or Formula (D-6) from a viewpoint of copolymerizability with another precursor, and a viewpoint of pigment dispersibility. The ethylenically unsaturated monomer represented by is preferable. By introducing a benzene ring into the side chain of the resin (D-B1), since the side chain benzene ring is oriented to the pigment, it promotes resin adsorption to the pigment and further suppresses aggregation of the pigment. In addition, benzyl acrylate and / or benzyl methacrylate are most preferable from the viewpoint of developability and dispersion stability.

Structural unit (D-b3) has a cyclic structure by the aliphatic ring group shown to the following formula (D-4) and formula (D-5), and it is affinity site | part with respect to the pigment composition which consists of a pigment or a pigment, a dispersing agent, etc. And it functions as a hydrophobic site with respect to alkaline developing solution. Based on the weight of all the structural units of resin (D-B1), structural unit (D-b3) is 2-60 weight% from a viewpoint of developability, the quality of a filter segment, and dispersion stability. If it is less than 2% by weight, there is a lack of affinity for a pigment or a pigment composition composed of a pigment and a dispersant, so that a high quality color filter is not obtained, or the storage stability of the color composition for color filters is deteriorated. Since the hydrophobicity is insufficient at the time of development, problems of pattern separation and defects of the pixel portion also occur. When it exceeds 60% by weight, the dissolution rate in the alkaline developer is slow, the developing time is long, and the productivity of the color filter is deteriorated.

The dicyclopentane moiety possessed by the structural unit (D-b3) can be expected to cause steric hindrance to the aggregated state of molecules in the filter segment without the ring having a planar structure.

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(51)

As a precursor of a structural unit (D-b3), the ethylenically unsaturated monomer shown by following formula (D-7), the ethylenically unsaturated monomer shown by following formula (D-8), etc. are mentioned.

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(53)

[In formula (D-7) and formula (D-8), R <^1> is a hydrogen atom or a methyl group, R <^2> is a C2 or 3 alkylene group and m is an integer of 0-2. ]

Examples of the ethylenically unsaturated monomer represented by formula (D-7) include Fancryl FA-513A [dicyclopentanyl acrylate, R ¹ : hydrogen atom, R ² : none, m manufactured by Hitachi Chemical Co., Ltd. = 0] or FA-513M [dicyclopentanyl methacrylate, R ¹ : hydrogen atom, R ² : none, m = 0] and the like, but are not limited to these and may be used in combination of two or more. It may be.

Examples of the ethylenically unsaturated monomer represented by formula (D-8) include Fancryl FA-511A [dicyclopentenyl acrylate, R ¹ : hydrogen atom, R ² : none, manufactured by Hitachi Chemical Co., Ltd .; m = 0], FA-512A [dicyclopentenyloxyethyl acrylate, R ¹ : hydrogen atom, R ² : ethylene group, m = 1], FA-512M [dicyclopentenyloxyethyl 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]; It is not limited to these and can also use together two or more types.

Other structural units are structural units other than the structural unit (D-b1), the structural unit (D-b2), and the structural unit (D-b3).

As precursors of other structural units, for example,

Methyl (meth) methacrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (Meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl acrylate, neopentyl (meth) acrylate, t-pentyl (meth) acrylate, 1-methylbutyl (meth ) Acrylate, hexyl (meth) acrylate, hepta (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, Alkyl or alkenyl (meth) acryl, such as stearyl (meth) acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) acrylate, allyl (meth) acrylate, or oleyl (meth) acrylate Latex, 2-hydroxyethyl (meth) a Relate, 2-hydroxypropyl (meth) acrylate, (beta) -carboxyethyl (meth) acrylate, polyethyleneglycol di (meth) acrylate, 1, 6- hexanediol di (meth) acrylate, triethylene glycol di (Meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) Acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, isobornyl (meth) acrylate, ester acrylate, epoxy (meth) acrylate, urethane acrylate Various acrylic acid esters and methacrylic acid ester, such as these, are mentioned, According to the objective, it is not limited to these, Another ethylenically unsaturated monomer can also be selected, You may use together two or more types.

As another ethylenically unsaturated monomer, for example,

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

Alkoxy polyalkylene glycol (meth) acrylates such as methoxy polypropylene glycol (meth) acrylate or ethoxy polyethylene glycol (meth) acrylate; or,

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

In addition, as a precursor of the structural unit of that excepting 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,

Fatty acid vinyls, such as vinyl acetate or a vinyl propionate, etc. are mentioned.

Furthermore, dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2'-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl Using monomer oligomers such as -2,2 '-[oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2'-[oxybis (methylene)] bis-2-propenoate It is also possible. The said structural unit other than an acryl structural unit can also be used together with the said acryl structural unit.

Moreover, in order to introduce an ethylenically unsaturated double bond by the method (Di) and method (D-ii) shown below, the ethylenically unsaturated monomer which has an epoxy group, or the ethylenically unsaturated monomer which has a hydroxyl group can also be used. These may be structural units other than other structural units depending on the modification, so that the final weight ratio of the structural unit (D-b1), the structural unit (D-b2), and the structural unit (D-b3) is considered. It is desirable to.

As the method (Di), for example, an unsaturated monobasic acid having an ethylenically unsaturated double bond is contained in a side chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group with another at least one ethylenically unsaturated monomer. There is a method in which a carboxyl group is added to a reaction, and the resulting hydroxyl group is allowed to react with a polybasic acid anhydride, introducing an ethylenically unsaturated double bond to give the function of a photosensitive resin, and introducing 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 to the epoxy group, it does not correspond to the structural unit (D-b1) of the resin (D-B1), but to other structural units, Since polybasic acid anhydride forms a carboxyl group after reaction with a hydroxyl group, it corresponds to the structural unit (D-b1) of resin (D-B1).

Examples of ethylenically unsaturated monomers having unsaturated epoxy groups, unsaturated monobasic acids and polybasic acid anhydrides include ethylenically unsaturated monomers, unsaturated monobasic acids and the same as the ethylenically unsaturated monomers, unsaturated monobasic acids and polybasic acid anhydrides in the fifth embodiment; And polybasic acid anhydrides.

As a method similar to the method (Di), for example, an ethylenically unsaturated monomer having an epoxy group in a part of the side chain carboxyl group of the copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group with one or more other ethylenically unsaturated monomers. There is a method of introducing an ethylenically unsaturated double bond and a carboxyl group by addition reaction. In this case, only the structural unit corresponding to the carboxyl group which is not used for addition reaction with an epoxy group corresponds to the structural unit (D-b1) of resin (D-B1).

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

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

The weight average molecular weight (Mw) of the resin (D-B1) is preferably in the range of 5,000 to 100,000, more preferably in the range of 5,000 to 80,000, and still more preferably in the range of 5,000 to 30,000. Moreover, the range of 5,000-50,000 is preferable, and, as for number average molecular weight (Mn), it is preferable that the value of Mw / Mn is 10 or less. When the weight average molecular weight (Mw) of resin (D-B1) exceeds 100,000, interaction between resin will become strong and the viscosity of the coloring composition for color filters will become high, and handling becomes difficult. Moreover, when weight average molecular weight (Mw) is less than 5,000, adhesiveness with respect to board | substrates, such as developability and glass, may fall.

Since content of resin (D-B1) is favorable in film-forming property and various tolerances, it is preferable to use in the amount of 30 weight part or more with respect to 100 weight part of pigments (A1) shown by Formula (1), and a coloring agent concentration It is high, and since it can express favorable color characteristic, it is preferable to use in the quantity of 500 weight part or less. More preferably, it is used in the quantity of 50-250 weight part.

`` Other resins ''

The coloring composition may further contain other resins other than resin (D-B1). As other resins, the transmittance is preferably 80% or more, more preferably 95% or more in the total wavelength region of 400 to 700 nm which is the visible light region. Other resins include thermoplastic resins, thermosetting resins and photosensitive resins, and these may be used alone or in combination of two or more thereof. As an example of resin, the resin similar to resin in 5th Embodiment is mentioned.

As photosensitive resin, the (meth) acryl compound and cinnamic acid (cinnamic acid) which have reactive substituents, such as an isocyanate group, an aldehyde group, and an epoxy group, and the cyanic acid (cinnamic acid) react with the linear polymer which has reactive substituents, such as a hydroxyl group, a carboxyl group, and an amino group, and (meth) acryl Resin which introduce | transduced photocrosslinkable groups, such as a loyl group and a styryl group, into the said linear polymer is used. Moreover, the linear polymer containing acid anhydrides, such as a styrene-maleic anhydride copolymer and the (alpha)-olefin-maleic anhydride copolymer, is made half by the (meth) acryl compound which has hydroxyl groups, such as hydroxyalkyl (meth) acrylate. The esterified thing is also used.

(solvent)

A solvent is used in order to make it easy to form a filter segment by disperse | distributing a pigment (A) fully in binder resin (DB) and apply | coating a coloring composition to substrates, such as a glass substrate, so that a dry film thickness may be set to 0.2-5 micrometers. do. As a solvent, an organic solvent is preferable. Preferable usage-amount of a solvent is the same as that of 5th Embodiment.

(Production method of photosensitive coloring composition)

The coloring composition of 6th Embodiment can be manufactured with the manufacturing method similar to the coloring composition of 5th Embodiment.

(Optional component)

In the coloring composition of 6th Embodiment, arbitrary components, such as a pigment dispersant (DC), a photoinitiator (DD), a sensitizer, a photopolymerizable compound, a polyfunctional thiol, a ultraviolet absorber, a polymerization inhibitor, a storage stabilizer, and other additives, are included It can be contained. Specific examples of these optional components are the same as in the fifth embodiment. Preferable examples, preferred amounts of use and the like are also the same as in the fifth embodiment.

(Removal of coarse particles)

It is preferable that the coloring composition of 6th Embodiment removes coarse particle similarly to the coloring composition of 3rd Embodiment.

[Solvent, optional component]

Hereinafter, the specific example of the solvent and arbitrary components which are used for the said coloring composition for color filters is shown.

(Other colorants (other pigments))

As other colorants (other pigments) that can be used in the coloring composition, for example CI 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, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52 : 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64 : 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112 , 113, 114, 122, 123, 144, 146, 147, 149, 151, 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, 243, 245, 246, 247, 249, 250, 251, 253, 254, 255, 264, 255, 256, 257, 258, 259 , 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274,275, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286 Or red pigments such as 287. Examples of the red dye include xanthene, monoazo (pyridone, barbituric acid, metal complex, etc.), disazo, anthraquinone and the like. Specifically, salt salt compounds of xanthene acid dyes, such as CI acid red 52, 87, 92, 289, 338, etc. are mentioned. These can be used individually or in mixture of 2 or more types.

For example CI Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 51, 55 Orange pigments and / or CI pigments yellow 1, 1: such as, 59, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, or 79 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, 126, 127, 127: 1, 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, 208, 213, 214, 218, 219, 220, or 221 Yellow pigments, such as these, can be used together. Examples of the orange dye and / or the yellow dye include quinoline, monoazo (pyridone, barbituric acid, metal complex, etc.), disazo, methine and the like. These can be used individually or in mixture of 2 or more types.

Among these, anthraquinone pigment, monoazo pigment, disazo pigment, xanthene dye, etc. are preferable as a coloring agent to be used together. Specifically, from the viewpoint of brightness and contrast, CI Pigment Red 48: 1, 122, 168, 176, 177, 185, 202, 206, 207, 209, 224, 242, 254, CI Pigment Orange 38, 71 And salt forming compounds of CI Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185 and CI Acid Red 52 are preferred. More preferably CI Pigment Red 177, 209, 224, 242, or 254, CI Pigment Yellow 83, 138, 139, 150, or 180.

(Organic solvent)

As an organic solvent which can be used for a coloring composition, for example, ethyl lactate, benzyl alcohol, 1,2, 3- trichloro propane, 1, 3- butanediol, 1, 3- butylene glycol, 1, 3- butyl Lenglycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5 -Trimethylcyclohexanone, 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutylacetate, 3-meth Oxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl Alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene , sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol Diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate , Ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl Ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol 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 Ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, Propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl, isoamyl acetate, acetic acid Sobutyl, propyl acetate, dibasic acid ester, etc. are mentioned. These solvents can be used individually or in mixture of 2 or more types in arbitrary ratios as needed.

Among them, alkyl lactates such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and ethylene glycol monomethyl ether acetate, in view of good dispersibility of the colorant, permeability and coating property of the coloring composition. It is preferable to use glycol acetates, such as ethylene glycol monoethyl ether acetate, alcohols, such as benzyl alcohol and diacetone alcohol, and ketones, such as cyclohexanone.

(Resin 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 serves to stabilize the dispersion of the colorant to the colorant carrier by adsorbing the colorant. Specific examples of the resinous dispersant include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) amine salt, polycarboxylic acid ammonium salt and polycarboxylic acid alkylamine salt, Polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl-containing polycarboxylic acid esters, amides thereof, salts thereof, etc. formed by the reaction of these modified substances, poly (lower alkyleneimines) and polyesters having free carboxyl groups; Water-soluble resins such as oil-based dispersants, (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone, Polyester-based, modified polyacrylate-based, ethylene oxide / propylene oxide addition compound, phosphate ester-based All. These may be used alone or in combination of two or more, but are not necessarily limited to these.

Commercially available resin type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 112, 116, 130, 140, 142, 154, 161, 162, 163, 164, 165, manufactured by BYK Chemie Japan KK, 166, 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164 or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, 21116, 21324, 21407, 21715 or Lactimon, Lactimon-WS or Bykumen, etc., SOLSPERSE-3000, 9000 from The Lubrizol Corporation , 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090 53095, 55000, 56000, 76500, etc. EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402 , 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501 , 1502, 1503, etc., Kusumoto Che Disparon 3600N, DISPARLON 1850 by Aicalo, Ltd., Ajisper PA111, PB711, PB821, PB822, PB824 by Ajinomoto Fine-Techno Co., Inc., etc. are mentioned. These can be used individually or in mixture of 2 or more types.

Preferably, Disperbyk-108, 110, 111, 112, 116, 142, 180, 2000, 2001 made by BYK Chemie Japan KK, which is a resin pigment dispersant having an acidic functional group, and SOLSPERSE- made by The Lubrizol Corporation 3000, 21000, 26000, 36600, 41000 or EFKA-4401, 4550 from Ciba Japan KK or DISPARLON 3600N, DISPARLON 1850 from Kusumoto Chemicals, Ltd., or Ajisper PA111 from Ajinomoto Fine-Techno Co., Inc. Although it may be mentioned, It is not limited to these.

(Surfactants)

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

(Photopolymerizable monomer (photopolymerizable compound))

As a monomer and oligomer which harden | cure by an ultraviolet-ray, a heat, etc. and produce a transparent resin, For example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy Oxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanedioldi (meth) acrylate, triethylene Glycoldi (meth) acrylate, tripropylene glycoldi (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6- Hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipenta Listhritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, (meth) acrylic acid ester of methylolated melamine, epoxy (meth) acrylate, Various acrylic acid esters such as urethane acrylate, methacrylic acid ester, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N- Hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile, and the like, but are not limited thereto. These photopolymerizable compounds can be used individually by 1 type or in mixture of 2 or more types in arbitrary ratio as needed.

(Photopolymerization initiator)

As a photoinitiator, 4-phenoxy dichloro acetophenone, 4-t-butyl- dichloro acetophenone, diethoxy acetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl propane-1- On, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2- (dimethylamino) -2-[(4 -Methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1 Acetophenone compounds such as -one; Benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; Benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenylsulfide, or 3,3 ', 4,4'-tetra ( benzophenone compounds such as t-butylperoxycarbonyl) benzophenone; Thioxanthones, such as a thioxanthone, 2-chloro thioxanthone, 2-methyl thioxanthone, isopropyl thioxanthone, 2, 4- diisopropyl thioxanthone, or 2, 4- diethyl thioxanthone compound; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis ( Trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho-1-yl) -4,6-bis (trichloromethyl) -s -Triazine, 2- (4-methoxy-naphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl)- Triazine-based compounds such as 6-triazine or 2,4-trichloromethyl- (4'-methoxystyryl) -6-triazine; Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), 1,2-octanedione, 1- [4 -(Phenylthio)-, 2- (O-benzoyloxime)], or O- (acetyl) -N- (1-phenyl-2-oxo-2- (4'-methoxy-naphthyl) ethylidene) Oxime ester type 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-phenanthrene quinone, camphor quinone and ethyl anthraquinone; Borate compounds; Carbazole compounds; Imidazole compound; Or a titanocene type compound etc. are used. These photoinitiators can be used 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

Among these, it is preferable to contain at least 1 type or more photoinitiators selected from the group which consists of an acetophenone type compound, a phosphine type compound, an imidazole type compound, and an oxime ester type compound as a photoinitiator. By including these photoinitiators, the pattern shape and linearity of a filter segment become more favorable.

(Sensitizer)

Examples of the sensitizer include unsaturated ketones represented by chalcone derivatives, dibenzal acetone and the like, 1,2-diketone derivatives represented by benzyl and camphorquinone, etc., benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, Polymethine pigments, acridine derivatives, azine derivatives such as xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives , Thiazine derivatives, oxazine derivatives, indolin derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinopolpyrazine Derivatives, phthalocyanine derivatives, tetraazapolpyrazine derivatives, tetraquinoxalinopolpyrazine derivatives, naphthalocyanates Nin derivatives, subphthalocyanine derivatives, pyryllium derivatives, thiopyryllium derivatives, tetrapyrine derivatives, anurene derivatives, spiropyrane derivatives, spiroxazine derivatives, thiospyropyran derivatives, metal arene complexes, organic ruthenium complexes, or mihilerketones Derivatives, biimidazole derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylatetalo, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4'-diethylisophate Talophenone, 3,3 'or 4,4'- tetra (t-butylperoxycarbonyl) benzophenone, 4,4'- diethylamino benzophenone, etc. are mentioned. Two or more kinds of sensitizers may be used at an arbitrary ratio as required.

More specifically, OKAWARA Makoto et al., "The Pigment Handbook" (1986, Kodansha Ltd.), OKAWARA Makoto et al., "Chemicals of functional pigments" (1981, CMC Publishing Co., Ltd.), IKEMORI Chuzaburo et al. And sensitizers described in the section "Special Functional Materials" (1986, CMC Publishing Co., Ltd.), but are not limited to these. Moreover, the sensitizer which shows absorption with respect to the light from ultraviolet to near infrared region can also be contained.

(Polyfunctional thiol)

The polyfunctional thiol is, for example, hexanedithiol, decandithiol, 1,4-butanediolbisthiopropionate, 1,4-butanediolbisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisioprop Cypionate, trimethylolpropane tristhioglycolate, trimethylolpropanetristyopionate, trimethylol ethanetris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), trimethylolpropane tris (3 Mercaptopropionate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakistiopionionate, pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate) Cionate), trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2, 4, 6-trimercapto-s-triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s-triazine, etc. are mentioned. These polyfunctional thiols can be used individually by 1 type or in mixture of 2 or more types in arbitrary ratio as needed.

(Ultraviolet absorber)

As the ultraviolet absorber, for example, 2- [4-[(2-hydroxy-3- (dodecyl and tridecyl) oxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2, 4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl)- Hydroxyphenyltriazines such as 1,3,5-triazine, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2H-benzotriazol-2-yl) -4,6 Benzotriazoles such as -bis (1-methyl-1-phenylethyl) phenol and 2- (3-tbutyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2,4-di Benzophenones such as hydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, phenylsalicylate, p-tert-butylphenylsalley Salicylates such as silates, cyanoacrylates such as ethyl-2-cyano-3,3'-diphenyl acrylate, 2,2,6,6, -tetramethylpiperidine-1- Oxyl (triacetone-amine-N- Oxyl), bis (2,2,6,6-tetramethyl-4-piperidyl) -sebacate, poly [[6-[(1,1,3,3-tetrabutyl) amino] -1,3 And hindered amines such as (5-, triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidinyl) imino]. These ultraviolet absorbers can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

(Polymerization inhibitor)

Examples of the polymerization inhibitor include methylhydroquinone, t-butylhydroquinone, 2,5-di-t-butylhydroquinone, 4-benzoquinone, 4-methoxyphenol, 4-methoxy-1-naphthol, hydroquinone derivatives such as t-butylcatechol and phenol compounds, amine compounds such as phenothiazine, bis- (1-dimethylbenzyl) phenothiazine and 3,7-dioctylphenothiazine, copper dibutyldithiocarbamate Copper and manganese salt compounds such as copper diethyldithiocarbamate, manganese diethyldithiocarbamate and manganese diphenyldithiocarbamate, 4-nitrosophenol, N-nitrosodiphenylamine and N-nitrosocyclo Nitroso compounds, such as hexyl hydroxylamine and N-nitrosophenyl hydroxylamine, its ammonium salt, an aluminum salt, etc. are mentioned. These polymerization inhibitors can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

(Antioxidant)

The "antioxidant" may be a compound having an ultraviolet absorbing function, a radical replenishing function, or a peroxide decomposition function. Specifically, as an antioxidant, a hindered phenol type, a hindered amine type, a phosphorus type, a sulfur type, a benzotriazole type, Benzophenone type, hydroxylamine type, salicylic acid ester type, and a triazine type compound are mentioned, A well-known ultraviolet absorber, antioxidant, etc. can be used. These antioxidant can be used individually by 1 type or in mixture of 2 or more types in arbitrary ratio as needed.

Among these antioxidants, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, or sulfur-based antioxidants are preferable as viewpoints of both 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- Dimethylamino benzoic acid 2-ethylhexyl, N, N-dimethyl paratoluidine, etc. are mentioned. These amine compounds can be used individually by 1 type or in mixture of 2 or more types in arbitrary ratio as needed.

(Leveling agent)

As a leveling agent, dimethylsiloxane which has a polyether structure or a polyester structure in a principal chain is preferable. As a specific example of the dimethylsiloxane which has a polyether structure in a principal chain, FZ-2122 by Dow Corning Toray Co., Ltd., BYK-333 by BYK-Chemie, etc. are mentioned. As a specific example of the dimethylsiloxane which has a polyester structure in a principal chain, BYK-310 by the BYK-Chemie company, BYK-370, etc. are mentioned. Dimethylsiloxane which has a polyether structure in a principal chain, and dimethylsiloxane which has a polyester structure in a principal chain can also be used together.

