TWI568802B - Colored composition, color filter, and display element - Google Patents

Description

Coloring composition, color filter, and display element

The present invention relates to a coloring composition, a color filter, and a display element, and more particularly to use in forming a transmissive or reflective type color liquid crystal display element, a solid-state imaging element, an organic EL display element, electronic paper, or the like. The color filter is a color filter for a color filter having a coloring layer, a color filter including a coloring layer formed of the coloring composition, and a display element including the color filter.

When a color filter is produced using a coloring sensitizing radiation composition, a method is known in which a pigment dispersion type radiation sensitizing radiation composition is applied onto a substrate and dried, and then the dried coating film is irradiated with radiation in a desired pattern shape ( Hereinafter, it is referred to as "exposure"), and development is performed to obtain a method of each color pixel (see, for example, Patent Documents 1 and 2). Further, a method of forming a black matrix by using a photopolymerizable composition in which carbon black is dispersed is also known (for example, see Patent Document 3). Further, a method of obtaining pixels of respective colors by an inkjet method using a pigment-dispersed resin composition is known (for example, see Patent Document 4).

In recent years, in the technical field of color filters, the trend of shortening the takt time by reducing the exposure amount has become mainstream. There is a strong demand for a colored composition which can be patterned at a low exposure amount and has high sensitivity. Further, since the heating (post-baking) step of more than 200 ° C is experienced in the manufacturing process of the color filter, heat resistance is also required for the color filter formed of the colored composition.

In response to such a request, it has been proposed to use a ruthenium polymer. For example, Patent Document 5 reports that a photosensitive resin composition containing a ruthenium polymer having a specific structure can be used to form a coating film with high sensitivity.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2-144502

[Patent Document 2] Japanese Patent Laid-Open No. 3-53201

[Patent Document 3] Japanese Patent Laid-Open No. Hei 6-35188

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2000-310706

[Patent Document 5] Japanese Patent No. 4733231

However, the present inventors have found that if only the specific ruthenium polymer reported in Patent Document 5 is used for the coloring composition, the storage stability of the colored composition is poor, and it is difficult to practically apply it.

Therefore, an object of the present invention is to provide a colored composition which contains a specific ruthenium polymer and which is excellent in storage stability. Further, another object of the present invention is to provide a color filter including a coloring layer composed of the above colored composition, and a display element including the color filter.

In view of the above, the present inventors conducted intensive studies and found that the above problems can be solved by adding a specific solvent, and thus the present invention has been completed.

In other words, the present invention provides a coloring composition comprising the following components (A), (B1), and (C): (A) a colorant, and (B1) having a structural unit represented by the following formula (1) The polymer (hereinafter also referred to as "(B1) specific polymer"), and (C) contains a solvent selected from at least one of an alcohol and a ketone, and the content ratio of the alcohol and the ketone is the total amount of the solvent. 3 to 50% by mass.

[In the formula (1), the ring Z ¹ and the ring Z ² independently of each other represent a monocyclic or condensed polycyclic hydrocarbon ring.

Y represents a residue obtained by removing four carboxyl groups from an organic compound having four carboxyl groups.

R ^1a and R ^1b independently of each other represent a hydrogen atom or an alkyl group.

R ^2a and R ^2b independently of each other represent a hydrocarbon group, an alkoxy group, a decyl group, an alkoxycarbonyl group, a halogen atom, a nitro group or a cyano group.

R ^3a and R ^3b independently of each other represent a hydrogen atom or a methyl group.

R ^a represents a group having a (meth)acryloxy group.

R ^b represents a group having a hydrogen atom or a (meth) propylene fluorenyloxy group.

K1 and k2 represent an integer of 0 to 4 independently of each other.

M1 and m2 represent an integer of 0 to 3 independently of each other.

N1 and n2 represent an integer of 0 to 10 independently of each other.

t and u represent an integer of 0 to 3 independently of each other. ]

Furthermore, the present invention provides a coloring composition comprising the following components (A), (B2), and (C): (A) a colorant, and (B2) at least a compound represented by the following formula (2); A polymer obtained by a step of adding a (meth) acrylate compound having an oxygen-saturated heterocyclic group to a polymer obtained by reacting a tetrabasic acid dianhydride (hereinafter also referred to as "(B2) specific) The polymers ") and (C) contain a solvent selected from at least one of an alcohol and a ketone, and the content ratio of the alcohol and the ketone is from 3 to 50% by mass based on the total amount of the solvent.