Particularly preferred as a leveling agent is one type of a so-called surfactant having a hydrophobic group and a hydrophilic group in a molecule, which has a hydrophilic group and a low solubility in water, and when added to a coloring composition, has a low surface tension lowering ability. Moreover, it is useful to have good wettability with respect to a glass plate, even if it has low surface tension fall ability, and it can use suitably what can fully suppress chargeability in the addition amount which the defect of a coating film by foaming does not appear. As the leveling agent having such desirable properties, dimethylpolysiloxanes having polyalkylene oxide units can be preferably used. As a polyalkylene oxide unit, there exist a polyethylene oxide unit and a polypropylene oxide unit, and dimethyl polysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

In addition, the bond form of the polyalkylene oxide unit with the dimethylpolysiloxane is repeated alternately with the pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of the dimethylpolysiloxane, the terminal modified form bonded to the terminal of the dimethylpolysiloxane, and the dimethylpolysiloxane. Any of the bonded linear block copolymer types may be used. Dimethylpolysiloxanes having polyalkylene oxide units are commercially available from Toray Dow Corning Co., Ltd., for example FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ -2203, FZ-2207, but is not limited to these. A leveling agent can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

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. As anionic surfactant added auxiliary to a leveling agent, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, the alkali salt of a styrene-acrylic acid copolymer, sodium alkylnaphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, la Monoylol amine sulfate, lauryl triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearic acid, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate ester, etc. have.

As cationic surfactant added auxiliary to a leveling agent, alkyl quaternary ammonium salts and these ethylene oxide addition products are mentioned. As a nonionic surfactant added auxiliary to a leveling agent, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostea Elate, polyethyleneglycol monolaurate, etc .; Alkyl betaines such as alkyldimethylaminoacetic acid betaine; amphoteric surfactants such as alkylimidazoline; and fluorine-based or silicone-based surfactants.

(Curing agent, curing accelerator)

As the curing agent, a phenolic resin, an amine compound, an acid anhydride, an active ester, a carboxylic acid compound, a sulfonic acid compound, or the like is effective, but is not particularly limited thereto, and any curing agent may be used as long as it can react with the thermosetting resin. Can be used Moreover, among these, the compound which has two or more phenolic hydroxyl groups in 1 molecule, and an amine hardening | curing agent are mentioned preferably. As said hardening accelerator, it is an amine compound (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N- dimethylbenzylamine, 4-methoxy-N, N-dimethyl, for example). Benzylamine, 4-methyl-N, N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (e.g. triethylbenzylammonium chloride, etc.), block isocyanate compounds (e.g. dimethylamine, etc.), imidazole derivatives Bicyclic amidine compounds and salts thereof (eg 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, and the like), phosphorus compound (for example, triphenylforce Pins), guanamine compounds (e.g. melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (e.g., 2,4-diamino-6-methacryloyl) Oxyethyl-S-tree Gin, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6-metha Chloroloyloxyethyl-S-triazine, isocyanuric acid adduct, etc.) etc. can be used. These may be used alone, or two or more of them may be used in combination.

(Storage stabilizer)

As a storage stabilizer, for example, 2,6-bis (1,1-dimethylethyl) -4-methylphenol and pentaerystyryl-tetrakis [3- (3,5-di-t-butyl-4- Hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) 1,3,5-triazine hindered phenols such as t-butyl pyrocatechol, organic phosphines such as tetraethylphosphine, triphenylphosphine, tetraphenylphosphine, zinc dimethyldithiophosphate, zinc dipropyldithiophosphate, dibutyldithi Phosphates such as molybdenum pentaphosphate, sulfur based such as dodecyl sulfide and benzothiophene, quaternary ammonium chloride such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ether thereof have. These storage stabilizers can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

(Adhesion improver)

Examples of the adhesion improving agent include (meth) such as vinylsilanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane. ) Acrylsilane, (beta)-(3, 4- epoxycyclohexyl) ethyltrimethoxysilane, (beta)-(3, 4- epoxycyclohexyl) methyl trimethoxysilane, (beta)-(3, 4- epoxycyclohexyl) Epoxy silanes such as ethyl triethoxysilane, β- (3,4-epoxycyclohexyl) methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyltriethoxysilane; N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ- Aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrie 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 promoters can be used individually by 1 type or in mixture of 2 or more types in arbitrary ratio as needed.

[Color Filter]

The color filter of the seventh embodiment will be described.

[Seventh Embodiment]

(Color filter)

The color filter of 7th Embodiment is formed using the said coloring composition for color filters. According to the seventh embodiment, it is possible to provide a high definition color filter having excellent brightness and contrast ratio. The color filter of 7th Embodiment can be used for a color liquid crystal display device, a color imaging tube element, etc.

The color filter includes 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 include a magenta filter segment, a cyan filter segment and a yellow filter segment.

The color filter generally includes the filter segment on a transparent substrate. As the transparent substrate, glass plates such as soda lime glass, low alkali borosilicate glass, alkali-free alumino borosilicate glass, and resin plates such as polycarbonate, polymethyl methacrylate and polyethylene terephthalate are used. Moreover, the transparent electrode which consists of indium oxide, tin oxide, etc. may be formed in the surface of a glass plate or a resin plate for liquid crystal drive after panelization.

It is preferable that the dry film thickness of a filter segment is 0.2-10 micrometers, More preferably, it is 0.2-5 micrometers. When drying a coating film, a pressure reduction dryer, a convection oven, an IR oven, a hotplate, etc. can also be used.

The green filter segment can be formed using a conventional green coloring composition comprising a green pigment and a colorant carrier. As green pigment, CI pigment green 7, 10, 36, 37, 58, etc. are used, for example.

Moreover, a yellow pigment or a yellow dye can be used together in a green coloring composition. As yellow pigment which can be used together, CI pigment yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35 : 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95 , 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147 , 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181 And yellow pigments such as 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, or 221. Or as a yellow dye which can be used together, a quinoline series, a monoazo system (pyridone system, barbituric acid system, a metal complex system, etc.), a disazo system, a methine system, etc. are mentioned.

The blue filter segment can be formed using a conventional blue coloring composition comprising a blue pigment and a colorant carrier. As a blue pigment, CI pigment blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, etc. are used, for example. Moreover, a purple pigment can be used together in a blue coloring composition. As a purple pigment which can be used together, purple pigments, such as CI pigment violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50, are mentioned. Moreover, you may use the salting compound of the basic dye which is blue or purple, and an acid dye. In the case of using a dye, xanthene-based dye is preferable in view of heat resistance and lightness.

(Production method of color filter)

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

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

When forming a filter segment by the photolithographic method, the coloring composition prepared as the said solvent developing type or alkali developing type coloring resist material is applied to application methods, such as a spray coat, a spin coat, a slit coat, and a roll coat, on a transparent substrate. By this, it is apply | coated so that dry film thickness may be 0.2-10 micrometers, Preferably it is 0.2-5 micrometers. The film dried as needed is subjected to ultraviolet exposure through a mask having a predetermined pattern provided in contact or non-contact state with the film. Thereafter, the developer can be immersed in a solvent or an alkaline developer, or sprayed the developer by spraying or the like to remove the uncured portion to form a desired pattern, and then the same operation can be repeated for other colors to produce a color filter. Furthermore, in order to accelerate superposition | polymerization of a coloring resist material, you may heat as needed. According to the photolithography method, a color filter having a higher precision than the printing method can be produced.

Thereafter, the developer may be immersed in a solvent or an alkaline developer, or sprayed with a spray or the like to remove the uncured portion to form a desired pattern to form a filter segment. Moreover, in order to accelerate superposition | polymerization of the filter segment formed by image development, you may heat as needed. According to the photolithography method, it is possible to form filter segments having a higher degree than the printing method.

At the time of image development, although aqueous solution, such as sodium carbonate and sodium hydroxide, is used as alkaline developing solution, organic alkalis, such as dimethylbenzylamine and a triethanolamine, can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution. As the development treatment method, a shower development method, a spray development method, a dip development method, a puddle development method, and the like can be applied.

On the other hand, in order to increase the ultraviolet exposure sensitivity, after coating and drying the coloring resist, a water-soluble or alkali water-soluble resin, for example, polyvinyl alcohol or water-soluble acrylic resin, etc. by coating and drying to form a film to prevent polymerization inhibition by oxygen Ultraviolet exposure can also be performed.

The color filter can be produced by an electrodeposition method, a transfer method, or the like in addition to the above 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 each color filter segment on a transparent conductive film by electrophoresis of colloidal particle using the transparent conductive film formed on the board | substrate. The transfer method is a method in which filter segments are formed in advance on the surface of the peelable transfer base sheet, and the filter segments are transferred onto a desired substrate.

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

Before forming the color filter segment on the transparent substrate or the reflective substrate, the black matrix may be formed in advance. As the black matrix, inorganic films such as chromium, chromium / chromium oxide, inorganic films such as titanium nitride, and resin films in which light-shielding agents are dispersed are used, but not limited to these. In addition, a thin film transistor (TFT) may be formed on the transparent substrate or the reflective substrate in advance, and thereafter, a color filter segment may be formed. Moreover, on a color filter, an overcoat film, a transparent conductive film, columnar spacer, a liquid crystal aligning film, etc. are formed as needed.

The color filter is bonded to the counter substrate using a sealing agent, the liquid crystal is injected from the injection hole provided in the sealing portion, and then the injection hole is sealed, and if necessary, the polarizing film or the retardation film is bonded to the outside of the substrate. A liquid crystal display panel is manufactured.

Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), optical convecend bend (OCB), and the like. It can be used for the liquid crystal display mode which colorizes using the color filter of.

Example

EMBODIMENT OF THE INVENTION Below, embodiment of this invention is described based on an Example, but this invention is not limited to this.

[ Example A]

Unless otherwise specified, "part" and "%" mean "mass part" and "mass%", respectively. In preparing the pigment composition and the coloring composition, a diketopyrrolopyrrole derivative of formula (6-3), a benzoisoindole derivative of formula (7-1), an anthraquinone derivative of formula (8-5) and a formula as a pigment derivative The quinophthalone derivative of (14-1) was used.

(Average primary particle size of pigment)

By the following method, the average primary particle diameter of the manufactured pigment composition was measured (calculated).

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

(Mass Average Molecular Weight of Binder Resin)

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

In addition, the mass average molecular weight (Mw) of acrylic resin was measured by using TSKgel column (made by Tosoh Corporation), GPC (made by Tosoh Corporation, HLC-8120GPC) equipped with RI detector, using THF as a developing solvent. It is the mass mean molecular weight (Mw) of polystyrene conversion.

First, it demonstrates through the diketopyrrolopyrrole pigment used for the Example and the reference example, the diketopyrrolopyrrole pigment composition, other pigments, a binder resin solution, and the green and blue photosensitive coloring composition.

(Brominated diketopyrrolopyrrole pigment formula (1))

In a stainless steel reaction vessel with a reflux tube, 200 parts of tert-amyl alcohol and 140 parts of sodium-tert-amyl alkoxide dehydrated with a molecular sieve were added under a nitrogen atmosphere, and heated to 100 ° C while stirring. Alcoholate solution was prepared. On the other hand, 88 parts of diisopropyl succinate and 153.6 parts of 4-bromobenzonitrile were added to the glass flask, and it heated and melt | dissolved at 90 degreeC, stirring, and prepared the solution of these mixtures. The heating solution of this mixture was slowly dripped at the fixed speed over 2 hours, stirring vigorously in the said alcoholate solution heated at 100 degreeC. After completion of the dropwise addition, heating and stirring were continued at 90 ° C. for 2 hours to obtain an alkali metal salt of a diketopyrrolopyrrole compound. And 600 parts of methanol, 600 parts of water, and 304 parts of acetic acid were added to the reaction container with a glass jacket, and it cooled to -10 degreeC. The cooled mixture was an alkali of a diketopyrrolopyrrole compound obtained by cooling to 75 ° C. while rotating a shared disk having a diameter of 8 cm at 4000 rpm using a high-speed stirring disperser. The metal salt solution was added in small portions. At this time, while the temperature of the mixture consisting of methanol, acetic acid and water is always maintained at a temperature of -5 ° C or lower, while cooling, adjusting the rate of addition of the alkali metal salt of the diketopyrrolopyrrole compound of 75 ° C, about 120 Add in small portions over minutes. 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 ° C., and then filtered (여; filtration separation) to obtain a red paste. This paste was redispersed in 3500 parts of methanol cooled to 0 degreeC, it was made into the suspension of methanol concentration about 90%, stirred for 3 hours at 5 degreeC, and the particle | grains which followed crystal transition and washing were performed. Then, 150.8 parts of brominated diketopyrrolopyrrole pigment represented by Formula (1) were obtained by filtering by water with the ultrafiltration and drying the water paste of the obtained diketopyrrolopyrrole type compound at 80 degreeC for 24 hours, and grind | pulverizing. .

(Specific hetero diketopyrrolopyrrole pigment A formula (A-2-1))

Into the reaction vessel 1, 220 parts of tert-amyl alcohol was added and 32 parts of 60% NaH was added while cooling in a water bath, followed by heating and stirring at 90 ° C. Subsequently, 100 mL of tert-amyl alcohol, 85.0 parts of the compound of formula (A-16) and 60.9 parts of 4-cyanobiphenyl were dissolved in reaction vessel 2 by the method of Tetrahedron, 58 (2002) 5547-5565. This was added dropwise to the reaction vessel 1 over 2 hours. After reacting at 120 ° C for 10 hours, the mixture was cooled to 60 ° C, 400 parts of methanol and 50 parts of acetic acid were added, followed by filtration and methanol washing, and the specific hetero diketopyrrolopyrrole represented by the formula (A-2-1). Pigment A 88.1 parts were obtained.

[Formula 54]

(Specific hetero diketopyrrolopyrrole pigment A formula (A-2-2))

Except having changed 60.9 parts of 4-cyanobiphenyl to 54.1 parts of 4-tert-butylbenzonitrile, it carried out similarly to manufacture of the specific hetero diketopyrrolopyrrole pigment A formula (A-2-1), and is a formula (A- 83.9 parts of specific hetero diketopyrrolopyrrole pigment A represented by 2-2) were obtained.

(Specific hetero diketopyrrolopyrrole pigment A formula (A-2-3a))

Except for changing 60.9 parts of 4-cyanobiphenyl to 68.7 parts of N-butyl-4-cyanobenzamide, it was carried out in the same manner as in the preparation of the specific hetero diketopyrrolopyrrole pigment A formula (A-2-1), 87.0 parts of specific hetero diketopyrrolopyrrole pigment A represented by (A-2-3a) were obtained.

(Specific hetero diketopyrrolopyrrole pigment A formula (A-2-3b))

Except for changing 60.9 parts of 4-cyanobiphenyl to 75.5 parts of N-phenyl-4-cyanobenzamide, it was carried out in the same manner as in the preparation of the specific hetero diketopyrrolopyrrole pigment A formula (A-2-1), 86.9 parts of specific hetero diketopyrrolopyrrole pigment A represented by (A-2-3b) were obtained.

(Specific hetero diketopyrrolopyrrole pigment A formula (A-2-4a))

In the same manner as in the preparation of the specific hetero diketopyrrolopyrrole pigment A formula (A-2-1), except that 60.9 parts of 4-cyanobiphenyl was changed to 87.8 parts of N, N-dibutyl-4-cyanobenzamide. It carried out and obtained 87.1 parts of specific hetero diketopyrrolopyrrole pigment A represented by Formula (A-2-4a).

(Specific hetero diketopyrrolopyrrole pigment A formula (A-2-4b))

In the same manner as in the preparation of the specific hetero diketopyrrolopyrrole pigment A formula (A-2-1), except that 60.9 parts of 4-cyanobiphenyl was changed to 87.8 parts of N, N-dibutyl-3-cyanobenzamide. It carried out and obtained 83.8 parts of specific hetero diketopyrrolopyrrole pigment A represented by Formula (A-2-4b).

(Specific hetero diketopyrrolopyrrole pigment A formula (A-2-9a))

Except having changed 60.9 parts of 4-cyanobiphenyl to 84.1 parts of 4- (octylthio) benzonitrile, it carried out similarly to manufacture of the specific hetero diketopyrrolopyrrole pigment A formula (A-2-1), and formula (A 85.5 parts of specific hetero diketopyrrolopyrrole pigment A represented by -2-9a) were obtained.

(Specific hetero diketopyrrolopyrrole pigment A formula (A-2-8))

Except for changing 60.9 parts of 4-cyanobiphenyl to 58.1 parts of 4- (trifluoromethyl) benzonitrile, the procedure was carried out in the same manner as in the preparation of the specific hetero diketopyrrolopyrrole pigment A formula (A-2-1); 85.8 parts of specific hetero diketopyrrolopyrrole pigment A represented by (A-2-8) were obtained.

(Specific hetero diketopyrrolopyrrole pigment mixture 1 (RC-1))

In a stainless steel reaction vessel with a reflux tube, 200 parts of tert-amyl alcohol and 140 parts of sodium-tert-amyl alkoxide dehydrated with a molecular sieve were added under a nitrogen atmosphere and heated to 100 ° C. while stirring to prepare an alcoholate solution. It prepared. 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 the glass flask, and it heated and dissolved at 90 degreeC, stirring, and prepared the solution of these mixtures. The heating solution of this mixture was slowly dripped at the fixed speed over 2 hours, stirring vigorously in the said alcoholate solution heated at 100 degreeC. After completion of the dropwise addition, heating and stirring were continued at 90 ° C. for 2 hours to obtain an alkali metal salt of a diketopyrrolopyrrole compound. And 600 parts of methanol, 600 parts of water, and 304 parts of acetic acid were added to the reaction container with a glass jacket, and it cooled to -10 degreeC. The cooled mixture was added with a small amount of an alkali metal salt solution of a diketopyrrolopyrrole compound obtained before cooling to 75 ° C. while rotating a shared disk having a diameter of 8 cm at 4000 rpm using a high-speed stirring dispenser. It was. At this time, while the temperature of the mixture consisting of methanol, acetic acid and water is always maintained at a temperature of -5 ° C or lower, while cooling, adjusting the rate of addition of the alkali metal salt of the diketopyrrolopyrrole compound of 75 ° C, about 120 Add in small portions over minutes. After addition of the alkali metal salt, red crystals precipitated and a red suspension was formed. Subsequently, the obtained red suspension was washed with the ultrafiltration apparatus at 5 degreeC, and it filtered and obtained the red paste. The paste was redispersed in 3500 parts of methanol cooled to 0 deg. C, made into a suspension having a methanol concentration of about 90%, stirred at 5 deg. C for 3 hours, and particle formation and washing followed by crystal transition were performed. Subsequently, 143.6 parts of specific hetero diketopyrrolopyrrole pigment mixture 1 (RC-1) was obtained by filtering by water with the ultrafilter and drying the obtained water paste of the diketopyrrolopyrrole type compound at 80 degreeC for 24 hours, and grind | pulverizing. The content of the obtained CI Pigment Red 254 and the specific hetero diketopyrrolopyrrole pigment A represented by the formula (A-2-1) was quantitatively analyzed using HPLC. As a result, CI Pigment Red 254 and the formula (A- Content of the specific hetero diketopyrrolopyrrole pigment A represented by 2-1) was 90.9 mass% and 9.1 mass%, respectively.

(Specific hetero diketopyrrolopyrrole pigment mixture 2 (RC-2))

A specific hetero diketopyrrolopyrrole was carried out in the same manner as the preparation of the specific hetero diketopyrrolopyrrole pigment mixture 1 (RC-1) except that 15.1 parts of 4-cyanobiphenyl were changed to 13.4 parts of 4-tert-butylbenzonitrile. 142.2 parts of pigment mixture 2 (RC-2) were obtained. The content of the obtained CI Pigment Red 254 and the specific hetero diketopyrrolopyrrole pigment A represented by the formula (A-2-2) was quantitatively analyzed using HPLC. As a result, CI Pigment Red 254 and the formula (A- Content of the specific hetero diketopyrrolopyrrole pigment A represented by 2-2) was 90.7 mass% and 9.3 mass%, respectively.

(Specific hetero diketopyrrolopyrrole pigment mixture 3 (RC-3))

The procedure was carried out in the same manner as in the preparation of the specific hetero diketopyrrolopyrrole pigment mixture 1 (RC-1) except that 15.1 parts of 4-cyanobiphenyl were changed to 19.3 parts of N, N-dibutyl-4-cyanobenzamide, 142.9 parts of specific hetero diketopyrrolopyrrole pigment mixture 3 (RC-3) were obtained. The content of the obtained CI Pigment Red 254 and the specific hetero diketopyrrolopyrrole pigment A represented by the formula (A-2-4a) was quantitatively analyzed using HPLC. As a result, CI Pigment Red 254 and the formula (A- Content of the specific hetero diketopyrrolopyrrole pigment A represented by 2-4a) was 90.8 mass% and 9.2 mass%, respectively.

(Preparation of acrylic resin solution 1)

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

(Preparation of acrylic resin solution 2)

207 parts of cyclohexanone were added to a detachable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube, and a stirring device, the temperature was raised to 80 ° C, and the nitrogen was replaced in the flask. 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate and 2,2'- A mixture of 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. Subsequently, the nitrogen gas was stopped and the drying air was injected for 1 hour with stirring for the entire amount of the obtained copolymer solution, followed by cooling to room temperature, followed by 2-methacryloyloxyethyl isocyanate (Karenz MOI manufactured by Showa Denko KK). ) A mixture of 6.5 parts, dibutyltin laurate 0.08 parts, and 26 parts of cyclohexanone was added dropwise at 70 ° C. over 3 hours. About 2 g of the resin solution was sampled, and it heat-dried at 180 degreeC for 20 minutes, the non-volatile content was measured, and cyclohexanone was added to the resin solution synthesize | combined previously so that the non-volatile content might be 20 mass%, and the acrylic resin solution 2 was prepared. The mass average molecular weight (Mw) was 18000.

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

The following mixture was stirred and mixed so as to be uniform, and then dispersed in an Eiger mill (“mini model M-250 MKII” manufactured by Eiger Japan Co., Ltd.) for 5 hours using 0.5 mm diameter zirconia beads, and then 5.0. Filtration was performed with a filter of μm, thereby producing Green Coloring Composition 1 (GP-1).

Green pigment (C.I. Pigment Green 36) 6.8

5.2 parts of yellow pigment (C.I. pigment yellow 150)

1.0 part of resin type dispersant ("EFKA4300" made 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 that it might become uniform, and it filtered with the filter of 1 micrometer, and produced the green photosensitive coloring composition 1 (GR-1).

42.0 parts of green coloring composition 1 (GP-1)

Acrylic resin solution 2 13.2 parts

2.8 parts of photopolymerizable monomer (`` Aronix M400 '' manufactured by Toagosei Co., Ltd.)

2.0 parts of photoinitiators ("Irgacure-907" made by Ciba Japan K.K.)

0.4 parts of sensitizers (`` EAB-F '' manufactured by Hodogaya Chemical Co., Ltd.)

Ethylene glycol monomethyl ether acetate 39.6 parts

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

The following mixture was stirred and mixed so as to be uniform, and then dispersed in an Eiger mill (“mini model M-250 MKII” manufactured by Eiger Japan Co., Ltd.) for 5 hours using 0.5 mm diameter zirconia beads, and then 5.0. It filtered by the micrometer filter and produced blue coloring composition 1 (BP-1).

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

4.8 parts of purple pigment (C.I. pigment violet 23)

1.0 part of resin type dispersant ("EFKA4300" made 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 that it might become uniform, and it filtered with the filter of 1 micrometer, and produced the blue photosensitive coloring composition 1 (BR-1).

34.0 parts of blue coloring composition 1 (BP-1)

Acrylic resin solution 2 15.2 parts

3.3 parts of photopolymerizable monomers (`` Aronix M400 '' manufactured by Toagosei Co., Ltd.)

2.0 parts of photoinitiators ("Irgacure-907" made by Ciba Japan K.K.)

Ethylene glycol monomethyl ether acetate 45.1 parts

Example 1

(Production of Pigment Composition 1 (R-1))

99.0 parts of brominated diketopyrrolopyrrole pigment of formula (1), 1.0 part of specific hetero diketopyrrolopyrrole pigment A of formula (A-2-1), 1000 parts of sodium chloride, and 120 parts of diethylene glycol, 1 gallon kneader made of stainless steel ( Inoue Manufacturing Co., Ltd. product), and it knead | mixed at 60 degreeC for 10 hours. Next, the kneaded mixture was poured into warm water, stirred for 1 hour while heating to about 80 ° C. to form a slurry, filtered and washed with water to remove salt and diethylene glycol, then at 80 ° C. overnight (day and night) 96.9 parts of diketopyrrolopyrrole pigment composition 1 (R-1) was obtained by drying and pulverizing. The average primary particle diameter was 37.0 nm.

[Example 2]

(Production of Pigment Composition 2 (R-2))

99.0 parts of brominated diketopyrrolopyrrole pigment of formula (1), 1.0 part of specific hetero diketopyrrolopyrrole pigment A of formula (A-2-1), 97.0 parts of brominated diketopyrrolopyrrole pigment of formula (1), Formula ( Except having changed into 3.0 parts of specific hetero diketopyrrolopyrrole pigment A of A-2-1), it carried out similarly to manufacture of pigment composition 1 (R-1), and the diketopyrrolopyrrole pigment composition 2 (R- 2) 96.5 parts were obtained. The average primary particle diameter was 36.8 nm.

[Example 3]

(Production of Pigment Composition 3 (R-3))

99.0 parts of brominated diketopyrrolopyrrole pigment of formula (1), 1.0 part of specific hetero diketopyrrolopyrrole pigment A of formula (A-2-1), 95.0 parts of brominated diketopyrrolopyrrole pigment of formula (1), Formula ( Except having changed into 5.0 parts of specific hetero diketopyrrolopyrrole pigment A of A-2-1), it carried out similarly to manufacture of pigment composition 1 (R-1), and the diketopyrrolopyrrole pigment composition 3 (R- 3) 97.2 parts were obtained. The average primary particle diameter was 30.5 nm.

Example 4

(Production of Pigment Composition 4 (R-4))

99.0 parts of brominated diketopyrrolopyrrole pigment of formula (1), 1.0 part of specific hetero diketopyrrolopyrrole pigment A of formula (A-2-1), 90.0 parts of brominated diketopyrrolopyrrole pigment of formula (1), Formula ( Except having changed into 10.0 parts of specific hetero diketopyrrolopyrrole pigment A of A-2-1), it carried out similarly to manufacture of pigment composition 1 (R-1), and the diketopyrrolopyrrole pigment composition 4 (R- 4) 96.9 parts were obtained. The average primary particle diameter was 28.5 nm.

[Example 5]

(Production of Pigment Composition 5 (R-5))

99.0 parts of brominated diketopyrrolopyrrole pigment of Formula (1), 1.0 part of specific hetero diketopyrrolopyrrole pigment A of Formula (A-2-1), 85.0 parts of brominated diketopyrrolopyrrole pigment of Formula (1), Formula ( Except having changed into 15.0 parts of specific hetero diketopyrrolopyrrole pigment A of A-2-1), it carried out similarly to manufacture of pigment composition 1 (R-1), and the diketopyrrolopyrrole pigment composition 5 (R- 5) 97.3 parts were obtained. The average primary particle diameter was 29.5 nm.

[Example 6]

(Production of Pigment Composition 6 (R-6))

Pigment composition 3 (R- except for changing the specific hetero diketopyrrolopyrrole pigment A of Formula (A-2-1) into the specific hetero diketopyrrolopyrrole pigment A of Formula (A-2-2). In the same manner as in the preparation of 3), 98.1 parts of diketopyrrolopyrrole pigment composition 6 (R-6) was obtained. The average primary particle diameter was 29.9 nm.

[Example 7]

(Production of Pigment Composition 7 (R-7))

Pigment composition 3 (R- except for changing the specific hetero diketopyrrolopyrrole pigment A of Formula (A-2-1) into the specific hetero diketopyrrolopyrrole pigment A of Formula (A-2-3a). 98.0 parts of diketopyrrolopyrrole pigment composition 7 (R-7) were obtained similarly to manufacture of 3). The average primary particle diameter was 30.7 nm.

[Example 8]

(Preparation of Pigment Composition 8 (R-8))

Pigment composition 3 (R- except for changing the specific hetero diketopyrrolopyrrole pigment A of Formula (A-2-1) into the specific hetero diketopyrrolopyrrole pigment A of Formula (A-2-3b). In the same manner as in the preparation of 3), 98.4 parts of diketopyrrolopyrrole pigment composition 8 (R-8) was obtained. The average primary particle diameter was 31.2 nm.

[Example 9]

(Production of Pigment Composition 9 (R-9))

Pigment composition 3 (R- except for changing the specific hetero diketopyrrolopyrrole pigment A of Formula (A-2-1) into the specific hetero diketopyrrolopyrrole pigment A of Formula (A-2-4a). 97.5 parts of diketopyrrolopyrrole pigment composition 9 (R-9) was obtained similarly to manufacture of 3). The average primary particle diameter was 35.4 nm.

[Example 10]

(Production of Pigment Composition 10 (R-10))

Pigment composition 3 (R- except for changing the specific hetero diketopyrrolopyrrole pigment A of Formula (A-2-1) into the specific hetero diketopyrrolopyrrole pigment A of Formula (A-2-4b). In the same manner as in the preparation of 3), 96.6 parts of diketopyrrolopyrrole pigment composition 10 (R-10) was obtained. The average primary particle diameter was 35.8 nm.

[Example 11]

(Production of Pigment Composition 11 (R-11))

Pigment composition 3 (R- except for changing the specific hetero diketopyrrolopyrrole pigment A of Formula (A-2-1) into the specific hetero diketopyrrolopyrrole pigment A of Formula (A-2-9a). 93.9 parts of diketopyrrolopyrrole pigment composition 11 (R-11) was obtained similarly to manufacture of 3). The average primary particle diameter was 32.4 nm.

[Example 12]

(Preparation of Pigment Composition 12 (R-12))

Pigment composition 3 (R- except for changing the specific hetero diketopyrrolopyrrole pigment A of Formula (A-2-1) into the specific hetero diketopyrrolopyrrole pigment A of Formula (A-2-8). In the same manner as in the preparation of 3), 95.7 parts of diketopyrrolopyrrole pigment composition 12 (R-12) was obtained. The average primary particle diameter was 29.8 nm.

[Example 13]

(Production of Pigment Composition 13 (R-13))

98.0 parts of brominated diketopyrrolopyrrole pigment of formula (1), 1.0 parts of commercially available CI Pigment Red 254 ("Irgaphor Red B-CF" by Ciba Specialty Chemicals Inc.), specific heteros of formula (A-2-1) 1.0 part of diketopyrrolopyrrole pigment A, 1000 parts of sodium chloride, and 120 parts of diethylene glycol were thrown into the 1 gallon kneader made from stainless steel (Inoue Manufacturing Co., Ltd.), and it knead | mixed at 60 degreeC for 10 hours. Next, the kneaded mixture was poured into warm water, stirred for 1 hour while heating to about 80 ° C. to form a slurry, filtered and washed to remove salt and diethylene glycol, and then dried at 80 ° C. overnight and ground. By doing this, 96.7 parts of diketopyrrolopyrrole pigment composition 13 (R-13) was obtained. The average primary particle diameter was 33.2 nm.

[Example 14]

Preparation of Pigment Composition 14 (R-14)

98.0 parts of brominated diketopyrrolopyrrole pigment of formula (1), 1.0 parts of commercially available CI Pigment Red 254 ("Irgaphor Red B-CF" by Ciba Specialty Chemicals Inc.), specific heteros of formula (A-2-1) 1.0 part of diketopyrrolopyrrole pigment A, 80.0 parts of brominated diketopyrrolopyrrole pigment of Formula (1), commercial CI Pigment Red 254 ("Irgaphor Red B-CF" by Ciba Specialty Chemicals Inc.) 18.0 parts, Formula ( A diketopyrrolopyrrole pigment composition 14 (R-14) was carried out in the same manner as in the preparation of the pigment composition 13 (R-13) except that the specific hetero diketopyrrolopyrrole pigment A 2.0 part of A-2-1) was changed. ) 98.3 parts were obtained. The average primary particle diameter was 30.2 nm.

[Example 15]

(Production of Pigment Composition 15 (R-15))

98.0 parts of brominated diketopyrrolopyrrole pigment of formula (1), 1.0 parts of commercially available CI Pigment Red 254 ("Irgaphor Red B-CF" by Ciba Specialty Chemicals Inc.), specific heteros of formula (A-2-1) 1.0 part of diketopyrrolopyrrole pigment A, 50.0 parts of brominated diketopyrrolopyrrole pigment of Formula (1), 45.0 parts of commercial CI Pigment Red 254 ("Irgaphor Red B-CF" by Ciba Specialty Chemicals Inc.), Formula ( A diketopyrrolopyrrole pigment composition 15 (R-15) was carried out in the same manner as in the preparation of the pigment composition 13 (R-13) except that the specific hetero diketopyrrolopyrrole pigment A 5.0 part in A-2-1) was changed. ) 97.0 parts. The average primary particle diameter was 26.7 nm.

[Example 16]

(Production of Pigment Composition 16 (R-16))

98.0 parts of brominated diketopyrrolopyrrole pigment of formula (1), 1.0 parts of commercially available CI Pigment Red 254 ("Irgaphor Red B-CF" by Ciba Specialty Chemicals Inc.), specific heteros of formula (A-2-1) 1.0 parts of diketopyrrolopyrrole pigment A, 20.0 parts of brominated diketopyrrolopyrrole pigment of formula (1), 72.0 parts of commercial CI Pigment Red 254 ("Irgaphor Red B-CF" by Ciba Specialty Chemicals Inc.), Formula ( Except having changed into 8.0 parts of specific hetero diketopyrrolopyrrole pigment A of A-2-1), it carried out similarly to manufacture of pigment composition 13 (R-13), and diketopyrrolopyrrole pigment composition 16 (R-16). ) 94.8 parts were obtained. The average primary particle diameter was 28.0 nm.

Example 17

Preparation of Pigment Composition 17 (R-17)

98.0 parts of brominated diketopyrrolopyrrole pigment of formula (1), 1.0 parts of commercially available CI Pigment Red 254 ("Irgaphor Red B-CF" by Ciba Specialty Chemicals Inc.), specific heteros of formula (A-2-1) 1.0 parts of diketopyrrolopyrrole pigment A, 20.0 parts of brominated diketopyrrolopyrrole pigment of Formula (1), 65.0 parts of CI pigment red 254 ("Irgaphor Red B-CF" by Ciba Specialty Chemicals Inc.), Formula ( A diketopyrrolopyrrole pigment composition 17 (R-17) was carried out in the same manner as in the preparation of the pigment composition 13 (R-13) except that the specific hetero diketopyrrolopyrrole pigment A of A-2-1) was changed to 15.0 parts. 96.2 parts were obtained. The average primary particle diameter was 29.3 nm.

[Example 18]

(Production of Pigment Composition 18 (R-18))

80.0 parts of brominated diketopyrrolopyrrole pigment of formula (1), 20.0 parts of specific hetero diketopyrrolopyrrole pigment mixture 1 (RC-1), 1000 parts of sodium chloride, and 120 parts of diethylene glycol, 1 gallon kneader made from stainless steel (Inoue Manufacturing) Co., Ltd. product), and the mixture was kneaded at 60 ° C for 10 hours. Next, the kneaded mixture was poured into warm water, stirred for 1 hour while heating to about 80 ° C. to form a slurry, filtered and washed to remove salt and diethylene glycol, and then dried at 80 ° C. overnight and ground. Thus, 96.9 parts of diketopyrrolopyrrole pigment composition 18 (R-18) was obtained. The average primary particle diameter was 29.2 nm.

[Example 19]

(Preparation of Pigment Composition 19 (R-19))

Same as the preparation of pigment composition 18 (R-18), except that certain hetero diketopyrrolopyrrole pigment mixture 1 (RC-1) was changed to specific hetero diketopyrrolopyrrole pigment mixture 2 (RC-2). As a result, 96.1 parts of diketopyrrolopyrrole pigment composition 19 (R-19) was obtained. The average primary particle diameter was 30.5 nm.

[Example 20]

(Production of Pigment Composition 20 (R-20))

Same as the preparation of pigment composition 18 (R-18), except that certain hetero diketopyrrolopyrrole pigment mixture 1 (RC-1) was changed to specific hetero diketopyrrolopyrrole pigment mixture 3 (RC-3). As a result, 95.4 parts of diketopyrrolopyrrole pigment composition 20 (R-20) was obtained. The average primary particle diameter was 31.1 nm.

Example 21

(Production of Pigment Composition 21 (R-21))

95.0 parts of brominated diketopyrrolopyrrole pigment of formula (1), 5.0 parts of specific hetero diketopyrrolopyrrole pigment A of formula (A-2-1), 5.0 parts of pigment derivative of formula (7-1), 1000 parts of sodium chloride, and 120 parts of diethylene glycol was thrown into the 1 gallon kneader made from stainless steel (made by Inoue Manufacturing Co., Ltd.), and it knead | mixed at 60 degreeC for 10 hours. Next, the kneaded mixture was poured into warm water, stirred for 1 hour while heating to about 80 ° C. to form a slurry, filtered and washed to remove salt and diethylene glycol, and then dried at 80 ° C. overnight and ground. By doing this, 91.8 parts of diketopyrrolopyrrole pigment composition 21 (R-21) was obtained. The average primary particle diameter was 27.4 nm.

[Example 22]

(Production of Pigment Composition 22 (R-22))

80.0 parts of brominated diketopyrrolopyrrole pigment of formula (1), 18.0 parts of commercially available CI Pigment Red 254 ("Irgaphor Red B-CF" by Ciba Specialty Chemicals Inc.), specific heteros of formula (A-2-1) 2.0 parts of diketopyrrolopyrrole pigment A, 5.0 parts of the pigment derivative of formula (7-1), 1000 parts of sodium chloride and 120 parts of diethylene glycol were charged into a stainless steel gallon kneader (manufactured by Inoue Manufacturing Co., Ltd.), It knead | mixed for 10 hours at 60 degreeC. Next, the kneaded mixture was poured into warm water, stirred for 1 hour while heating to about 80 ° C. to form a slurry, filtered and washed to remove salt and diethylene glycol, and then dried at 80 ° C. overnight and ground. By doing this, 91.3 parts of diketopyrrolopyrrole pigment composition 22 (R-22) was obtained. The average primary particle diameter was 29.1 nm.

[Referential Example 1]

(Production of Pigment Composition 23 (R-23))

Pigment composition 4 (R-4) except that the brominated diketopyrrolopyrrole pigment of formula (1) was changed to the commercial CI Pigment Red 254 ("Irgaphor Red B-CF" by Ciba Specialty Chemicals Inc.). ), 96.0 parts of diketopyrrolopyrrole pigment composition 23 (R-23) was obtained. The average primary particle diameter was 30.9 nm.

[Reference Example 2]

(Production of Pigment Composition 24 (R-24))

100.0 parts of brominated diketopyrrolopyrrole pigment of Formula (1), 1000 parts of sodium chloride, and 120 parts of diethylene glycol were thrown in the stainless gallon kneader (Inoue Manufacturing Co., Ltd.), and it knead | mixed at 60 degreeC for 10 hours. . Next, the kneaded mixture was poured into warm water, stirred for 1 hour while heating to about 80 ° C. to form a slurry, filtered and washed to remove salt and diethylene glycol, and then dried at 80 ° C. overnight and ground. By doing this, 96.9 parts of diketopyrrolopyrrole pigment composition 24 (R-24) was obtained. The average primary particle diameter was 33.1 nm.

[Referential Example 3]

(Production of Pigment Composition 25 (R-25))

95.0 parts of brominated diketopyrrolopyrrole pigment of formula (1) and 5.0 parts of specific hetero diketopyrrolopyrrole pigment A of formula (A-2-1), 70.0 parts of brominated diketopyrrolopyrrole pigment of formula (1) and formula ( A diketopyrrolopyrrole pigment composition 25 (R-) was carried out in the same manner as in the preparation of the pigment composition 1 (R-1), except that 30.0 parts of the specific hetero diketopyrrolopyrrole pigment A of A-2-1) was changed. 25) 98.0 parts were obtained. The average primary particle diameter was 28.6 nm.

[Reference Example 4]

(Production of Pigment Composition 26 (R-26))

98.0 parts of brominated diketopyrrolopyrrole pigment of formula (1), 1.0 parts of commercially available CI Pigment Red 254 ("Irgaphor Red B-CF" by Ciba Specialty Chemicals Inc.), specific heteros of formula (A-2-1) 1.0 part of diketopyrrolopyrrole pigment A, 15.0 parts of brominated diketopyrrolopyrrole pigment of Formula (1), 65.0 parts of commercial CI Pigment Red 254 ("Irgaphor Red B-CF" by Ciba Specialty Chemicals Inc.), Formula ( A diketopyrrolopyrrole pigment composition 26 (R-26) was carried out in the same manner as in the preparation of the pigment composition 13 (R-13), except that the specific hetero diketopyrrolopyrrole pigment A in A-2-1) was changed to 20.0 parts. 95.1 parts were obtained. The average primary particle diameter was 29.5 nm.

[Reference Example 5]

(Production of Pigment Composition 27 (R-27))

Pigment composition 24 (R-24) except having changed the brominated diketopyrrolopyrrole pigment of Formula (1) into commercial CI Pigment Red 254 ("Irgaphor Red B-CF" by Ciba Specialty Chemicals Inc.). ), 98.1 parts of diketopyrrolopyrrole pigment composition 27 (R-27) was obtained. The average primary particle diameter was 34.9 nm.

[Referential Example 6]

Preparation of Pigment Composition 28 (R-28)

It synthesize | combined by the method similar to Example 1016 of Unexamined-Japanese-Patent No. 2011-523433, and obtained the pigment composition 28 (R-28) which consists of a diketopyrrolopyrrole pigment of Formula (1) and following formula (A-17).

(55)

[Reference Example 7]

Preparation of Pigment Composition 29 (R-29)

It synthesize | combined by the method similar to Example 1039 of Unexamined-Japanese-Patent No. 2011-523433, and obtained the pigment composition 29 (R-29) which consists of a diketopyrrolopyrrole pigment of Formula (1) and following formula (A-18).

(56)

The contents of the prepared pigment compositions 1 to 29 (R-1 to 29) are shown in Table A-1. "PR254" described in Table A-1 means CI Pigment Red 254.

TABLE A-1

[Example 23]

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

The following mixture was stirred and mixed so as to be uniform, and then dispersed in an Eiger mill (“mini model M-250 MKII” manufactured by Eiger Japan Co., Ltd.) for 5 hours using 0.5 mm diameter zirconia beads, and then 5.0. It filtered with the filter of micrometers, and produced coloring composition 1 (RP-1).

Diketopyrrolopyrrole pigment composition 1 (R-1) 11.0 parts

1.0 part of pigment derivative (14-1)

Acrylic resin solution 1 40.0 parts

Propylene glycol monomethyl ether acetate 48.0 parts

Examples 24 to 44

(Production of Colored Compositions 2 to 22 (RP-2 to 22))

Colored compositions 2 to 22 (RP-2 to 22) were produced by the same method as the coloring composition 1 (RP-1) except that the pigment composition 1 (R-1) was changed to the pigment composition described in Table A-2. It was.

[Example 45]

(Production of Coloring Composition 23 (RP-23))

The following mixture was stirred and mixed so as to be uniform, and then dispersed in an Eiger mill (“mini model M-250 MKII” manufactured by Eiger Japan Co., Ltd.) for 5 hours using 0.5 mm diameter zirconia beads, and then 5.0. It filtered by the micrometer filter and produced coloring composition 23 (RP-23).

Diketopyrrolopyrrole pigment composition 2 (R-2) 11.0 parts

1.0 part of pigment derivative (6-3)

6.0 parts of resin type dispersant

(By BYK-Chemie company `` BYK161 '' (30% solution))

Acrylic resin solution 1 31.0 parts

Propylene glycol monomethyl ether acetate 51.0 parts

[Example 46]

(Production of Coloring Composition 24 (RP-24))

The following mixture was stirred and mixed so as to be uniform, and then dispersed in an Eiger mill (“mini model M-250 MKII” manufactured by Eiger Japan Co., Ltd.) for 5 hours using 0.5 mm diameter zirconia beads, and then 5.0. It filtered by the micrometer filter and produced coloring composition 24 (RP-24).

Diketopyrrolopyrrole pigment composition 2 (R-2) 12.0 parts

3.6 parts of resin type dispersant

(`` 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 8-14]

(Production of colored composition 25-31 (RP-25-31))

Coloring compositions 25-31 (RP-25-31) were produced by the same method as coloring composition 1 (RP-1), except that the pigment composition 1 (R-1) was changed to the pigment composition shown in Table A-2. It was.

&Lt; Evaluation of coloring composition >

(Production of Contrast Measurement Board)

The coloring composition obtained in Examples 23-46 and Reference Examples 8-14 was apply | coated to the film thickness which becomes x = 0.640 in C light source on the glass substrate of 100 mm x 100 mm, 0.7 mm thickness, and dried. And the red coating film was obtained by heating at 230 degreeC for 60 minutes.

(Contrast Ratio Evaluation of Coating Film)

The measuring method of the contrast ratio of a coating film is demonstrated. The light emitted from the backlight unit for liquid crystal display is polarized through the polarizing plate, passes through the dry coating film of the coloring composition applied on the glass substrate, and reaches the polarizing plate. When the polarizing plane of the polarizing plate and the polarizing plate are parallel, 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 dry coating film of the coloring composition, scattering due to pigment particles occurs, and when a part of the polarizing plane is displaced, when the polarizing plates are parallel, the amount of light passing through the polarizing plate decreases, and the polarizing plate At this time (orthogonal), some light transmits through the polarizing plate. This transmitted light was measured as the brightness | luminance on a polarizing plate, and the ratio (contrast ratio) of the brightness | luminance when a polarizing plate is parallel, and the brightness | luminance at the time of going straight was computed.

(Contrast ratio) = (parallel brightness) / (parallel brightness)

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

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

(Measurement of Initial Viscosity and Thickening Rate)

The viscosity of the coloring composition measured the initial viscosity in 25 degreeC using the E-type viscosity meter ("ELD type viscometer" by Toki Sangyo Co., Ltd.) on the day which prepared the coloring composition. And after counting from the day which prepared the coloring composition, and standing still at 40 degreeC for 7 days, after returning a sample temperature to 25 degreeC, a viscosity with time is measured by the said viscosity measuring method, and a time-dependent thickening rate is calculated | required from the following formula. It was.

Thickening rate = (viscosity over time) / (initial viscosity) x 100 (%)

(Evaluation of initial viscosity, thickening rate with time)

About viscosity stability, evaluation was performed through the thickening rate with time. As time-dependent thickening rate is 80% or more and less than 120%, it can be practically tolerated. If it deteriorates or thickens beyond this range, when coating a coloring composition to a glass substrate, it cannot apply on the same coating conditions, and a problem arises in productivity. More preferably, it is 90% or more and less than 110% of range.

○: over time thickening rate 90% or more less than 110%

(Triangle | delta): 80% or more and less than 90%, or 110% or more and less than 120%

X: Thickness ratio less than 80% or 120% or more

TABLE A-2

(Production of Coloring Composition 32 (RP-32))

The following mixture was stirred and mixed so as to be uniform, and then dispersed in an Eiger mill (“mini model M-250 MKII” manufactured by Eiger Japan Co., Ltd.) for 5 hours using 0.5 mm diameter zirconia beads, and then 5.0. It filtered by the filter of micrometers, and produced the coloring composition 32 (RP-32).

10.8 parts of dianthraquinone pigments (PR177-1)

1.2 parts of pigment derivative formula (8-5)

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

38.4 parts of coloring composition 1 (RP-1)

3.6 parts of coloring composition 32 (RP-32)

Acrylic resin solution 2 13.2 parts

2.0 parts of photoinitiators ("Irgacure-907" made by Ciba Japan K.K.)

Ethylene glycol monomethyl ether acetate 39.6 parts

[Examples 48-72]

(Production of Photosensitive Coloring Compositions 2 to 24 (RR-2 to 24))

Colored composition 1 (RP-1) was changed to coloring composition 2-24 (RP-2-24), and coloring composition 2-24 (RP-2-24) and coloring composition so that it might be the same chromaticity as Example 47. Except having adjusted the ratio of 32 (RP-32), the photosensitive coloring compositions 2-24 (RP-2-24) were produced by the method similar to Example 47.

[Reference Examples 15 to 21]

(Production of the photosensitive coloring composition 25-31 (RR-25-31))

The coloring composition 1 (RP-1) was changed into the coloring compositions 25-31 (RP-25-31), and also the coloring composition 25-31 (RP-25-31) and coloring composition so that it may be the same chromaticity as Example 47. Except having adjusted the ratio of 32 (RP-32), the photosensitive coloring compositions 25-31 (RR-25-31) were produced by the method similar to Example 47.

(Color characteristic, contrast ratio (CR) evaluation)

The photosensitive coloring composition obtained in Examples 47-72 and Reference Examples 15-21 was apply | coated on the glass substrate of 100 mm x 100 mm and 0.7 mm thickness by the film thickness which becomes x = 0.640 and y = 0.328 in C light source, After drying, ultraviolet rays of 300 mJ / cm 2 were irradiated with an ultra-high pressure mercury lamp. And the red coating film was obtained by heating at 230 degreeC for 60 minutes. Then, the brightness (Y) and contrast ratio (CR) of the obtained coating film were measured.

In addition, chromaticity and lightness (Y) were measured with the microscopic spectrophotometer ("OSP-SP200" by Olympus Optical Co., Ltd.).

(Evaluation of crystallization on the surface of coating film)

The photosensitive coloring composition obtained in Examples 47-72 and Reference Examples 15-21 was apply | coated on the glass substrate of 100 mm x 100 mm and 0.7 mm thickness with the film thickness which becomes x = 0.640 in C light source, After drying, ultraviolet rays of 300 mJ / cm 2 were irradiated with an ultra-high pressure mercury lamp. Subsequently, after heat-processing for 60 minutes at 230 degreeC, heat processing was repeated twice at 60 degreeC for 60 minutes. After the heat treatment, the coating film surface of the substrate was observed with an optical microscope, and the presence or absence of crystal precipitation was determined according to the following criteria.

(Double-circle): No heat-treatment after heat processing at 230 degreeC for 60 minutes, after heat processing at 240 degreeC for 60 minutes, and further heating at 240 degreeC for 60 minutes.

○: no crystal precipitation after heat treatment at 230 ° C. for 60 minutes and additionally heat treatment at 240 ° C. for 60 minutes (crystal precipitation during heat treatment at 240 ° C. for 60 minutes)

(Triangle | delta): There is no crystal precipitation after heat processing at 230 degreeC for 60 minutes, but there exists crystallization by heat processing at 240 degreeC for 60 minutes further

X: crystallization exists after heat treatment at 230 ° C. for 60 minutes

Table A-3

From the results of Table A-3, in the color filter formation, in the diketopyrrolopyrrole pigment composition containing a brominated diketopyrrolopyrrole pigment and a specific hetero diketopyrrolopyrrole pigment A, specific hetero diketopyrrolopyrrole pigment A The embodiment using the diketopyrrolopyrrole pigment composition having a content of 1% by mass to 15% by mass based on the total mass of the diketopyrrolopyrrole pigment is particularly excellent in brightness, has high contrast, and is heated. Crystal precipitation of the diketopyrrolopyrrole pigment by the step was suppressed.

&Lt; Fabrication of color filter &

The green photosensitive coloring composition and blue photosensitive resin composition used for preparation of a color filter were produced. In addition, the photosensitive coloring composition 2 (RR-2) of this Example A was used about red.

The black matrix was pattern-processed on the glass substrate, and the photosensitive coloring composition 2 (RR-2) was apply | coated with the film thickness which becomes x = 0.640 and y = 0.328 by the spin coater on this substrate, and the coloring film was formed. This film was irradiated with ultraviolet light of 300 mJ / cm 2 using an ultra-high pressure mercury lamp through a photomask. Subsequently, spray development was carried out with an alkaline developer composed of 0.2% by mass aqueous sodium carbonate solution to remove the unexposed portions, which was then washed with ion-exchanged water, and the substrate was heated at 230 ° C. for 20 minutes to form a red filter segment. By the same method, the green photosensitive coloring composition 1 (GR-1) is set to x = 0.300 and y = 0.600, and x = 0.150 and y = 0.060 are obtained using blue photosensitive coloring composition 1 (BR-1). It apply | coated with the film thickness used respectively, the green filter segment and the blue filter segment were formed, and the color filter was obtained.

By using the photosensitive coloring composition 2 (RR-2), the color filter which was high brightness and high contrast, and without crystal precipitation in the heating process was able to be produced.

[ Example B]

(Average primary particle size of pigment)

Propylene glycol monomethyl ether acetate was added to the powder of the pigment composition, a small amount of Disperbyk-161 was added as a resinous dispersant, and treated with ultrasonic waves for 1 minute to prepare a sample for measurement. Three samples (at 3: o'clock) of the sample which can confirm the primary particle of 100 or more pigments were taken by this transmission electron microscope (TEM), and the size of 100 primary particle is measured in order from an upper left corner, respectively. It was. Specifically, the minor axis diameter and the major axis diameter of the primary particles of each pigment are measured in nm units, the average is the primary particle diameter of the pigment particles, and 300 distributions are made every 5 nm in total, and every 5 nm. The number average particle diameter was computed by approximating the median value (for example, 8 nm in case of 6 nm or more and 10 nm or less) as the particle diameter of these particles, and calculating based on each particle diameter and the number.

Example 1

(Production of Pigment Composition 1 (R-1))

In a stainless steel reaction vessel with a reflux tube, 200 parts of tert-amyl alcohol and 140 parts of sodium-tert-amyl alkoxide dehydrated with a molecular sieve were added under a nitrogen atmosphere and heated to 100 ° C. while stirring to prepare an alcoholate solution. It prepared. On the other hand, 88 parts of diisopropyl succinate and 153.6 parts of 4-bromobenzonitrile were added to the glass flask, and it heated and melt | dissolved at 90 degreeC, stirring, and prepared the solution of these mixtures. The heating solution of this mixture was slowly dripped at the fixed speed over 2 hours, stirring vigorously in the said alcoholate solution heated at 100 degreeC. After completion of the dropwise addition, heating and stirring were continued at 90 ° C. for 2 hours to obtain an alkali metal salt of a diketopyrrolopyrrole compound. And 600 parts of methanol, 600 parts of water, and 304 parts of acetic acid were added to the reaction container with a glass jacket, and it cooled to -10 degreeC. The cooled mixture was added with a small amount of an alkali metal salt solution of a diketopyrrolopyrrole compound obtained before cooling to 75 ° C. while rotating a shared disk having a diameter of 8 cm at 4000 rpm using a high-speed stirring dispenser. It was. At this time, while the temperature of the mixture consisting of methanol, acetic acid and water is always maintained at a temperature of -5 ° C or lower, while cooling, adjusting the rate of addition of the alkali metal salt of the diketopyrrolopyrrole compound of 75 ° C, about 120 Add in small portions over minutes. After addition of the alkali metal salt, red crystals precipitated and a red suspension was formed. Subsequently, the obtained red suspension was washed with the ultrafiltration apparatus at 5 degreeC, and it filtered and obtained the red paste. The paste was redispersed in 3500 parts of methanol cooled to 0 deg. C, made into a suspension having a methanol concentration of about 90%, stirred at 5 deg. C for 3 hours, and particle formation and washing followed by crystal transition were performed. Subsequently, the water paste of the diketopyrrolopyrrole compound obtained by filtration with an ultrafilter was dried at 80 ° C for 24 hours and pulverized to obtain 150.8 parts of brominated diketopyrrolopyrrole pigment of formula (1).

Subsequently, 220 parts of tert-amyl alcohol were added to the reaction vessel 1, 32 parts of 60% NaH was added while cooling in a water bath, and the mixture was heated and stirred at 90 ° C. Subsequently, 99.2 parts of the compound of the following formula (B-16) synthesized by the method of tert-amyl alcohol, Tetrahedron, 58 (2002) 5547-5565 in Reaction Vessel 2 and benzo of formula (B-3-1) 60.9 parts of nitrile compounds were heated and dissolved, and this was added dropwise to the reaction vessel 1 over 2 hours. After reacting at 120 ° C for 10 hours, the mixture was cooled to 60 ° C, 400 parts of methanol and 50 parts of acetic acid were added, followed by filtration and methanol washing, and the specific hetero diketopyrrolopyrrole represented by the formula (B-2-1). Pigment B 87.8 parts were obtained.

(57)

And 97.0 parts of brominated diketopyrrolopyrrole pigment obtained by Formula (1), 3.0 parts of specific hetero diketopyrrolopyrrole pigments of Formula (B-2-1), 1000 parts of sodium chloride, and 120 parts of diethylene glycol are made of stainless steel 1 It put in gallon kneader (made by Inoue Manufacturing Co., Ltd.), and knead | mixed at 60 degreeC for 10 hours. Next, the kneaded mixture was poured into warm water, stirred for 1 hour while heating to about 80 ° C. to form a slurry, filtered and washed to remove salt and diethylene glycol, and then dried at 80 ° C. overnight and ground. By this, 96.5 parts of pigment composition 1 (R-1) which is a diketopyrrolopyrrole pigment composition were obtained. The average primary particle diameter was 36.8 nm.

[Example 2]

(Production of Pigment Composition 2 (R-2))

95.0 parts of brominated diketopyrrolopyrrole pigment of formula (1) used in the preparation of pigment composition 1, 5.0 parts of specific hetero diketopyrrolopyrrole pigment B of formula (B-2-1), sodium chloride 1000 parts and diethylene glycol 120 parts was put in the stainless steel 1 gallon kneader (made by Inoue Manufacturing Co., Ltd.), and it knead | mixed at 60 degreeC for 10 hours. Next, the kneaded mixture was poured into warm water, stirred for 1 hour while heating to about 80 ° C. to form a slurry, filtered and washed to remove salt and diethylene glycol, and then dried at 80 ° C. overnight and ground. By this, 97.2 parts of pigment composition 2 (R-2) which is a diketopyrrolopyrrole pigment composition were obtained. The average primary particle diameter was 30.5 nm.

[Example 3]

(Production of Pigment Composition 3 (R-3))

95.0 parts of brominated diketopyrrolopyrrole pigment of formula (1) and 5.0 parts of specific hetero diketopyrrolopyrrole pigment B of formula (B-2-1), 90.0 parts of brominated diketopyrrolopyrrole pigment of formula (1) and formula ( Pigment composition 3 which is a diketopyrrolopyrrole pigment composition similarly to manufacture of pigment composition 2 (R-2) except having changed into 10.0 parts of specific hetero diketopyrrolopyrrole pigment B of B-2-1). 96.9 parts of (R-3) were obtained. The average primary particle diameter was 26.5 nm.

Example 4

(Production of Pigment Composition 4 (R-4))

95.0 parts of brominated diketopyrrolopyrrole pigment of formula (1) and 5.0 parts of specific hetero diketopyrrolopyrrole pigment B of formula (B-2-1), 85.0 parts of brominated diketopyrrolopyrrole pigment of formula (1) and formula ( Pigment composition 4 which is a diketopyrrolopyrrole pigment composition similarly to manufacture of pigment composition 2 (R-2) except having changed into 15.0 parts of specific hetero diketopyrrolopyrrole pigment B of B-2-1). 97.1 parts (R-4) were obtained. The average primary particle diameter was 28.5 nm.

[Example 5]

(Production of Pigment Composition 5 (R-5))

Specific hetero diketopyrrole carried out in pigment composition 1 (R-1), except that 60.2 parts of the benzonitrile compound of formula (B-3-1) was changed to 54.2 parts of the benzonitrile compound of formula (B-3-2). It carried out similarly to manufacture of pyrrole pigment B, and obtained 85.2 parts of specific hetero diketopyrrolopyrrole pigment B represented by Formula (B-2-2).

Subsequently, 95.0 parts of brominated diketopyrrolopyrrole pigment of Formula (1), 5.0 parts of specific hetero diketopyrrolopyrrole pigment B of Formula (B-2-2), 1000 parts of sodium chloride, and 120 parts of diethylene glycol are made of stainless steel 1 It put in gallon kneader (made by Inoue Manufacturing Co., Ltd.), and knead | mixed at 60 degreeC for 10 hours. Next, the kneaded mixture was poured into warm water, stirred for 1 hour while heating to about 80 ° C. to form a slurry, filtered and washed to remove salt and ethylene glycol, and then dried at 80 ° C. overnight, and ground. 96.2 parts of pigment composition 5 (R-5) which is a diketopyrrolopyrrole pigment composition were obtained. The average primary particle diameter was 31.6 nm.

[Example 6]

(Production of Pigment Composition 6 (R-6))

First, a specific heterodiche carried out in pigment composition 1 (R-1) except that 60.2 parts of the benzonitrile compound of formula (B-3-1) was changed to 58.2 parts of the benzonitrile compound of formula (B-3-3). 82.2 parts of specific hetero diketopyrrolopyrrole pigment B represented by Formula (B-2-3) were obtained in the same manner as in the preparation of topyrrolopyrrole pigment B.

Subsequently, 95.0 parts of brominated diketopyrrolopyrrole pigment of Formula (1), 5.0 parts of specific hetero diketopyrrolopyrrole pigment B of Formula (B-2-3), 1000 parts of sodium chloride, and 120 parts of diethylene glycol are made of stainless steel 1 It put in gallon kneader (made by Inoue Manufacturing Co., Ltd.), and knead | mixed at 60 degreeC for 10 hours. Next, the kneaded mixture was poured into warm water, stirred for 1 hour while heating to about 80 ° C. to form a slurry, filtered and washed to remove salt and diethylene glycol, and then dried at 80 ° C. overnight and ground. By this, 95.9 parts of pigment composition 6 (R-6) which is a diketopyrrolopyrrole pigment composition were obtained. The average primary particle diameter was 34.6 nm.

[Example 7]

(Production of Pigment Composition 7 (R-7))

Specific hetero diketopyrrole carried out in pigment composition 1 (R-1), except that 60.2 parts of the benzonitrile compound of formula (B-3-1) was changed to 84.1 parts of the benzonitrile compound of formula (B-3-4a). 94.1 parts of specific hetero diketopyrrolopyrrole pigment B represented by Formula (B-2-4a) were obtained similarly to manufacture of pyrrole pigment B.

Subsequently, 95.0 parts of brominated diketopyrrolopyrrole pigment of Formula (1), 5.0 parts of specific hetero diketopyrrolopyrrole pigment B of Formula (B-2-4a), 1000 parts of sodium chloride, and 120 parts of diethylene glycol are made of stainless steel 1 It put in gallon kneader (made by Inoue Manufacturing Co., Ltd.), and knead | mixed at 60 degreeC for 10 hours. Next, the kneaded mixture was poured into warm water, stirred for 1 hour while heating to about 80 ° C. to form a slurry, filtered and washed to remove salt and diethylene glycol, and then dried at 80 ° C. overnight and ground. By doing this, 97.9 parts of Pigment Composition 7 (R-7) as a diketopyrrolopyrrole pigment composition were obtained. The average primary particle diameter was 28.6 nm.

[Example 8]

(Preparation of Pigment Composition 8 (R-8))

95.0 parts of brominated diketopyrrolopyrrole pigment of formula (1) and 5.0 parts of specific hetero diketopyrrolopyrrole pigment B of formula (B-2-4a), 85.0 parts of brominated diketopyrrolopyrrole pigment of formula (1) and formula ( Pigment composition 8 (diketopyrrolopyrrole pigment composition) in the same manner as in the preparation of pigment composition 7 (R-7) except for changing to specific hetero diketopyrrolopyrrole pigment B 15.0 parts of B-2-4a) R-8) 96.1 parts were obtained. The average primary particle diameter was 25.5 nm.

[Example 9]

(Production of Pigment Composition 9 (R-9))

Specific hetero diketopyrrole carried out in pigment composition 1 (R-1) except that 60.2 parts of the benzonitrile compound of formula (B-3-1) was changed to 71.8 parts of the benzonitrile compound of formula (B-3-4b). It carried out similarly to manufacture of pyrrole pigment B, and obtained 79.1 parts of specific hetero diketopyrrolopyrrole pigment B represented by Formula (B-2-4b).

Subsequently, 95.0 parts of brominated diketopyrrolopyrrole pigment of Formula (1), 5.0 parts of specific hetero diketopyrrolopyrrole pigments of Formula (B-2-4b), 1000 parts of sodium chloride, and 120 parts of diethylene glycol are made of stainless steel 1 It put in gallon kneader (made by Inoue Manufacturing Co., Ltd.), and knead | mixed at 60 degreeC for 10 hours. Next, the kneaded mixture was poured into warm water, stirred for 1 hour while heating to about 80 ° C. to form a slurry, filtered and washed to remove salt and diethylene glycol, and then dried at 80 ° C. overnight and ground. By this, 96.5 parts of pigment compositions 9 (R-9) which are diketopyrrolopyrrole pigment compositions were obtained. The average primary particle diameter was 31.1 nm.

[Example 10]

(Production of Pigment Composition 10 (R-10))

Specific hetero diketopyrrole carried out in pigment composition 1 (R-1) except that 60.2 parts of the benzonitrile compound of formula (B-3-1) was changed to 49.7 parts of the benzonitrile compound of formula (B-3-5). 66.9 parts of specific hetero diketopyrrolopyrrole pigment B represented by the formula (B-2-5) were obtained in the same manner as the production of pyrrole pigment B.

Subsequently, 95.0 parts of brominated diketopyrrolopyrrole pigment of Formula (1), 5.0 parts of specific hetero diketopyrrolopyrrole pigment B of Formula (B-2-5), 1000 parts of sodium chloride, and 120 parts of diethylene glycol are made of stainless steel 1 It put in gallon kneader (made by Inoue Manufacturing Co., Ltd.), and knead | mixed at 60 degreeC for 10 hours. Next, the kneaded mixture was poured into warm water, stirred for 1 hour while heating to about 80 ° C. to form a slurry, filtered and washed to remove salt and diethylene glycol, and then dried at 80 ° C. overnight and ground. By this, 97.5 parts of pigment composition 10 (R-10) which is a diketopyrrolopyrrole pigment composition was obtained. The average primary particle diameter was 33.1 nm.

[Example 11]

(Production of Pigment Composition 11 (R-11))

Specific hetero diketopyrrole carried out in pigment composition 1 (R-1) except that 60.2 parts of the benzonitrile compound of formula (B-3-1) was changed to 106.9 parts of the benzonitrile compound of formula (B-3-6b). It carried out similarly to manufacture of pyrrole pigment B, and obtained 90.7 parts of specific hetero diketopyrrolopyrrole pigment B represented by Formula (B-2-6b).

Subsequently, 95.0 parts of brominated diketopyrrolopyrrole pigment of Formula (1), 5.0 parts of specific hetero diketopyrrolopyrrole pigments of Formula (B-2-6b), 1000 parts of sodium chloride, and 120 parts of diethylene glycol are made of stainless steel 1 It put in gallon kneader (made by Inoue Manufacturing Co., Ltd.), and knead | mixed at 60 degreeC for 10 hours. Next, the kneaded mixture was poured into warm water, stirred for 1 hour while heating to about 80 ° C. to form a slurry, filtered and washed to remove salt and diethylene glycol, and then dried at 80 ° C. overnight and ground. By this, 98.1 parts of pigment compositions 11 (R-11) which are diketopyrrolopyrrole pigment compositions were obtained. The average primary particle diameter was 28.9 nm.

[Example 12]

(Preparation of Pigment Composition 12 (R-12))

Specific hetero diketopyrrole carried out in pigment composition 1 (R-1) except that 60.2 parts of the benzonitrile compound of formula (B-3-1) was changed to 75.6 parts of the benzonitrile compound of formula (B-3-6c). 100.8 parts of specific hetero diketopyrrolopyrrole pigment B represented by Formula (B-2-6c) were obtained similarly to manufacture of pyrrole pigment B.

Subsequently, 95.0 parts of brominated diketopyrrolopyrrole pigment of Formula (1), 5.0 parts of specific hetero diketopyrrolopyrrole pigments of Formula (B-2-6c), 1000 parts of sodium chloride, and 120 parts of diethylene glycol are made of stainless steel 1 It put in gallon kneader (made by Inoue Manufacturing Co., Ltd.), and knead | mixed at 60 degreeC for 10 hours. Next, the kneaded mixture was poured into warm water, stirred for 1 hour while heating to about 80 ° C. to form a slurry, filtered and washed to remove salt and diethylene glycol, and then dried at 80 ° C. overnight and ground. This obtained 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]

(Production of Pigment Composition 13 (R-13))

Specific hetero diketopyrrole carried out in pigment composition 1 (R-1) except that 60.2 parts of the benzonitrile compound of formula (B-3-1) was changed to 87.8 parts of the benzonitrile compound of formula (B-3-7). It carried out similarly to manufacture of pyrrole pigment B, and obtained 85.2 parts of specific hetero diketopyrrolopyrrole pigment B represented by Formula (B-2-7).

Subsequently, 95.0 parts of brominated diketopyrrolopyrrole pigment of Formula (1), 5.0 parts of specific hetero diketopyrrolopyrrole pigments of Formula (B-2-7), 1000 parts of sodium chloride, and 120 parts of diethylene glycol are made of stainless steel 1 It put in gallon kneader (made by Inoue Manufacturing Co., Ltd.), and knead | mixed at 60 degreeC for 10 hours. Next, the kneaded mixture was poured into warm water, stirred for 1 hour while heating to about 80 ° C. to form a slurry, filtered and washed to remove salt and diethylene glycol, and then dried at 80 ° C. overnight and ground. By this, 96.3 parts of pigment composition 13 (R-13) which is a diketopyrrolopyrrole pigment composition were obtained. The average primary particle diameter was 28.2 nm.

[Example 14]

Preparation of Pigment Composition 14 (R-14)

95.0 parts of brominated diketopyrrolopyrrole pigment of formula (1) and 5.0 parts of specific hetero diketopyrrolopyrrole pigment B of formula (B-2-7), 85.0 parts of brominated diketopyrrolopyrrole pigment of formula (1) and formula ( Pigment composition 14 (diketopyrrolopyrrole pigment composition) in the same manner as in the preparation of pigment composition 13 (R-13) except for changing to specific hetero diketopyrrolopyrrole pigment B 15.0 parts of B-2-7) R-14) 95.1 parts were obtained. The average primary particle diameter was 26.5 nm.

[Example 15]

(Production of Pigment Composition 15 (R-15))

Specific hetero diketopyrrole carried out in pigment composition 1 (R-1), except that 60.2 parts of the benzonitrile compound of formula (B-3-1) was changed to 50.0 parts of the benzonitrile compound of formula (B-3-8). It carried out similarly to manufacture of pyrrole pigment B, and obtained 64.5 parts of specific hetero diketopyrrolopyrrole pigment B represented by Formula (B-2-8).

Subsequently, 95.0 parts of brominated diketopyrrolopyrrole pigment of Formula (1), 5.0 parts of specific hetero diketopyrrolopyrrole B of Formula (B-2-8), 1000 parts of sodium chloride, and 120 parts of diethylene glycol, 1 gallon of stainless steel It put in the kneader (made by Inoue Manufacturing Co., Ltd.), and knead | mixed at 60 degreeC for 10 hours. Next, the kneaded mixture was poured into warm water, stirred for 1 hour while heating to about 80 ° C. to form a slurry, filtered and washed to remove salt and diethylene glycol, and then dried at 80 ° C. overnight and ground. By this, 97.3 parts of pigment composition 15 (R-15) which is a diketopyrrolopyrrole pigment composition were obtained. The average primary particle diameter was 34.2 nm.

[Example 16]

(Production of Pigment Composition 16 (R-16))

In a stainless steel reaction vessel with a reflux tube, 200 parts of tert-amyl alcohol and 140 parts of sodium-tert-amyl alkoxide dehydrated with a molecular sieve were added under a nitrogen atmosphere and heated to 100 ° C. while stirring to prepare an alcoholate solution. It prepared. On the other hand, 88 parts of diisopropyl succinate, 146.0 parts of 4-bromobenzonitrile, and 7.6 parts of benzonitrile compounds of a formula (B-3-1) are added to a glass flask, and it heats and melts at 90 degreeC, stirring, and these are these, A solution of the mixture was prepared. The heating solution of this mixture was slowly dripped at the fixed speed over 2 hours, stirring vigorously in the said alcoholate solution heated at 100 degreeC. After completion of the dropwise addition, heating and stirring were continued at 90 ° C. for 2 hours to obtain an alkali metal salt of a diketopyrrolopyrrole compound. And 600 parts of methanol, 600 parts of water, and 304 parts of acetic acid were added to the reaction container with a glass jacket, and it cooled to -10 degreeC. The cooled mixture was added with a small amount of an alkali metal salt solution of a diketopyrrolopyrrole compound obtained before cooling to 75 ° C. while rotating a shared disk having a diameter of 8 cm at 4000 rpm using a high-speed stirring dispenser. It was. At this time, while the temperature of the mixture consisting of methanol, acetic acid and water is always maintained at a temperature of -5 ° C or lower, while cooling, adjusting the rate of addition of the alkali metal salt of the diketopyrrolopyrrole compound of 75 ° C, about 120 Add in small portions over minutes. After addition of the alkali metal salt, red crystals precipitated and a red suspension was formed. Subsequently, the obtained red suspension was washed with the ultrafiltration apparatus at 5 degreeC, and it filtered and obtained the red paste. The paste was redispersed in 3500 parts of methanol cooled to 0 deg. C, made into a suspension having a methanol concentration of about 90%, stirred at 5 deg. C for 3 hours, and particle formation and washing followed by crystal transition were performed. Subsequently, the water paste of the diketopyrrolopyrrole compound obtained by filtration with an ultrafilter was dried at 80 degreeC for 24 hours, and it grind | pulverized, and 145.8 parts of diketopyrrolopyrrole pigment compositions were obtained.

About content of the brominated diketopyrrolopyrrole pigment represented by Formula (1) in the obtained diketopyrrolopyrrole pigment composition and the specific hetero diketopyrrolopyrrole pigment B represented by Formula (B-2-1), using HPLC As a result of quantitative analysis, the mass ratio of the brominated diketopyrrolopyrrole pigment represented by formula (1) and the specific hetero diketopyrrolopyrrole pigment B represented by formula (B-2-1) was 94.3: 5.7. HPLC measurement conditions and holding time are as follows. In addition, the calibration curve required for quantification is brominated diketopyrrolopyrrole pigment of formula (1) synthesized in the preparation of pigment composition 1 (R-1) and specific hetero diketopyrrolopyrrole pigment B of formula (B-2-1) It was written using.

Device; Gulliver series made by JASCO Corporation

Detector; JASCO Corporation UV-970 Detector

column; Symmetry C18 (5 micrometers, 2.1mm diameter * 150mm) made by Waters Corporation

Mobile phase A solution; Dimethylformamide / Water (1: 1)

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

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

wavelength; 510 nm

Column temperature; 35 ℃

flux; 0.3mL / min

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

Equation (1) holding time; 11.9-12.9 min

Holding 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 introduced into a stainless 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, stirred for 1 hour while heating to about 80 ° C. to form a slurry, filtered and washed to remove salt and diethylene glycol, and then dried at 80 ° C. overnight and ground. By this, 97.6 parts of pigment composition 16 (R-16) which is a diketopyrrolopyrrole pigment composition was obtained. The average primary particle diameter was 32.2 nm.

Example 17

Preparation of Pigment Composition 17 (R-17)

In a stainless steel reaction vessel with a reflux tube, 200 parts of tert-amyl alcohol and 140 parts of sodium-tert-amyl alkoxide dehydrated with a molecular sieve were added under a nitrogen atmosphere and heated to 100 ° C. while stirring to prepare an alcoholate solution. It prepared. On the other hand, 88 parts of diisopropyl succinate, 146.0 parts of 4-bromobenzonitrile, and 7.6 parts of benzonitrile compounds of a formula (B-3-1) are added to a glass flask, and it heats and melts at 90 degreeC, stirring, and these are these, A solution of the mixture was prepared. The heating solution of this mixture was slowly dripped at the fixed speed over 2 hours, stirring vigorously in the said alcoholate solution heated at 100 degreeC. After completion of the dropwise addition, heating and stirring were continued at 90 ° C. for 2 hours to obtain an alkali metal salt of a diketopyrrolopyrrole compound. And 600 parts of methanol, 600 parts of water, and 304 parts of acetic acid were added to the reaction container with a glass jacket, and it cooled to -10 degreeC. The cooled mixture was added with a small amount of an alkali metal salt solution of a diketopyrrolopyrrole compound obtained before cooling to 75 ° C. while rotating a shared disk having a diameter of 8 cm at 4000 rpm using a high-speed stirring dispenser. It was. At this time, while the temperature of the mixture consisting of methanol, acetic acid and water is always maintained at a temperature of -5 ° C or lower, while cooling, adjusting the rate of addition of the alkali metal salt of the diketopyrrolopyrrole compound of 75 ° C, about 120 Add in small portions over minutes. After addition of the alkali metal salt, red crystals precipitated and a red suspension was formed. Subsequently, the obtained red suspension was washed with the ultrafiltration apparatus at 5 degreeC, and it filtered and obtained the red paste. The paste was redispersed in 3500 parts of methanol cooled to 0 deg. C, made into a suspension having a methanol concentration of about 90%, stirred at 5 deg. C for 3 hours, and particle formation and washing followed by crystal transition were performed. Then, the resultant was filtered with an ultrafilter to obtain a red paste of a diketopyrrolopyrrole compound. After redispersing the obtained red paste in 3000 ml of water, a pigment derivative slurry in which 5.5 parts of a pigment derivative of the benzoisoindole derivative represented by the formula (7-1) was added to 100 parts of water was added under stirring, After stirring for 1 hour, it was filtered and washed to obtain a water paste of a diketopyrrolopyrrole compound. 154.8 parts of diketopyrrolopyrrole pigment compositions were obtained by drying this water paste at 80 degreeC for 24 hours and grind | pulverizing.

In the same manner as in the preparation of the pigment composition 16 (R-16), the brominated diketopyrrolopyrrole pigment represented by the formula (1) in the diketopyrrolopyrrole pigment composition and the specific hetero represented by the formula (B-2-1) The content of diketopyrrolopyrrole pigment B was quantitatively analyzed using HPLC, and as a result, the brominated diketopyrrolopyrrole pigment represented by formula (1) and the specific hetero diketopyrrole 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 introduced into a stainless 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, stirred for 1 hour while heating to about 80 ° C. to form a slurry, filtered and washed to remove salt and diethylene glycol, and then dried at 80 ° C. overnight and ground. By this, 96.6 parts of pigment composition 17 (R-17) which is a diketopyrrolopyrrole pigment composition were obtained. The average primary particle diameter was 27.2 nm.

[Example 18]

(Production of Pigment Composition 18 (R-18))

In the same manner as in the preparation of the pigment composition 16 (R-16), the brominated diketopyrrolopyrrole pigment represented by the formula (1) in the diketopyrrolopyrrole pigment composition and the specific hetero represented by the formula (B-2-1) The content of diketopyrrolopyrrole pigment B was quantitatively analyzed using HPLC, and as a result, the brominated diketopyrrolopyrrole pigment represented by formula (1) and the specific hetero diketopyrrole 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 pigment derivatives of the benzoisoindole derivative of formula (7-1), 1000 parts of sodium chloride and 120 parts of diethylene glycol were made of stainless steel 1 gallon kneader (Inoue Manufacturing Co.) , Ltd.), and the mixture was kneaded at 60 ° C for 10 hours. Next, the kneaded mixture was poured into warm water, stirred for 1 hour while heating to about 80 ° C. to form a slurry, filtered and washed to remove salt and diethylene glycol, and then dried at 80 ° C. overnight and ground. By this, 95.6 parts of pigment compositions 18 (R-18) which are diketopyrrolopyrrole pigment compositions were obtained. The average primary particle diameter was 26.2 nm.

[Example 19]

(Preparation of Pigment Composition 19 (R-19))

In a stainless steel reaction vessel with a reflux tube, 200 parts of tert-amyl alcohol and 140 parts of sodium-tert-amyl alkoxide dehydrated with a molecular sieve were added under a nitrogen atmosphere and heated to 100 ° C. while stirring to prepare an alcoholate solution. It prepared. On the other hand, 88 parts of diisopropyl succinate, 138.3 parts of 4-bromobenzonitrile, and 15.1 parts of benzonitrile compounds of a formula (B-3-1) are added to a glass flask, and it heats and melts at 90 degreeC, stirring, and these are these, A solution of the mixture was prepared. The heating solution of this mixture was slowly dripped at the fixed speed over 2 hours, stirring vigorously in the said alcoholate solution heated at 100 degreeC. After completion of the dropwise addition, heating and stirring were continued at 90 ° C. for 2 hours to obtain an alkali metal salt of a diketopyrrolopyrrole compound. And 600 parts of methanol, 600 parts of water, and 304 parts of acetic acid were added to the reaction container with a glass jacket, and it cooled to -10 degreeC. The cooled mixture was added with a small amount of an alkali metal salt solution of a diketopyrrolopyrrole compound obtained before cooling to 75 ° C. while rotating a shared disk having a diameter of 8 cm at 4000 rpm using a high-speed stirring dispenser. It was. At this time, while the temperature of the mixture consisting of methanol, acetic acid and water is always maintained at a temperature of -5 ° C or lower, while cooling, adjusting the rate of addition of the alkali metal salt of the diketopyrrolopyrrole compound of 75 ° C, about 120 Add in small portions over minutes. After addition of the alkali metal salt, red crystals precipitated and a red suspension was formed. Subsequently, the obtained red suspension was washed with the ultrafiltration apparatus at 5 degreeC, and it filtered and obtained the red paste. The paste was redispersed in 3500 parts of methanol cooled to 0 deg. C, made into a suspension having a methanol concentration of about 90%, stirred at 5 deg. C for 3 hours, and particle formation and washing followed by crystal transition were performed. Subsequently, the water paste of the diketopyrrolopyrrole compound obtained by filtration with an ultrafilter was dried at 80 degreeC for 24 hours, and it grind | pulverized, and 145.8 parts of diketopyrrolopyrrole pigment compositions were obtained.

In the same manner as in the preparation of the pigment composition 16 (R-16), the brominated diketopyrrolopyrrole pigment represented by the formula (1) in the diketopyrrolopyrrole pigment composition and the specific hetero represented by the formula (B-2-1) The content of diketopyrrolopyrrole pigment B was quantitatively analyzed using HPLC, and as a result, the brominated diketopyrrolopyrrole pigment represented by formula (1) and the specific hetero diketopyrrole 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 introduced into a stainless 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, stirred for 1 hour while heating to about 80 ° C. to form a slurry, filtered and washed to remove salt and diethylene glycol, and then dried at 80 ° C. overnight and ground. This obtained 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]

(Production of Pigment Composition 20 (R-20))

100.0 parts of brominated diketopyrrolopyrrole pigment of Formula (1), 1000 parts of sodium chloride, and 120 parts of diethylene glycol were thrown in the stainless gallon kneader (Inoue Manufacturing Co., Ltd.), and it knead | mixed at 60 degreeC for 10 hours. . Next, the kneaded mixture was poured into warm water, stirred for 1 hour while heating to about 80 ° C. to form a slurry, filtered and washed to remove salt and diethylene glycol, and then dried at 80 ° C. overnight and ground. By this, 96.6 parts of pigment composition 20 (R-20) which is a diketopyrrolopyrrole pigment composition were obtained. The average primary particle diameter was 38.9 nm.

[Reference Example 2]

(Production of Pigment Composition 21 (R-21))

70.0 parts of brominated diketopyrrolopyrrole pigment of Formula (1), 30.0 parts of specific hetero diketopyrrolopyrrole pigment B of Formula (B-2-1), 1000 parts of sodium chloride, and 120 parts of diethylene glycol, 1 gallon kneader made of stainless steel ( Inoue Manufacturing Co., Ltd. product), and it knead | mixed at 60 degreeC for 10 hours. Next, the kneaded mixture was poured into warm water, stirred for 1 hour while heating to about 80 ° C. to form a slurry, filtered and washed to remove salt and diethylene glycol, and then dried at 80 ° C. overnight and ground. By this, 95.8 parts of pigment composition 21 (R-21) which is a diketopyrrolopyrrole pigment composition were obtained. The average primary particle diameter was 28.4 nm.

[Referential Example 3]

(Production of Pigment Composition 22 (R-22))

50.0 parts of brominated diketopyrrolopyrrole pigment of formula (1), 50.0 parts of specific hetero diketopyrrolopyrrole pigment B of formula (B-2-1), 1000 parts of sodium chloride, and 120 parts of diethylene glycol, 1 gallon kneader made of stainless steel ( Inoue Manufacturing Co., Ltd. product), and it knead | mixed at 60 degreeC for 10 hours. Next, the kneaded mixture was poured into warm water, stirred for 1 hour while heating to about 80 ° C. to form a slurry, filtered and washed to remove salt and diethylene glycol, and then dried at 80 ° C. overnight and ground. By this, 94.8 parts of pigment composition 22 (R-22) which is a diketopyrrolopyrrole pigment composition were obtained. The average primary particle diameter was 35.4 nm.

[Reference Example 4]

(Production of Pigment Composition 23 (R-23))

80.0 parts of specific hetero diketopyrrolopyrrole pigment B of Formula (B-2-1), 1000 parts of sodium chloride, and 110 parts of diethylene glycol are charged in a stainless steel gallon kneader (manufactured by Inoue Manufacturing Co., Ltd.), and 60 It knead | mixed for 10 hours at ° C. Next, the kneaded mixture was poured into warm water, stirred for 1 hour while heating to about 80 ° C. to form a slurry, filtered and washed to remove salt and diethylene glycol, and then dried at 80 ° C. overnight and ground. By this, 76.8 parts of pigment compositions 23 (R-23) which are diketopyrrolopyrrole pigment compositions were obtained. The average primary particle diameter was 39.4 nm.

[Reference Example 5]

(Production of Pigment Composition 24 (R-24))

70.0 parts of brominated diketopyrrolopyrrole pigment of Formula (1), 30.0 parts of specific hetero diketopyrrolopyrrole pigment B of Formula (B-2-4a), 1000 parts of sodium chloride, and 120 parts of diethylene glycol, 1 gallon kneader made of stainless steel ( Inoue Manufacturing Co., Ltd. product), and it knead | mixed at 60 degreeC for 10 hours. Next, the kneaded mixture was poured into warm water, stirred for 1 hour while heating to about 80 ° C. to form a slurry, filtered and washed to remove salt and diethylene glycol, and then dried at 80 ° C. overnight and ground. By this, 95.8 parts of pigment composition 24 (R-24) which is a diketopyrrolopyrrole pigment composition were obtained. The average primary particle diameter was 27.3 nm.

[Referential Example 6]

(Production of Pigment Composition 25 (R-25))

100.0 parts of commercial CI Pigment Red 254 (`` Irgaphor Red B-CF '' made by Ciba Specialty Chemicals Inc.), 1000 parts of sodium chloride and 120 parts of diethylene glycol, 1 gallon kneader (manufactured by Inoue Manufacturing Co., Ltd.) It was thrown in and knead | mixed at 60 degreeC for 10 hours. Next, the kneaded mixture was poured into warm water, stirred for 1 hour while heating to about 80 ° C. to form a slurry, filtered and washed to remove salt and diethylene glycol, and then dried at 80 ° C. overnight and ground. By this, 97.8 parts of pigment compositions 25 (R-25) which are diketopyrrolopyrrole pigment compositions were obtained. The average primary particle diameter was 36.3 nm.

[Reference Example 7]

(Production of Pigment Composition 26 (R-26))

90.0 parts of commercial CI Pigment Red 254 (“Irgaphor Red B-CF” manufactured by Ciba Specialty Chemicals Inc.), 10.0 parts of specific hetero diketopyrrolopyrrole pigment B of formula (B-2-1), sodium chloride 1000 parts, and di 120 parts of ethylene glycol was thrown in the 1 gallon kneader made from stainless steel (made by Inoue Manufacturing Co., Ltd.), and it knead | mixed at 60 degreeC for 10 hours. Next, the kneaded mixture was poured into warm water, stirred for 1 hour while heating to about 80 ° C. to form a slurry, filtered and washed to remove salt and diethylene glycol, and then dried at 80 ° C. overnight and ground. By this, 95.8 parts of pigment composition 26 (R-26) which is a diketopyrrolopyrrole pigment composition were obtained. The average primary particle diameter was 31.4 nm.

The contents of the prepared pigment compositions 1 to 26 (R-1 to 26) are shown in Table B-1. "PR254" described in Table B-1 is C.I. It means Pigment Red 254.

[Table B-1]

(Production of Dianthraquinone Pigment 1 (PR177-1))

90 parts of dianthraquinone pigments (CI Pigment Red 177), 900 parts of sodium chloride, and 110 parts of diethylene glycol were introduced into a stainless 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, stirred for 1 hour while heating to about 80 ° C. to form a slurry, filtered and washed to remove salt and diethylene glycol, and then dried at 80 ° C. overnight and ground. By doing this, 85.0 parts of dianthraquinone pigment 1 (PR177-1) were obtained. The average primary particle diameter was 38.2 nm.

(Production of Azo Pigment 1 (PY150-1))

90 parts of azo pigments (CI Pigment Yellow 150), 900 parts of sodium chloride, and 110 parts of diethylene glycol were charged into a stainless 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, stirred for 1 hour while heating to about 80 ° C. to form a slurry, filtered and washed to remove salt and diethylene glycol, and then dried at 80 ° C. overnight and ground. Thus, 85.0 parts of azo pigment 1 (PY150-1) were obtained. The average primary particle diameter was 26.2 nm.

(Preparation of acrylic resin solution 1)

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

(Preparation of acrylic resin solution 2)

Into a detachable four-necked flask, 207 parts of cyclohexanone were added to a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube, and a stirring device, and the temperature was raised to 80 ° C. 20 parts of methacrylic acid, 20 parts of paracumyl phenol ethylene oxide modified acrylates (made by Toagosei Co., Ltd., Aronix M110), 45 parts of methyl methacrylates, and 8.5 parts of 2-hydroxyethyl methacrylates And a mixture of 1.33 parts of 2,2'-azobisisobutyronitrile were 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 copolymer solution obtained, after stirring while stopping nitrogen gas and injecting dry air for 1 hour, after cooling to room temperature, 2-methacryloyloxyethyl isocyanate (Karenz MOI manufactured by Showa Denko KK) The mixture of 6.5 parts, dibutyltin laurate 0.08 parts, and 26 parts of cyclohexanone was dripped at 70 degreeC over 3 hours. After completion of the dropwise addition, the reaction was continued for another 1 hour to obtain a solution of an acrylic resin. After cooling to room temperature, about 2 parts of a resin solution was sampled, and it heat-dried at 180 degreeC for 20 minutes, and measured a non volatile matter, and cyclohexanone was added to the resin solution synthesize | combined previously so that a non-volatile content might be 20 mass%, and an acrylic resin was carried out. Solution 2 was prepared. The weight average molecular weight (Mw) was 18000.

(Weight Average Molecular Weight of Binder Resin)

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

[Example 20]

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

The mixture of the compounding compositions shown below was stirred and mixed uniformly, dispersed in PICO MILL (manufactured by ASADA Iron Works Co., Ltd.) for 8 hours using 0.1 mm diameter zirconia beads, and then filtered with a 5 μm filter. Thus, coloring composition 1 (RP-1) was produced.

Diketopyrrolopyrrole pigment composition 1 (R-1) 11.0 parts

1.0 part of pigment derivative (14-1)

Acrylic resin solution 1 40.0 parts

Propylene glycol monomethyl ether acetate 48.0 parts

EXAMPLES 21-38

(Production of Colored Compositions 2 to 19 (RP-2 to 19))

Coloring compositions 2 to 19 (RP-2 to 19) were produced by the same method as the coloring composition 1 (RP-1) except that the pigment composition 1 (R-1) was changed to the pigment composition shown in Table B-2. It was.

[Example 39]

(Production of Coloring Composition 20 (RP-20))

The mixture of the compounding compositions shown below was stirred and mixed uniformly, dispersed in PICO MILL for 8 hours using 0.1 mm diameter zirconia beads, and then filtered through a 5 μm filter to obtain a colored composition 20 (RP-20). Produced.

Diketopyrrolopyrrole pigment composition 19 (R-19) 11.0 parts

1.0 part of pigment derivative (6-3)

6.0 parts of resin type dispersant (BYK161 by BYK-Chemie company (30% solution))

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 compounding compositions shown below was uniformly stirred and mixed, dispersed in PICO MILL for 8 hours using 0.1 mm diameter zirconia beads, filtered through a 5 μm filter, and the colored composition 21 (RP-21) was filtered. Produced.

Diketopyrrolopyrrole pigment composition 19 (R-19) 12.0 parts

3.6 parts of resin type dispersant (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 8-14]

(Production of Coloring Compositions 22-28 (RP-22-28))

Coloring compositions 22-28 (RP-22-28) were produced by the same method as coloring composition 1 (RP-1), except that the pigment composition 1 (R-1) was changed to the pigment composition shown in Table B-2. It was.

[Table B-2]

(Production of Coloring Composition 29 (RP-29))

The mixture of the compounding compositions shown below was stirred and mixed uniformly, dispersed in PICO MILL for 8 hours using 0.1 mm diameter zirconia beads, filtered through a 5 μm filter, and the colored composition 29 (RP-29) was obtained. Produced.

10.8 parts of dianthraquinone pigments (PR177-1)

1.2 parts of dye derivatives (8-5)

Acrylic resin solution 1 40.0 parts

Propylene glycol monomethyl ether acetate 48.0 parts

(Production of Coloring Composition 30 (YP-30))

The mixture of the compounding compositions shown below was uniformly stirred and mixed, dispersed in PICO MILL for 8 hours using 0.1 mm diameter zirconia beads, and filtered through a 5 μm filter to obtain a colored composition 30 (YP-30). Produced.

Azo pigment (PY150-1) 12.0 parts

6.0 parts of resin type dispersants (BYK6919 made by BYK-Chemie) (50% solution)

Acrylic resin solution 1 25.0 parts

Propylene glycol monomethyl ether acetate 57.0 parts

[Example 41]

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

38.2 parts of coloring composition 1 (RP-1)

3.8 parts coloring composition 29 (RP-29)

Acrylic resin solution 2 13.2 parts

2.0 parts of photoinitiators ("Irgacure-907" made by Ciba Japan K.K.)

Ethylene glycol monomethyl ether acetate 39.6 parts

EXAMPLES 42-61

(Production of Photosensitive Coloring Compositions 2 to 21 (RR-2 to 21))

The coloring composition 1 (RP-1) is changed to coloring compositions 2-21 (RP-2-21), and the ratio of coloring compositions 2-21 (RP-2-21) and coloring composition 29 (RP-29) is again Photosensitive coloring compositions 2-21 (RP-2-21) were produced by the method similar to Example 41 except having changed (a ratio change in 42 parts of total amounts of a coloring composition). On the other hand, about a ratio change, the ratio of coloring composition 2-21 (RP-2-21) and coloring composition 29 (RP-29) so that it may match x chromaticity of x = 0.640 and y = 0.328 by C light source at the time of coating film evaluation. Changed.

[Reference Examples 15-18, 20, 21]

(Production of the photosensitive coloring composition 22-25, 27, 28 (RR-22-25, 27, 28))

Coloring composition 1 (RP-1) was changed to coloring compositions 22-25, 27, 28 (RP-22-25, 27, 28), and coloring compositions 22-25, 27, 28 (RP-22-25, 27, 28) and the photosensitive coloring composition 22-25, by the method similar to Example 41 except having changed the ratio of the coloring composition 29 (RP-29) within 42 parts of total amounts of a coloring composition). 27, 28 (RR-22-25, 27, 28) was produced. On the other hand, about ratio change, coloring composition 22-25, 27, 28 (RP-22-25, 27, 28) and coloring composition are matched with chromaticity of x = 0.640 and y = 0.328 by C light source at the time of coating film evaluation. The ratio of 29 (RP-29) was changed.

[Reference Example 19]

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

Change coloring composition 1 (RP-1) to coloring composition 26 (RP-26) and coloring composition 29 (RP-29) to coloring composition 30 (YP-30), and again with coloring composition 26 (RP-26) A photosensitive coloring composition 26 (RR-26) was produced in the same manner as in Example 41 except that the ratio of the coloring composition 30 (YP-30) was changed (a ratio was changed within 42 parts of the total amount of the coloring composition). . On the other hand, about a ratio change, the ratio of the coloring composition 26 (RP-26) and the coloring composition 30 (YP-30) was changed so that it might match x chromaticity of x = 0.640 and y = 0.328 by C light source at the time of coating film evaluation.

Evaluation of the crystal characteristic by the color characteristic, contrast ratio, and heat of the red coating film produced using the obtained photosensitive coloring composition (RR-1-28) was performed by the following method. The kind and evaluation result of the coloring composition in the photosensitive coloring composition are shown in Table B-3.

(Evaluation of Color Properties of Coating Film)

On the glass substrate 100 mm x 100 mm and 0.7 mm thick, the photosensitive coloring composition was apply | coated with the film thickness of x = 0.640 and y = 0.328 in a C light source, and after drying, it was 300 mJ / cm <2> using an ultrahigh pressure mercury lamp. Ultraviolet rays were irradiated. And the red coating film was obtained by heating at 230 degreeC for 60 minutes. Then, the brightness (Y) of the obtained coating film was measured with the microscopic spectrophotometer ("OSP-SP200" by Olympus Optical Co., Ltd.). In addition, chromaticity was also measured with the microscopic spectrophotometer ("OSP-SP200" by Olympus Optical Co., Ltd.).

(Contrast Ratio Evaluation of Coating Film)

The measuring method of the contrast ratio of a coating film is demonstrated. The light emitted from the backlight unit for liquid crystal display is polarized through the polarizing plate, passes through the dry coating film of the coloring composition applied on the glass substrate, and reaches the polarizing plate. If the polarizing plane of the polarizing plate and the polarizing plate are parallel, light is transmitted through the polarizing plate, but when the polarizing plane is straight, the light is blocked by the polarizing plate. However, when light polarized by the polarizing plate passes through the dry coating film of the coloring composition, scattering due to pigment particles occurs, and when a part of the polarizing plane is displaced, when the polarizing plates are parallel, the amount of light passing through the polarizing plate decreases, and the polarizing plate In this case, some light passes through the polarizing plate. This transmitted light was measured as the brightness | luminance on a polarizing plate, and the ratio (contrast ratio) of the brightness | luminance at the time of parallel (orthogonal) and the brightness | luminance when a polarizing plate is parallel was computed.

(Contrast ratio) = (parallel brightness) / (parallel brightness)

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

(Evaluation of crystallization on the surface of coating film)

On the 100 mm x 100 mm and 0.7 mm thick glass substrate, the photosensitive coloring composition was apply | coated with the film thickness of x = 0.640 in C light source, and it dried and irradiated with 300mJ / cm <2> ultraviolet-rays using the ultrahigh pressure mercury lamp. . Subsequently, after heat processing for 60 minutes at 230 degreeC, the heat processing for 60 minutes was repeated twice at 240 degreeC. After the heat treatment, the coating film surface of the substrate was observed with an optical microscope, and the presence or absence of crystal precipitation was determined according to the following criteria.

(Circle): After heat-processing at 230 degreeC for 60 minutes, there is no crystal | crystallization even after heat processing at 240 degreeC for 60 minutes (Crystal precipitation in the heat processing for 60 minutes at the 2nd 240 degreeC)

X: crystallization exists after heat treatment at 230 ° C. for 60 minutes

[Table B-3]

From the results of Table B-3, in forming the color filter, a diketopyrrolopyrrole system containing a brominated diketopyrrolopyrrole pigment and a specific hetero diketopyrrolopyrrole pigment B in a specific ratio (mass ratio 97: 3 to 85:15) The example using the pigment composition was found to be particularly excellent in brightness, to have high contrast, and to suppress crystallization of diketopyrrolopyrrole pigments by a heating step.

In the comparison of Example 43 and Reference Example 21, the photosensitive coloring composition using the diketopyrrolopyrrole pigment composition containing a brominated diketopyrrolopyrrole pigment and a specific hetero diketopyrrolopyrrole pigment B is conventionally used CI pig As a result, the crystal brightness was higher than that of the photosensitive coloring composition containing cement red 254. In addition, it was found that the brominated diketopyrrolopyrrole pigment containing no specific hetero diketopyrrolopyrrole pigment B of Reference Example 15 was excellent in brightness but low in contrast, and crystal precipitation was not suppressed. And from the result of Example 42, Examples 45-47, and Examples 49-53, it was also confirmed that the effect by using specific hetero diketopyrrolopyrrole pigment B depends on the kind.

In Examples 41 to 44 and Reference Examples 15 to 18, the higher the content ratio of the specific hetero diketopyrrole pigment of the formula (B-2-1), the lower the brightness, but the crystal precipitation inhibiting effect tends to increase. I found out. In addition, there is an optimum point for contrast, and it has been found that a balance between brightness and contrast can be achieved by controlling the content ratio of specific hetero diketopyrrole pigments.

In Examples 42 and 56, a pigment composition prepared by the succinic acid diester co-synthesis method, a brominated diketopyrrolopyrrole pigment and a specific hetero diketopyrrolopyrrole pigment B were separately synthesized and mixed during the salt milling process. It has been found that the same effect is obtained in one pigment composition. Moreover, the same effect was confirmed also in the comparison of Example 43 and Example 59.

In Examples 56 to 58, it was found that the dye derivative treatment is effective in suppressing high contrast and crystallization.

&Lt; Fabrication of color filter &

The green photosensitive coloring composition and blue photosensitive coloring composition used for preparation of a color filter were produced. In addition, about red, the photosensitive coloring composition 16 (RR-16) of this Example B was used.

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

The mixture of the compounding compositions shown below was uniformly stirred and mixed, dispersed in PICO MILL for 8 hours using 0.1 mm diameter zirconia beads, and then filtered through a 5 μm filter to obtain a green coloring composition 1 (GP-1). Was produced.

Green pigment (C.I. Pigment Green 36) 6.8

5.2 parts of yellow pigment (C.I. pigment yellow 150)

1.0 part of resin type dispersant ("EFKA4300" made 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 of the following composition was stirred and mixed to make it uniform, and it filtered with the filter of 1 micrometer, and produced the green photosensitive coloring composition 1 (GR-1).

42.0 parts of green coloring composition 1 (GP-1)

Acrylic resin solution 2 13.2 parts

2.0 parts of photoinitiators ("Irgacure-907" made by Ciba Japan K.K.)

Ethylene glycol monomethyl ether acetate 39.6 parts

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

The mixture of the compounding compositions shown below was stirred and mixed uniformly, dispersed for 8 hours in PICO MILL using 0.1 mm diameter zirconia beads, filtered through a 5 μm filter, and then the blue coloring composition 1 (BP-1). Was produced.

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

4.8 parts of purple pigment (C.I. pigment violet 23)

1.0 part of resin type dispersant ("EFKA4300" made 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 of the following composition was stirred and mixed to make it uniform, and it filtered with the filter of 1 micrometer, and produced the blue photosensitive coloring composition 1 (BR-1).

34.0 parts of blue coloring composition 1 (BP-1)

Acrylic resin solution 2 15.2 parts

2.0 parts of photoinitiators ("Irgacure-907" made by Ciba Japan K.K.)

Ethylene glycol monomethyl ether acetate 45.1 parts

The black matrix was pattern-processed on the glass substrate, and the photosensitive coloring composition 16 (RR-16) was apply | coated to the film thickness which becomes x = 0.640 and y = 0.328 by the spin coater on this substrate, and the coloring film was formed. This film was irradiated with ultraviolet light of 300 mJ / cm 2 using an ultra-high pressure mercury lamp through a photomask. Subsequently, spray development was carried out with an alkaline developer consisting of 0.2% by weight aqueous sodium carbonate solution to remove unexposed portions, and then washed with ion-exchanged water, and the substrate was heated at 230 ° C. for 20 minutes to form a red filter segment. By the same method, the green photosensitive coloring composition 1 (GR-1) is set to x = 0.300 and y = 0.600, and x = 0.150 and y = 0.060 are obtained using blue photosensitive coloring composition 1 (BR-1). It apply | coated with the film thickness used respectively, the green filter segment and the blue filter segment were formed, and the color filter was obtained.

By using the photosensitive coloring composition 16 (RR-16), the color filter which was high brightness and high contrast, and has no crystal precipitation in the heating process was able to be produced.

[ Example C]

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

(Specific surface area of pigment)

The specific surface area of the pigment particle was calculated | required by the BET method by nitrogen adsorption. In addition, the automatic steam adsorption amount measuring apparatus ("BELSORP 18" by BEL Japan, Inc.) was used for the measurement.

(Average primary particle size of pigment)

The average primary particle diameter of the pigment was measured by the method of directly measuring the size of a primary particle from the electron microscope photograph. Specifically, the short axis diameter and long axis diameter of the primary particles of each pigment were measured, and the average was made the particle diameter of the pigment particle. Next, about 100 or more pigment particles, the volume (weight) of each particle was calculated | required approximated by the cube of the particle size calculated | required, and the volume average particle diameter was made into the average primary particle diameter. On the other hand, the electron microscope used a transmission type (TEM).

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

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

(Acid value of resin)

80 ml of acetone and 10 ml of water were added to 0.5-1 g of the resin solution, stirred, and dissolved uniformly. An 0.1 mol / L aqueous KOH solution was used as a titration solution, and an automatic titration device ("COM-555" Hiranuma Sangyo Co., Ltd. ), And the acid value of the resin solution was measured. And the acid value per solid content of resin was computed from the acid value of the resin solution and the solid content concentration of the resin solution.

(Contrast ratio of coating film)

The light emitted from the backlight unit for liquid crystal display is polarized through the polarizing plate, passes through the dry coating film of the coloring composition applied on the glass substrate, and reaches the polarizing plate. If the polarizing plane of the polarizing plate and the polarizing plate are parallel, light is transmitted through the polarizing plate, but when the polarizing plane is straight, the light is blocked by the polarizing plate. However, when light polarized by the polarizing plate passes through the dry coating film of the coloring composition, scattering due to pigment particles occurs, and when a part of the polarizing plane is displaced, when the polarizing plates are parallel, the amount of light passing through the polarizing plate decreases, and the polarizing plate In this case, some light passes through the polarizing plate. This transmitted light was measured as the brightness | luminance on a polarizing plate, and the ratio (contrast ratio) of the brightness | luminance when a polarizing plate is parallel, and the brightness | luminance at the time of going straight was computed.

(Contrast ratio) = (parallel brightness) / (parallel brightness)

Prior to the examples, the binder resin (B) solution used in the examples and the reference examples, the pigment (A1) shown in the formula (1), the micronized pigment, and the production method of the pigment dispersion will be described.

[Alkali Soluble Photosensitive Resin (B1-1)]

370 parts of cyclohexanone were added to a detachable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube, and a stirring device, and the temperature was raised to 80 ° C. Cumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.) 18 parts, benzyl methacrylate 10 parts, glycidyl methacrylate 18.2 parts, methyl methacrylate 25 parts and 2,2'-azo A mixture of 2.0 parts of bisisobutyronitrile was added dropwise over 2 hours. After dripping was made to react at 100 degreeC again for 3 hours, the thing which melt | dissolved 1.0 part of azobisisobutyronitrile with 50 parts of cyclohexanone was added, and reaction was continued at 100 degreeC for 1 hour. Next, the inside of the container was replaced with air substitution, 0.5 parts of trisdimethylaminophenol and 0.1 part of hydroquinone were added to 9.3 parts of acrylic acid (equivalent to glycidyl group) in the container, and the reaction was continued at 120 ° C. for 6 hours to give a solid acid value of 0.5. The reaction was complete | finished at the time of becoming, and the solution of acrylic resin was obtained. Then, 19.5 parts of tetrahydrophthalic anhydride (equivalent of the produced hydroxyl group) and 0.5 part of triethylamine were added, and it reacted at 120 degreeC for 3.5 hours, and obtained the solution of acrylic resin.

After cooling to room temperature, approximately 2 g of the resin solution was sampled, dried at 180 ° C. for 20 minutes, and the non-volatile content was measured. PGMEA was added to the non-volatile content of 20 wt% to the resin solution synthesized above to give an alkali-soluble photosensitive resin. (B1-1) A solution was obtained. The weight average molecular weight (Mw) was 19000.

[Acrylic Resin Solution 1]

370 parts of cyclohexanone were put into the reaction vessel, and heated to 80 ° C while injecting nitrogen gas into the container, and 20.0 parts of methacrylic acid, 10.0 parts of methyl methacrylate, 55.0 parts of n-butyl methacrylate and 2- at the same temperature. A mixture of 15.0 parts of hydroxyethyl methacrylate and 4.0 parts of 2,2'-azobisisobutyronitrile was added dropwise over 1 hour to conduct a polymerization reaction. After completion | finish of dripping, after making it react at 80 degreeC again for 3 hours, the thing which melt | dissolved 1.0 part of azobisisobutyronitrile in 50 parts of cyclohexanone was added, and reaction was continued at 80 degreeC for 1 hour further, and the acrylic resin solution was obtained. .

After cooling to room temperature, about 2 g of the acrylic resin solution was sampled and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the acrylic resin solution synthesized so that the nonvolatile content was 20% by weight. An acrylic resin solution 1 was obtained. The weight average molecular weight (Mw) was 40000.

First, 200 parts of tert-amyl alcohol and 140 parts of sodium-tert-amyl alkoxide dehydrated with a molecular sieve were added to a stainless steel reaction vessel with a reflux tube, and heated to 100 ° C. while stirring to give an alcoholate. The solution was prepared. On the other hand, 88 parts of diisopropyl succinate and 153.6 parts of 4-bromobenzonitrile were added to the glass flask, and it heated and melt | dissolved at 90 degreeC, stirring, and prepared the solution of these mixtures. The heating solution of this mixture was slowly dripped at the fixed speed over 2 hours, stirring vigorously in the said alcoholate solution heated at 100 degreeC. After completion of the dropwise addition, heating and stirring were continued at 90 ° C. for 2 hours to obtain an alkali metal salt of a diketopyrrolopyrrole compound. And 600 parts of methanol, 600 parts of water, and 304 parts of acetic acid were added to the reaction container with a glass jacket, and it cooled to -10 degreeC. The cooled mixture was added with a small amount of an alkali metal salt solution of a diketopyrrolopyrrole compound obtained before cooling to 75 ° C. while rotating a shared disk having a diameter of 8 cm at 4000 rpm using a high-speed stirring dispenser. It was. At this time, while the temperature of the mixture consisting of methanol, acetic acid and water is always maintained at a temperature of -5 ° C or lower, while cooling, adjusting the rate of addition of the alkali metal salt of the diketopyrrolopyrrole compound of 75 ° C, about 120 Add in small portions over minutes. After addition of the alkali metal salt, red crystals precipitated and a red suspension was formed. Subsequently, the obtained red suspension was washed with the ultrafiltration apparatus at 5 degreeC, and it filtered and obtained the red paste. The paste was redispersed in 3500 parts of methanol cooled to 0 deg. C, made into a suspension having a methanol concentration of about 90%, stirred at 5 deg. C for 3 hours, and particle formation and washing followed by crystal transition were performed. Subsequently, the water paste of the diketopyrrolopyrrole compound obtained by filtration with an ultrafilter was dried at 80 ° C. for 24 hours, and pulverized to obtain brominated diketopyrrolopyrrole pigment 1, which is the pigment (A1) shown in formula (1). 150.8 parts were obtained.

[Brominated diketopyrrolopyrrole pigment (A1-1)]

Brominated diketopyrrolopyrrole pigment 1 was charged in 100.0 parts, 1000 parts of sodium chloride, 120 parts of diethylene glycol, and 1 gallon kneader made from stainless steel (Inoue Manufacturing Co., Ltd.), and it knead | mixed at 60 degreeC for 2 hours. Next, the kneaded mixture was poured into warm water, stirred for 1 hour while heating to about 80 ° C. to form a slurry, filtered and washed to remove salt and diethylene glycol, and then dried at 80 ° C. overnight and ground. Thus, 96.5 parts of brominated diketopyrrolopyrrole pigment (A1-1) shown in Formula (1) were obtained. 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 thrown into the stainless gallon kneader (Inoue Manufacturing Co., Ltd.), and it knead | mixed at 60 degreeC for 4 hours. Next, the kneaded mixture was poured into warm water, stirred for 1 hour while heating to about 80 ° C. to form a slurry, filtered and washed to remove salt and diethylene glycol, and then dried at 80 ° C. overnight and ground. Thus, 96.6 parts of brominated diketopyrrolopyrrole pigment (A1-2) were obtained. The average primary particle diameter was 55 nm and specific surface area was 45 m ² / g.

[Brominated diketopyrrolopyrrole pigment (A1-3)]

100.0 parts of brominated diketopyrrolopyrrole pigment 1, 1000 parts of sodium chloride, and 120 parts of diethylene glycol were thrown into the stainless gallon kneader (Inoue Manufacturing Co., Ltd.), and it knead | mixed at 60 degreeC for 8 hours. Next, the kneaded mixture was poured into warm water, stirred for 1 hour while heating to about 80 ° C. to form a slurry, filtered and washed to remove salt and diethylene glycol, and then dried at 80 ° C. overnight and ground. 96.5 parts of brominated diketopyrrolopyrrole pigments (A1-3) were obtained by doing this. 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 brominated diketopyrrolopyrrole pigment 1, 1000 parts of sodium chloride, and 120 parts of diethylene glycol were thrown into the stainless gallon kneader (Inoue Manufacturing Co., Ltd.), and it knead | mixed at 60 degreeC for 12 hours. Next, the kneaded mixture was poured into warm water, stirred for 1 hour while heating to about 80 ° C. to form a slurry, filtered and washed to remove salt and diethylene glycol, and then dried at 80 ° C. overnight and ground. 96.2 parts of brominated diketopyrrolopyrrole pigment (A1-4) were obtained by this. The average primary particle diameter was 30 nm and specific surface area was 120 m ² / g.

[Brominated diketopyrrolopyrrole pigment (A1-5)]

100.0 parts of brominated diketopyrrolopyrrole pigment 1, 1000 parts of sodium chloride, and 120 parts of diethylene glycol were thrown into the stainless gallon kneader (Inoue Manufacturing Co., Ltd.), and it knead | mixed at 60 degreeC for 24 hours. Next, the kneaded mixture was poured into warm water, stirred for 1 hour while heating to about 80 ° C. to form a slurry, filtered and washed to remove salt and diethylene glycol, and then dried at 80 ° C. overnight and ground. 96.2 parts of brominated diketopyrrolopyrrole pigment (A1-5) were obtained by this. The average primary particle diameter was 19 nm and specific surface area was 180 m ² / g.

[Bromide Diketopyrrolopyrrole Pigment (A1-6)]

100.0 parts of brominated diketopyrrolopyrrole pigment 1, 1000 parts of sodium chloride, and 120 parts of diethylene glycol were thrown into the stainless gallon kneader (Inoue Manufacturing Co., Ltd.), and it knead | mixed at 60 degreeC for 48 hours. Next, the kneaded mixture was poured into warm water, stirred for 1 hour while heating to about 80 ° C. to form a slurry, filtered and washed to remove salt and diethylene glycol, and then dried at 80 ° C. overnight and ground. 96.2 parts of brominated diketopyrrolopyrrole pigment (A1-6) were obtained by this. The average primary particle diameter was 9 nm and specific surface area was 270 m ² / g.

The content of the produced brominated diketopyrrolopyrrole pigment (A1-1-6) is shown in Table C-1.

TABLE C-1

&Lt; Production method of pigment dispersion >

[Pigment Dispersion (P-1)]

The mixture of the following composition was uniformly stirred and mixed, and then dispersed in an Eiger mill (“mini model M-250 MKII” manufactured by Eiger Japan Co., Ltd.) for 5 hours using zirconia beads having a diameter of 1 mm. Filtration was carried out with a micrometer filter to obtain a red pigment dispersion (P-1).

8.78 parts of brominated diketopyrrolopyrrole pigment (A1-1)

1.74 parts of acidic resin pigment dispersants

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

Diketopyrrolopyrrole pigment derivative 2.05 parts

(58)

Derivative 1

Acrylic resin solution 1 5.83 parts

81.60 parts cyclohexanone

[Pigment Dispersion (P-2)]

Red pigment dispersion (P-) in the same manner as red pigment dispersion (P-1) except for changing the brominated diketopyrrolopyrrole pigment (A1-1) to the brominated diketopyrrolopyrrole pigment (A1-2). 2) was obtained.

[Pigment Dispersion (P-3)]

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

Pigment Dispersion (P-4)

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

[Pigment Dispersion (P-5)]

Pigment dispersion (P-5) in the same manner as red pigment dispersion (P-1) except for changing the brominated diketopyrrolopyrrole pigment (A1-1) to the brominated diketopyrrolopyrrole pigment (A1-5). )

[Pigment Dispersion (P-6)]

Red pigment dispersion (P-) in the same manner as red pigment dispersion (P-1) except for changing the brominated diketopyrrolopyrrole pigment (A1-1) to the brominated diketopyrrolopyrrole pigment (A1-6). 6) was obtained.

[Pigment Dispersion (P-7)]

Red pigment dispersion (P) except that the brominated diketopyrrolopyrrole pigment (A1-1) was changed to a chlorinated diketopyrrolopyrrole pigment (CI Pigment Red 254; "Irgaphor Red B-CF" manufactured by Ciba Japan KK) Red pigment dispersion (P-7) was obtained by the same method as -1).

[Pigment Dispersion (P-8)]

The mixture of the following composition was uniformly stirred and mixed, and then dispersed in an Eiger mill (“mini model M-250 MKII” manufactured by Eiger Japan Co., Ltd.) for 5 hours using zirconia beads having a diameter of 1 mm. Filtration was carried out with a 탆 filter to obtain a pigment dispersion (P-8).

6.82 parts of brominated diketopyrrolopyrrole pigment (A1-3)

1.08parts of anthraquinone pigments (C.I.Pigment Red 177)

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

0.88 parts of nickel azo complex pigment (C.I.Pigment Yellow 150)

(`` E4GN '' made in Lanxess Corporation)

1.74 parts of acidic resin pigment dispersants

(`` Solsperse 21000 '' made 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 cyclohexanone

[Pigment Dispersion (P-9 ~ 20)]

Pigment dispersion (P-9-20) by the same method as a pigment dispersion (P-8) except having changed into the kind and compounding quantity of a pigment, a pigment derivative, and a resinous pigment dispersant shown in Table C-2. Got.

TABLE C-2

Abbreviations in Table C-2 are as follows.

PR254; Diketopyrrolopyrrole pigment C.I. Pigment Red 254

`` Irgaphor Red B-CF '' made by Ciba Japan K.K.

PO71; Diketopyrrolopyrrole pigment C.I. Pigment Orange 71

`` Irgazin DPP orange 398 '' made by Ciba Japan K.K.

PR242; Azo pigment C.I. Pigment Red 242

Clariant (Japan) K.K.Novoperm

PR179; Perylene Pigment C.I. Pigment Red 179

`` FastogenSuper Maroon PSK '' by Dainippon Ink and Chemicals, Inc.

PR122; Quinacridone pigments C.I. Pigment Red 122

`` Hostaperm '' made by Clariant (Japan) K.K.

PY180; Benzimidazolone Pigment C.I. Pigment Yellow 180

Clariant (Japan) K.K.``PV Fast Yellow HG

PY138; Quinoline Pigment C.I. Pigment Yellow 180

`` Paliotol Yellow K0960-HD '' made by BASF Corporation

Pigment Derivatives

(60)

Derivative 2

(61)

Derivative 3

(62)

Derivative 4

Example 1

(Red coloring composition (DR-1))

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

40.5 parts of red pigment dispersion (P-1)

8.6 parts of alkali-soluble photosensitive resin (B1-1)

50.9 parts of cyclohexanone

[Examples 2 to 6 and Reference Example 1]

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

Red coloring composition (DR-2-7) by the method similar to red coloring composition (DR-1) except having changed the red pigment dispersion (P-1) into the red pigment dispersion shown in Table C-3. )

[Reference Example 2]

(Red coloring composition (DR-8))

A red coloring composition (DR-8) was obtained by the same method as red coloring composition (DR-1) except having changed alkali-soluble photosensitive resin (B1-1) into acrylic resin solution 1.

[Evaluation of Red Coloring Composition]

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

(Color characteristic, contrast ratio (CR) evaluation)

The obtained red coloring composition was applied on a 100 mm x 100 mm, 0.7 mm thick glass substrate with a film thickness of x = 0.644 and y = 0.340 (within ± (plus minus) 0.001) in a C light source, at 70 ° C. It dried with the hot-air oven for 20 minutes, and again heated at 230 degreeC for 60 minutes, and obtained the red coating film. Thereafter, brightness (Y) and contrast ratio (CR) of the obtained coated substrate were measured.

(Evaluation of crystallization on the surface of coating film)

The board | substrate obtained by color characteristic and contrast ratio (CR) evaluation was repeated twice with heat processing for 60 minutes at 240 degreeC. 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 determined according to the following criteria. In the evaluation results, ◎ and 양호 are good because there is no crystal precipitation, △ is a level where crystal precipitation is present but there is no problem in use, and x corresponds to a state that cannot be used due to crystal precipitation.

X: crystallization exists after heat treatment at 230 ° C. for 60 minutes

TABLE C-3

Although the coloring composition for color filters containing the pigment (A1) and alkali-soluble photosensitive resin (B1) shown by Formula (1) are all high brightness and high contrast ratio, crystal precipitation of a diketopyrrolopyrrole pigment is also performed by a heating process. Good results have been obtained that this does not occur.

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

(Photosensitive coloring composition)

Each material was mixed and stirred with the composition and compounding quantity shown to Table C-4-9, it filtered with the filter of 1 micrometer, and obtained the photosensitive coloring composition.

Table C-4

Table C-5

Table C-6

Table C-7

Table C-8

Table C-9

It shows below about the abbreviation in Tables C-4-9.

Photoinitiator D1: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one

(`` Irgacure 907 '' made by Ciba Japan K.K.)

Photoinitiator D2: 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone

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

Photoinitiator D3: ethan-1-one, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl], 1- (O-acetyloxime)

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

Photoinitiator D4: 2,2'-bis (o-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole

(`` Biimidazole '' made by Kuroganee Kasei Co., Ltd.)

Photoinitiator D5: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide

(`` Lucirin TPO '' made by BASF Corporation)

Sensitizer E1: 2, 4- diethyl thioxanthone

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

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

(`` EAB-F '' made by Hodogaya Chemical Co., Ltd.)

Photopolymerizable compound: dipentaerythritol hexaacrylate

(`` Aronix M-402 '' made by Toagosei Co., Ltd.)

Multifunctional thiol F1: trimethylol ethane tris (3-mercapto butyrate)

(`` TEMB '' made by Showa Denko K.K.)

Multifunctional thiol F2: trimethylolpropane tri (3-mercaptobutyrate)

(`` TPMB '' made by Showa Denko K.K.)

Multifunctional thiol F3: pentaerythritol tetrakis (3-mercaptopropionate)

(`` PEMP '' made by Sakai Chemical Industry Co., Ltd.)

UV absorber G1: 2- [4-[(2-hydroxy-3- (dodecyl and tridecyl) oxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl ) -1,3,5-triazine

(`` TINUVIN 400 '' made by Ciba Japan K.K.)

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

(`` TINUVIN 900 '' made in Ciba Japan KK)

Polymerization inhibitor H1: N-nitrosophenylhydroxylamine aluminum salt

(`` Q-1301 '' made by Wako Pure Chemical Industries, Ltd.)

Polymerization inhibitor H2: methylhydroquinone

(`` MH '' made by Seiko Chemical Co., Ltd.)

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

(`` BHT '' made by Honshu Chemical Industry Co., Ltd.)

Storage stabilizer J2: triphenylphosphine

(`` TPP '' made by Hokko Chemical Industry Co., Ltd.)

Organic solvents: cyclohexanone

[Evaluation of the photosensitive coloring composition]

About the obtained photosensitive coloring composition, color characteristics, contrast ratio (CR), crystal precipitation, sensitivity, linearity, pattern shape, resolution, image development resistance, chemical resistance, and aging stability of the coating film surface were evaluated by the following method. The results are shown in Table C-10. In each evaluation result, (circle) was a very good level, (circle) was a good level, (triangle | delta) was the level which does not interfere with use, and x made it the level which is not preferable for use.

(Color characteristic, contrast ratio (CR) evaluation)

The obtained photosensitive coloring composition was applied on a 100 mm × 100 mm, 0.7 mm thick glass substrate with a film thickness of x = 0.640 and y = 0.328 in a C light source after post-treatment, and dried at 70 ° C. for 20 minutes in a hot air oven. Thereafter, using an ultrahigh pressure mercury lamp, ultraviolet exposure was performed at an accumulated light amount of 150 mJ, followed by heating and cooling at 230 ° C for 1 hour to obtain a red coating film. Thereafter, brightness (Y) and contrast ratio (CR) of the obtained coated substrate were measured.

(Evaluation of crystallization on the surface of coating film)

The board | substrate obtained by color characteristic and contrast ratio (CR) evaluation was further heated and left to cool at 260 degreeC for 1 hour. 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 determined according to the following criteria. In the evaluation results, ◎ is very good without crystallization, 는 is a good level with some crystallization, △ is a level with crystallization but no problem in use, and × corresponds to a state that cannot be used due to crystallization. .

◎: 0 crystals

○: 1 or more and less than 10 crystals

△: 10 or more crystals and less than 100 crystals

×: 100 or more crystals

(Sensitivity, linearity, pattern shape, resolution, development resistance, chemical resistance evaluation)

After coating the obtained photosensitive coloring composition on a glass substrate of 100 mm x 100 mm and 0.7 mm thickness, it heated for 20 minutes at 70 degreeC in a clean oven, and removed the solvent, and obtained the coating film of about 2 micrometers. Subsequently, after cooling this board | substrate to room temperature, the ultra-high pressure mercury lamp was used and the ultraviolet-ray was exposed through the photomask of a 100 micrometer width (pitch 200 micrometer) and a 25 micrometer width (pitch 50 micrometer) stripe pattern. Thereafter, the substrate was spray-developed using an aqueous 23 ° C. sodium carbonate solution, washed with ion-exchanged water, and air dried, and heated at 230 ° C. for 330 minutes in a clean oven. Spray development was performed with respect to the coating film in each photosensitive coloring composition in the shortest time which can form a pattern without image development residue, and made it the appropriate image development time.

The film thickness of the coating film was performed using Dektak 3030 (made by Japan Vacuum Technology Co., Ltd. (now ULVAC, Inc.)).

(Sensitivity evaluation)

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

○: less than 50 mJ / cm 2

Δ: 50 mJ / cm 2 or more but less than 100 mJ / cm 2

×: 100 mJ / cm 2 or more

(Linearity evaluation)

The pattern in the 100 micrometer photomask part of the filter segment formed by the said method was evaluated after observation using the optical microscope. The rank of evaluation is as follows.

○: good linearity

△ partially defective linearity

X: linearity defect

(Pattern Shape Evaluation)

The cross section of the pattern in the 100 micrometer photomask part of the filter segment formed by the said method was evaluated after observation using the electron microscope. The pattern cross section has a good taper. The rank of evaluation is as follows.

○: cross section forward tapered

×: Cross section inverse taper shape

(Resolution evaluation)

The pattern in the 25 micrometer photomask part of the filter segment formed by the said method was evaluated after observation using the optical microscope. The rank of evaluation is as follows. Resolution defect means that adjacent stripe patterns are connected or a defect generate | occur | produces.

◎: good resolution and linearity

○: slightly inferior in linearity but good resolution

△: partially poor resolution

×: poor resolution

(Impact Tolerance Evaluation)

At the time of spray development, the pattern film thickness in the 100 micrometer photomask part of the filter segment formed by developing at twice the titration time was measured, and it compared with the pattern film thickness formed by developing in the appropriate development time. The rank of evaluation is as follows.

◎: within 20% of the film thickness difference

○: film thickness greater than 20%, less than 40%

△: film thickness difference is greater than 40%

X: defect or peeling (torn off) occurs due to double phenomenon

(Drug Resistance Evaluation)

The filter segment formed by the above method was immersed in N-methylpyrrolidone solution for 30 minutes, washed with ion-exchanged water, and air-dried, and evaluated after observing the pattern in the 100-micrometer photomask part using the optical microscope. The rank of evaluation is as follows.

◎: Good without change in appearance and color

(Circle): Wrinkle etc. generate in some parts, but color is favorable without a change.

△: slight discoloration (color fading) occurs

×: peeling or discoloration occurs

(Time stability evaluation of a coloring composition)

About the obtained photosensitive coloring composition, the viscosity after 1 month of initial stage and room temperature was measured, and the grade of viscosity increase with respect to initial stage viscosity was computed and evaluated. The rank of evaluation is as follows.

(Time-viscosity change rate) = | [(initial viscosity)-(time-viscosity viscosity)] / (initial viscosity) | x100 (%)

(Double-circle): The rate of viscosity increase is good in 5% or less.

○: The rate of increase in viscosity is greater than 5% and less than 10%

×: rate of viscosity increase is greater than 10%

Table C-10

As shown in Table C-10, the coloring composition for color filters containing the pigment (A1) and photosensitive resin (B1) shown by Formula (1) obtained the high level of evaluation result in all the evaluations.

(Manufacture of color filter)

4.54 parts of the pigment and pigment derivative in the photosensitive coloring composition (RR-1) were CI Pigment Green 58 / CI Pigment Yellow 150 = 2.72 parts / 1.82 parts in the green photosensitive coloring composition, and CI Pigment Blue 15 in the blue photosensitive coloring composition. : A pigment dispersion was prepared in the same manner as the pigment dispersion (P-3) except that 6 / CI Pigment Violet 23 was substituted with 3.63 parts / 0.91 parts, and further, a pigment dispersion of the photosensitive coloring composition (RR-1). Was substituted with each color pigment dispersion, and the green photosensitive coloring composition for color filters and the blue photosensitive coloring composition for color filters were obtained.

The photosensitive coloring composition (RR-1) was coated by a die coater on a 100 mm x 100 mm glass substrate to a thickness of about 2 m, and the solvent was removed by drying for 20 minutes in an oven at 70 ° C. Subsequently, stripe pattern exposure was performed by ultraviolet rays using an exposure apparatus. The exposure amount was 100 mJ / cm 2. Again, the developer was spray-developed with a developer solution of aqueous sodium carbonate to remove the unexposed portions, and then washed with ion-exchanged water. The substrate was heated at 230 ° C. for 30 minutes to form a red filter segment having a line width of about 50 μm. Subsequently, in the same manner, the green filter segment is formed by using the green photosensitive coloring composition next to the red filter segment, and then the blue filter segment is formed by using the blue photosensitive coloring composition, and three color filter segments are provided on the same glass substrate. A color filter was obtained.

When the coloring composition for color filters mentioned above was used, the high-definition color filter which has the red filter segment which was excellent in color characteristic and heat resistance in a wide chromaticity range was able to be produced.

Example D

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

(Specific surface area of pigment)

(Average primary particle size of pigment)

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

(Acid value of resin)

(Contrast ratio of coating film)

(Contrast ratio) = (parallel brightness) / (parallel brightness)

[Resin Solution (B1-1)]

(Step 1: Polymerization of Resin Main Chain)

In a detachable four-necked flask, 100 parts of propylene glycol monomethyl ether acetate (PGMAC) was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirring device, and heated to 120 ° C while injecting nitrogen gas into the vessel. At the same temperature, a mixture of 16.2 parts of styrene, 35.5 parts of glycidyl methacrylate, 41.0 parts of dicyclopentanyl methacrylate and 1.0 part of azobisisobutyronitrile as a catalyst necessary for the compounding of the precursor in this step was prepared from 2.5 It dripped over time and performed the polymerization reaction.

(Step 2: Polymerization for Epoxy Group)

Subsequently, the flask was air-substituted, 0.3 parts of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were charged as 17.0 parts of acrylic acid and the catalyst required for polymerization of the precursor in this step, and the reaction was carried out at 120 ° C. for 5 hours to give a weight. A resin solution having an average molecular weight of about 12000 (measured by GPC) was obtained. Since the added acrylic acid is ester-bonded to the terminal of the epoxy group of the glycidyl methacrylate structural unit, it does not produce a carboxyl group in the resin structure.

(Step 3: polymerization on hydroxyl groups)

Furthermore, as a catalyst required for the polymerization of 30.4 parts of tetrahydrophthalic anhydride and the precursor in this step, 0.5 part of triethylamine was added and reacted at 120 ° C for 4 hours. In the added tetrahydrophthalic anhydride, one of the two carboxyl groups generated by cleaving the carboxylic acid anhydride site is ester-bonded to the hydroxyl group in the resin structure, and the other produces the carboxyl end.

(Step 4: Adjustment of nonvolatile matters)

Propylene glycol monomethyl ether acetate was added so that a non volatile matter might be 40%, and the resin solution (B1-1) was obtained.

The weight ratio of the structural unit in the resin solution (B1-1) is tetrahydrophthalic anhydride as the structural unit (D-b1); 21.7 weight% styrene as a structural unit (D-b2); 11.6 weight%, dicyclopentanyl methacrylate as a structural unit (D-b3); 29.3% by weight, total of glycidyl methacrylate and acrylic acid ester-bonded to its glycidyl terminal as other structural units; 37.4% by weight.

[Resin Solution (B1-2)]

Synthetic reaction was carried out in the same manner as for the resin solution (B1-1), except that dicyclopentanyl methacrylate of the resin solution (B1-1) was used as the dicyclopentenyl methacrylate. )

[Resin Solution (B1-3)]

Synthetic reaction was carried out in the same manner as the resin solution (B1-1), except that dicyclopentanyl methacrylate of the resin solution (B1-1) was used as dicyclopentenyloxyethyl methacrylate. -3) was prepared.

[Resin Solution (B1-4)]

370 parts of PGMEA were added to a detachable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube, and a stirring device, and the temperature was raised to 80 ° C. After nitrogen replacement of the flask, the paracumylphenol was added from the dropping tube. 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'-azobisiso A mixture of 2.0 parts of butyronitrile was added dropwise over 2 hours. After dripping was made to react at 100 degreeC again for 3 hours, the thing which melt | dissolved 1.0 part of azobisisobutyronitrile with 50 parts of cyclohexanone was added, and reaction was continued at 100 degreeC for 1 hour. Next, the inside of the container was replaced with air substitution, 0.5 parts of trisdimethylaminophenol and 0.1 part of hydroquinone were added to 9.3 parts (equivalent of epoxy group) of acrylic acid in the container, and the reaction was continued at 120 ° C. for 6 hours to give a solid acid value of 0.5. At that point, the reaction was terminated to obtain a solution of acrylic resin. Then, 19.5 parts of tetrahydrophthalic anhydride (equivalent of the produced hydroxyl group) and 0.5 part of triethylamine were added, and it reacted at 120 degreeC for 3.5 hours, and obtained the solution of acrylic resin.

After cooling to room temperature, about 2 g of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the nonvolatile content, and PGMEA was added to the above synthesized resin solution so that the nonvolatile content was 20% by weight to the acrylic resin solution (B1). -4) was prepared. The weight average molecular weight (Mw) was 19000.

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

Resin solution (B1-5)-(B1-15) and (B2-1)-(B2-5) were prepared by the method similar to resin solution (B1-1).

That is, precursors corresponding to structural units (D-b1) to (D-b3) and other structural units in the manufacturing method of the resin solution (B1-1) were replaced in accordance with Table D-1. In the case of the resin solution in which GMA-AA or GMA-MAA does not exist in the table, all precursors are mixed to perform only steps 1 and 4 of the preparation. If GMA-AA or GMA-MAA is present in the table and THPA is present, GMA-AA or GMA-MAA is first selected from GMA and structural units (D-b2), (D-b3) and other structural units. Step 1 of Preparation was carried out by mixing the precursors excluded, followed by Step 2 of Preparation by adding epoxy equivalent AA or MAA of GMA as a precursor, followed by Step 3 and Step 4 of Preparation by adding THPA as a precursor. Is carried out. If GMA-AA or GMA-MAA is present in the table, and THPA is not present, GMA-AA or GMA-MAA is first selected from GMA and structural units (D-b1) to (D-b3) and other structural units. Except the precursor was mixed to carry out step 1 of the preparation, and then step 2 of the preparation was carried out by adding AA or MAA of an epoxy equivalent of GMA as a precursor, followed by step 4 again. The number of copies of the catalyst required for each step is mixed in proportion to the total number of precursors mixed in each step.

The composition and weight ratio of the obtained resin solution (B1-1-15) and resin solution (B2-1-4) are shown in Table D-1. The parenthesis shows the weight ratio (weight%) of the structural unit in the resin solid content.

TABLE D-1

Explanation of the abbreviation of the precursor and structural unit of a structural unit in Table D-1

MAA: methacrylic acid

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

BzMA: benzyl methacrylate

St: Styrene

M110: paracumyl phenol ethylene oxide modified acrylate

DCPMA: Dicyclopentanyl methacrylate

GMA: glycidyl methacrylate

GMA-AA: Acrylic acid is added to the structural unit GMA by reaction

GMA-MAA: The addition of methacrylic acid to the structural unit GMA

BMA: n-butyl methacrylate

[Preparation of Resin Solution (B2-5)]

After cooling to room temperature, about 2 g of the acrylic resin solution was sampled and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the acrylic resin solution synthesized so that the nonvolatile content was 20% by weight. Resin solution (B2-5) was prepared. The weight average molecular weight (Mw) was 40000.

[Brominated diketopyrrolopyrrole pigment (A1-1)]

In a stainless steel reaction vessel with a reflux tube, 200 parts of tert-amyl alcohol and 140 parts of sodium-tert-amyl alkoxide dehydrated with a molecular sieve were added under a nitrogen atmosphere and heated to 100 ° C. while stirring to prepare an alcoholate solution. It prepared. On the other hand, 88 parts of diisopropyl succinate and 153.6 parts of 4-bromobenzonitrile were added to the glass flask, and it heated and dissolved at 90 degreeC, stirring, and prepared the solution of these mixtures. The heating solution of this mixture was slowly dripped at the fixed speed over 2 hours, stirring vigorously in the said alcoholate solution heated at 100 degreeC. After completion of the dropwise addition, heating and stirring were continued at 90 ° C. for 2 hours to obtain an alkali metal salt of a diketopyrrolopyrrole compound. And 600 parts of methanol, 600 parts of water, and 304 parts of acetic acid were added to the reaction container with a glass jacket, and it cooled to -10 degreeC. The cooled mixture was added with a small amount of an alkali metal salt solution of a diketopyrrolopyrrole compound obtained before cooling to 75 ° C. while rotating a shared disk having a diameter of 8 cm at 4000 rpm using a high-speed stirring dispenser. It was. At this time, while the temperature of the mixture consisting of methanol, acetic acid and water is always maintained at a temperature of -5 ° C or lower, while cooling, adjusting the rate of addition of the alkali metal salt of the diketopyrrolopyrrole compound of 75 ° C, about 120 Add in small portions over minutes. After addition of the alkali metal salt, red crystals precipitated and a red suspension was formed. Subsequently, the obtained red suspension was washed with the ultrafiltration apparatus at 5 degreeC, and it filtered and obtained the red paste. The paste was redispersed in 3500 parts of methanol cooled to 0 deg. C, made into a suspension having a methanol concentration of about 90%, stirred at 5 deg. C for 3 hours, and particle formation and washing followed by crystal transition were performed. Subsequently, the bromine diketopyrrolopyrrole pigment, which is the pigment (A1) shown in formula (1), was pulverized by filtration with an ultrafilter and drying the water paste of the obtained diketopyrrolopyrrole compound at 80 ° C. for 24 hours, followed by grinding. Got boo.

100.0 parts of the obtained brominated diketopyrrolopyrrole pigment, 1000 parts of sodium chloride, and 120 parts of diethylene glycol were thrown into the stainless gallon kneader (Inoue Manufacturing Co., Ltd. product), and it knead | mixed at 60 degreeC for 8 hours. Next, the kneaded mixture was poured into warm water, stirred for 1 hour while heating to about 80 ° C. to form a slurry, filtered and washed to remove salt and diethylene glycol, and then dried at 80 ° C. overnight and ground. Thus, 96.5 parts of brominated diketopyrrolopyrrole pigment (A1-1) shown in Formula (1) were obtained. 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 of the following composition was uniformly stirred and mixed, and then dispersed in an Eiger mill (“mini model M-250 MKII” manufactured by Eiger Japan Co., Ltd.) for 5 hours using zirconia beads having a diameter of 1 mm. Filtration was carried out with a micrometer filter to obtain a pigment dispersion (P-1).

8.78 parts of brominated diketopyrrolopyrrole pigment (A1-1)

1.74 parts of acidic resin pigment dispersants

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

Pigment derivative 1 2.05 parts

(63)

Derivative 1

5.83 parts of resin solution (B2-5)

81.60 parts cyclohexanone

[Pigment Dispersion (P-2)]

Pigment dispersion (P- except for changing the brominated diketopyrrolopyrrole pigment (A1-1) to chlorinated diketopyrrolopyrrole pigment (CI Pigment Red 254; "Irgaphor Red B-CF" manufactured by Ciba Japan KK) The pigment dispersion (P-2) was obtained by the same method as 1).

[Pigment Dispersion (P-3)]

The mixture of the following composition was uniformly stirred and mixed, and then dispersed in an Eiger mill (“mini model M-250 MKII” manufactured by Eiger Japan Co., Ltd.) for 5 hours using zirconia beads having a diameter of 1 mm. Filtration was carried out with a 탆 filter to obtain a pigment dispersion (P-3).

6.82 parts of brominated diketopyrrolopyrrole pigment (A1-1)

1.08parts of anthraquinone pigments (C.I.Pigment Red 177)

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

0.88 parts Nickel-Azo Pigment Pigment (C.I.Pigment Yellow 150)

(`` E4GN '' made in Lanxess Corporation)

1.74 parts of acidic resin pigment dispersants

(Solsperse 21000 made by The Lubrizol Corporation)

Pigment derivative 1 2.05 parts

&Lt; EMI ID =

Derivative 1

5.83 parts of resin solution (B2-5)

81.60 parts cyclohexanone

[Pigment Dispersion (P-4 ~ 10)]

Pigment dispersion (P-4-11) by the method similar to pigment dispersion (P-3) except having changed into the kind and compounding quantity of a pigment, a pigment derivative, and a resinous pigment dispersant shown in Table D-2. Got.

TABLE D-2

The abbreviation in Table D-2 is shown below.

PR254; Diketopyrrolopyrrole Pigment C.I. Pigment Red 254

`` Irgaphor Red B-CF '' made by Ciba Japan K.K.

PO71; Diketopyrrolopyrrole Pigment C.I. Pigment Orange 71

`` Irgazin DPP orange 398 '' made by Ciba Japan K.K.

PR242; Azo pigments C.I. Pigment Red 242

Clariant (Japan) K.K.Novoperm

PR179; Perylene Pigment C.I. Pigment Red 179

`` FastogenSuper Maroon PSK '' by Dainippon Ink and Chemicals, Inc.

PR122; Quinacridone pigments C.I. Pigment Red 122

`` Hostaperm '' made by Clariant (Japan) K.K.

PY180; Benzimidazolone Pigment C.I. Pigment Yellow 180

Clariant (Japan) K.K.``PV Fast Yellow HG

PY138; Quinoline Pigments C.I. Pigment Yellow 180

`` Paliotol Yellow K0960-HD '' made by BASF Corporation

Pigment Derivatives

(65)

Derivative 2

(66)

Derivative 3

(67)

Derivative 4

Example 1

(Red coloring composition (DR-1))

40.5 parts of red pigment dispersion (P-R1)

8.6 parts of Resin Solution (B1-1)

50.9 parts of cyclohexanone

[Examples 2 to 6 and Reference Example 1]

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

Except having changed resin solution (B1-1) into the resin solution shown in Table D-2, the red coloring composition (DR-2-7) was obtained by the method similar to red coloring composition (DR-1). .

[Reference Example 2]

(Red coloring composition (DR-8))

Red coloring composition (DR-8) was obtained by the same method as red coloring composition (DR-1) except having changed the red pigment dispersion (P-R1) into red pigment dispersion (P-R2). .

[Evaluation of Red Coloring Composition]

The following method evaluated the color characteristic, contrast ratio (CR), and crystal precipitation of the coating film surface of the obtained red coloring composition. The results are shown in Table D-3.

(Color characteristic, contrast ratio (CR) evaluation)

The obtained red coloring composition was applied on a 100 mm × 100 mm, 0.7 mm thick glass substrate with a film thickness of x = 0.644 and y = 0.340 (within ± 0.001) in a C light source, followed by a hot air oven at 70 ° C. for 20 minutes. After drying with, the red coating film was obtained by further heating at 230 degreeC for 60 minutes. Thereafter, brightness (Y) and contrast ratio (CR) of the obtained coated substrate were measured.

(Evaluation of crystallization on the surface of coating film)

X: crystallization exists after heat treatment at 230 ° C. for 60 minutes

Table D-3

Although the coloring composition for color filters containing the pigment (A1) shown to Formula (1) and resin (D-B1) which has structural unit (D-b1)-(D-b3) is all high brightness and high contrast ratio, And the favorable result that the crystal precipitation of a diketopyrrolopyrrole pigment does not arise also by the heating process.

[Examples 7-31, Reference Examples 3-9]

(Photosensitive coloring composition (RR-1-32))

Each material was mixed and stirred with the composition and compounding quantity shown to Table D-4-10, it filtered with the filter of 1 micrometer, and obtained the photosensitive coloring composition (RR-1-32).

Table D-4

Table D-5

Table D-6

Table D-7

Table D-8

Table D-9

Table D-10

It shows below about the abbreviation in Tables D-4-10.

(`` Irgacure 907 '' made by Ciba Japan K.K.)

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

Photoinitiator D3: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide

(`` Lucirin TPO '' made by BASF Corporation)

(`` Biimidazole '' made by Kuroganee Kasei Co., Ltd.)

Photoinitiator D5: p-dimethylaminoacetophenone

(DAIKI FINECHEMICAL Co., Ltd. `` DMA '')

Photoinitiator D6: ethan-1-one, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl], 1- (O-acetyloxime)

(`` Irgacure OXE02 '' made in Ciba Japan KK)

Sensitizer E1: 2, 4-diethyl thioxanthone

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

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

(`` EAB-F '' made by Hodogaya Chemical Co., Ltd.)

Photopolymerizable compound C1: dipentaerythritol hexaacrylate

(`` Aronix M-402 '' made by Toagosei Co., Ltd.)

Multifunctional thiol F1: trimethylol ethane tris (3-mercapto butyrate)

(`` TEMB '' made by Showa Denko K.K.)

Multifunctional thiol F2: trimethylolpropane tri (3-mercaptobutyrate)

(`` TPMB '' made by Showa Denko K.K.)

Multifunctional thiol F3: pentaerythritol tetrakis (3-mercaptopropionate)

(`` PEMP '' made by Sakai Chemical Industry Co., Ltd.)

(`` TINUVIN 400 '' made by Ciba Japan K.K.)

(`` TINUVIN 900 '' made in Ciba Japan KK)

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

(`` BHT '' made by Honshu Chemical Industry Co., Ltd.)

Storage stabilizer J2: triphenylphosphine

(`` TPP '' made by Hokko Chemical Industry Co., Ltd.)

PGMAC: propylene glycol monomethyl ether acetate

[Evaluation of the photosensitive coloring composition]

About the obtained photosensitive coloring composition (RR-1-32), a color characteristic, contrast ratio (CR), crystal precipitation, sensitivity, linearity, pattern shape, resolution, image development resistance, chemical resistance, time-lapse stability, and the like of a coating film surface are as follows. Evaluated. The results are shown in Table D-11. In each evaluation result, (circle) was a very good level, (circle) was a good level, (triangle | delta) was the level which does not interfere with use, and x made it the level which is not preferable for use.

(Color characteristic, contrast ratio (CR) evaluation)

The obtained photosensitive coloring composition was applied onto a glass substrate 100 mm × 100 mm and 0.7 mm thick with a film thickness of x = 0.640 and y = 0.328 after post-treatment in a C light source, and dried at 70 ° C. for 20 minutes in a hot air oven. Subsequently, using an ultra-high pressure mercury lamp, ultraviolet light exposure was carried out with an integrated light quantity of 150 mJ, and then heated at 230 ° C. for 1 hour, and allowed to cool, thereby obtaining a red coating film. Thereafter, brightness (Y) and contrast ratio (CR) of the obtained coated substrate were measured.

(Evaluation of crystallization on the surface of coating film)

The board | substrate obtained by color characteristic and contrast ratio (CR) evaluation was further heated and left to cool at 260 degreeC for 1 hour. 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 determined according to the following criteria. In the evaluation results, ◎ is very good because there is no crystal precipitation, ○ is a good level with some crystal precipitation, △ is a level where crystal precipitation is present but no problem in use, and × corresponds to a state that cannot be used due to crystal precipitation. .

◎: 0 crystals

○: 1 or more and less than 10 crystals

△: 10 or more crystals and less than 100 crystals

×: 100 or more crystals

After coating the obtained photosensitive coloring composition on a glass substrate of 100 mm x 100 mm and 0.7 mm thickness, it heated for 20 minutes at 70 degreeC in a clean oven, and removed the solvent, and obtained the coating film of about 2 micrometers. Subsequently, after cooling this board | substrate to room temperature, the ultra-high pressure mercury lamp was used and the ultraviolet-ray was exposed through the photomask of a 100 micrometer width (pitch 200 micrometer) and a 25 micrometer width (pitch 50 micrometer) stripe pattern. Thereafter, the substrate was spray-developed using a 23 ° C. aqueous sodium carbonate solution, washed with ion-exchanged water, air dried, and heated at 230 ° C. for 330 minutes in a clean oven. Spray development was performed with respect to the coating film in each photosensitive coloring composition in the shortest time which can form a pattern without image development residue, and made it the appropriate image development time.

The film thickness of the coating film was performed using Dektak 3030 (made by Japan Vacuum Technology Co., Ltd.).

(Sensitivity evaluation)

○: less than 50 mJ / cm 2

Δ: 50 mJ / cm 2 or more but less than 100 mJ / cm 2

×: 100 mJ / cm 2 or more

(Linearity evaluation)

○: good linearity

△ partially defective linearity

X: linearity defect

(Pattern Shape Evaluation)

○: cross section forward tapered

×: Cross section inverse taper shape

(Resolution evaluation)

The pattern in the 25 micrometer photomask part of the filter segment formed by the said method was evaluated after observation using the optical microscope. The rank of evaluation is as follows. Resolution defect means that adjacent stripe patterns are connected or a defect generate | occur | produces. The rank of evaluation is as follows.

◎: good resolution and linearity

○: slightly inferior in linearity but good resolution

△: partially poor resolution

×: poor resolution

(Impact Tolerance Evaluation)

◎: within 20% of the film thickness difference

○: film thickness greater than 20%, less than 40%

△: film thickness difference is greater than 40%

X: defect or peeling occurs due to double phenomenon

(Drug Resistance Evaluation)

◎: Good without change in appearance and color

(Circle): Wrinkles generate | occur | produce in some parts, but color is favorable without a change.

△: slight discoloration occurs

×: peeling or discoloration occurs

(Time stability evaluation of a coloring composition)

(Double-circle): The rate of viscosity increase is good in 5% or less.

○: The rate of increase in viscosity is greater than 5% and less than 10%

×: rate of viscosity increase is greater than 10%

Table D-11

As shown in Table D-11, the coloring composition for color filters containing pigment (A1) shown in Formula (1) and resin (D-B1) which has structural units (D-b1)-(D-b3) In all evaluations, a high level of evaluation was obtained.

That is, in the combination with the pigment (A1), in the structure containing a large amount of the structural unit (D-b1) of the resin (D-B1), the improvement of contrast and stabilization of the stability over time are the structural unit (D-b2) In the composition containing a lot, the improvement of brightness and the chemical-resistance improved, and in the composition containing a large number of structural units (D-b3), the effect which suppresses the crystal precipitation of a pigment in a heating process and the effect which suppresses the resolution tends to be confirmed. However, if all of the structural units meet a specific content ratio, it is possible to obtain a photosensitive coloring composition having a high performance. By using an appropriate unit ratio, a high performance and balanced color filter segment can be obtained.

Furthermore, if a photoinitiator (D) is a combination with any one of an acetophenone type compound, a phosphine type compound, an imidazole type compound, and an oxime ester type compound, a sensitivity, linearity, and a resolution are more favorable.

Among them, the photopolymerization initiator (D) is ethan-1-one, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl], 1- (O-acetyloxime) photosensitive In the coloring composition, development resistance was further superior.

Furthermore, in the photosensitive coloring composition containing a polyfunctional thiol, image development resistance was more excellent.

Furthermore, in the photosensitive coloring composition containing a ultraviolet absorber, resolution was more excellent.

Furthermore, in the photosensitive coloring composition containing a storage stabilizer, stability with time was more excellent.

On the other hand, in the photosensitive coloring composition of Reference Examples 3-9, neither the brightness nor the contrast ratio was low, and it was not able to obtain all that was satisfactory also in evaluation of the filter segment including crystal precipitation and sensitivity of the pigment in a heating process.

(Manufacture of color filter)

4.39 parts of a total of the pigment and pigment derivative in the photosensitive coloring composition (RR-1) were CI Pigment Green 58 / CI Pigment Yellow 150 = 2.63 parts / 1.76 parts in the green photosensitive coloring composition, and CI Pigment Blue 15 in the blue photosensitive coloring composition. : 6 / CI Pigment Violet 23 A pigment dispersion was prepared in the same manner as in the pigment dispersion (P-3) except that it was substituted so that it was 3.51 parts / 0.88 parts, and further, the pigment dispersion of the photosensitive coloring composition (RR-1). The sieve was substituted with each color pigment dispersion, and the green photosensitive coloring composition for color filters and the blue photosensitive coloring composition for color filters were obtained.

By using the coloring composition for color filters mentioned above, the high-definition color filter which has the red filter segment which was excellent in color characteristics and heat resistance in a wide chromaticity range was able to be manufactured.

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 same while having good brightness and contrast, and hardly causing crystal precipitation of diketopyrrolopyrrole pigments even by a heating step. .

Claims

In the diketopyrrolopyrrole pigment composition for color filters containing a diketopyrrolopyrrole pigment represented by formula (1) and a diketopyrrolopyrrole pigment represented by formula (A-2), the formula (A-2) Content of the diketopyrrolopyrrole pigment displayed is 1 mass%-15 mass% with respect to the total mass of a diketopyrrolopyrrole pigment, The diketopyrrolopyrrole pigment composition for color filters characterized by the above-mentioned.
[Chemical Formula 1]

[In formula (A-2),
A and B are each independently 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 are each independently 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.
However, A and B do not become hydrogen atoms at the same time.]

The method of claim 1,
The diketopyrrolopyrrole pigment represented by the formula (A-2) is formula (A-2-1), formula (A-2-2), formula (A-2-3) and formula (A-2- 4) a diketopyrrolopyrrole pigment composition for color filters, characterized in that any one selected from the group consisting of.
(2)

[In formula (A-2-3) and formula (A-2-4),
R ⁶ to R ⁸ are each independently an alkyl group having 1 to 12 carbon atoms or a phenyl group which may have a substituent.]

3. The method according to claim 1 or 2,
A diketopyrrolopyrrole pigment composition for color filters, further comprising CI pigment red 254 as a diketopyrrolopyrrole pigment.

The method of claim 3,
Based on the total mass of the diketopyrrolopyrrole pigment, the total content of the diketopyrrolopyrrole pigment represented by the formula (1) and CI Pigment Red 254 is 85% by mass to 99% by mass for color filters Diketopyrrolopyrrole pigment composition.

The method according to claim 3 or 4,
The mass ratio of the diketopyrrolopyrrole pigment represented by Formula (1) and CI Pigment Red 254 is 20: 80-99: 1, The diketopyrrolopyrrole pigment composition for color filters characterized by the above-mentioned.

In the diketopyrrolopyrrole pigment composition for color filters containing a diketopyrrolopyrrole pigment represented by formula (1) and a diketopyrrolopyrrole pigment represented by formula (B-2), formula (1) and formula ( The mass ratio of B-2) is 97: 3-85:15 diketopyrrolopyrrole pigment composition for color filters.
(3)

In 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 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 are each independently 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.
However, A and B do not become hydrogen atoms at the same time.]

The method according to claim 6,
Formula (B-2) is formula (B-2-1), formula (B-2-2), formula (B-2-3), formula (B-2-4), formula (B-2) -5), diketopyrrolopyrrole pigment composition for color filters, characterized in that any one selected from the group consisting of (B-2-6) and (B-2-7).
[Chemical Formula 4]

[In Formula (B-2-4), Formula (B-2-6), and Formula (B-2-7),
R ¹² to R ¹⁵ are each independently a phenyl group which may have an alkyl group having 1 to 12 carbon atoms or a substituent.]

8. The method according to any one of claims 1 to 7,
A diketopyrrolopyrrole pigment composition for color filters, further comprising a dye derivative.

The coloring composition containing a coloring agent, binder resin, and the organic solvent WHEREIN: The coloring agent contains the diketopyrrolopyrrole pigment composition in any one of Claims 1-8, The coloring composition for color filters characterized by the above-mentioned.

10. The method of claim 9,
The coloring composition for color filters which further contains a photopolymerizable monomer and / or a photoinitiator.

In the coloring composition for color filters containing a pigment (A), binder resin (CB), and a solvent, Pigment (A) contains the pigment (A1) shown by Formula (1), and binder resin (CB) An alkali soluble photosensitive resin (C-B1) is contained, The coloring composition for color filters characterized by the above-mentioned.
[Chemical Formula 5]

In the coloring composition for color filters containing a pigment (A), binder resin (DB), and a solvent, Pigment (A) contains the pigment (A1) shown by Formula (1), and binder resin (DB) The resin composition (D-B1) which has structural unit (D-b1)-(D-b3) is included, The coloring composition for color filters characterized by the above-mentioned.
[Chemical Formula 6]

(D-b1) Structural unit having a carboxyl group: 2 to 60 wt%
(D-b2) Structural unit which has an aromatic ring group shown by Formula (D-2) or (D-3): 2-80 weight%
(D-b3) Structural unit which has an aliphatic ring group shown by Formula (D-4) or (D-5): 2-60 weight%
(7)

[Chemical Formula 8]

[In formula (D-2) and (D-3), R is a C1-C20 alkyl group which may have a hydrogen atom or a benzene ring. The dashed portion in formula (D-3) represents a cyclic structure containing one or more saturated or unsaturated heterocycles which may have a substituent adjacent to the benzene ring.]
[Chemical Formula 9]

[Formula 10]

13. The method according to claim 11 or 12,
Pigment (A) is a group consisting of diketopyrrolopyrrole pigments, azo pigments, anthraquinone pigments, perylene pigments, quinacridone pigments, benzimidazolone pigments and quinoline pigments other than pigment (A1) It further contains at least 1 sort (s) or more selected from the color composition for color filters characterized by the above-mentioned.

14. The method according to any one of claims 11 to 13,
The coloring composition for color filters which further contains at least 1 type or more photoinitiators selected from the group which consists of an acetophenone type compound, a phosphine type compound, an imidazole type compound, and an oxime ester type compound.

The color filter provided with the filter segment formed from the coloring composition for color filters in any one of Claims 9-14.