In the formula (2), the ring Z ¹ and the ring Z ² independently of each other represent a monocyclic or condensed polycyclic hydrocarbon ring.

R ^1a and R ^1b independently of each other represent a hydrogen atom or an alkyl group.

R ^2a and R ^2b independently of each other represent a hydrocarbon group, an alkoxy group, a decyl group, an alkoxycarbonyl group, a halogen atom, a nitro group or a cyano group.

R ^3a and R ^3b independently of each other represent a hydrogen atom or a methyl group.

K1 and k2 represent an integer of 0 to 4 independently of each other.

M1 and m2 represent an integer of 0 to 3 independently of each other.

N1 and n2 represent an integer of 0 to 10 independently of each other.

P1 and p2 represent an integer of 1 to 4 independently of each other. ]

Further, the present invention provides a color filter including a coloring layer formed using the colored composition, and a display including the color filter. Here, the "colored layer" refers to each color pixel, black matrix, black spacer, or the like used in the color filter.

The coloring composition of the present invention has good storage stability. Further, the coloring composition is highly sensitive and can form a coloring layer exhibiting high heat resistance. In addition, the colored composition of the present invention can also be used to form A coloring layer excellent in solvent resistance.

Therefore, the colored composition of the present invention can be used very well for a color filter for a color liquid crystal display element, a color separation color filter for a solid-state image sensor, a color filter for an organic EL element, and a color filter for an electronic paper. Light sheets are the production of various color filters.

[Formation of the Invention]

Hereinafter, the present invention will be described in detail.

Coloring Composition Next, the constituent components of the coloring composition of the present invention will be described.

- (A) colorant -

The coloring agent (A) in the present invention can be used without particular limitation, and the color and material can be appropriately selected depending on the use of a color filter or the like. Specific examples of the coloring agent include a pigment, a dye, and a natural coloring matter. These coloring agent components may be used singly or in combination of two or more. Among them, from the viewpoint of obtaining pixels having high luminance, contrast, and color purity, an organic pigment is preferable as the pigment, and an organic dye is preferable as the dye.

As the organic pigment, for example, a compound classified as a pigment in a pigment index (C.I.; The Society of Dyers and Colourists, Inc.), that is, a compound having a pigment index (C.I.) number attached below may be mentioned.

C.I. Pigment Red 166, C.I. Pigment Red 177, C.I. Pigment Red 224, red pigment of CI Pigment Red 242, CI Pigment Red 254, CI Pigment Red 264, etc.; green pigment of CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58, etc.; CI Pigment Blue 15:6, CI Pigment Blue Blue pigment such as 80; CI Pigment Yellow 83, CI Pigment Yellow 129, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 179, CI Pigment Yellow 180, CI Pigment Yellow 185, CI Pigment Yellow 211, yellow pigment such as CI Pigment Yellow 215; orange pigment such as CI Pigment Orange 38; purple pigment such as CI Pigment Violet 23; black pigment such as CI Pigment Black 1, CI Pigment Black 7.

Further, as the pigment, a lake pigment can also be used. In the present invention, "lake pigment" means a substance obtained by using a precipitating agent to make a soluble dye into an insoluble pigment. The present inventors have found that a color filter having a coloring layer formed using a conventional coloring composition containing a lake pigment is inferior in balance between heat resistance and solvent resistance. This problem can be solved by using a lake pigment-containing coloring agent together with (B1) a specific polymer or (B2) a specific polymer.

In the present embodiment, as the lake pigment, there is no particular limitation, and for example, A lake-like pigment, a triarylmethane lake pigment, an azo lake pigment, a phthalocyanine lake pigment, and the like. In the present embodiment, it is preferably A lake-like pigment, a triaryl methane-based lake pigment, and particularly preferably a triarylmethane-based pigment.

On the other hand, as a precipitant for lake formation, for example Examples thereof include barium chloride, calcium chloride, ammonium sulfate, aluminum chloride, aluminum acetate, lead acetate, tannic acid, katanol, tamol, homopoly acid, heteropoly acid and the like. Examples of the polypoly acid include the same polytungstic acid, the same polyvanadic acid, and the same polymolybdic acid. Examples of the heteropoly acid include phosphotungstic acid, phosphomolybdic acid, phosphotungstic acid, and cerium. Tungstomolybdic acid, tungstic acid, lanthanum molybdate, and the like. Among them, a lake pigment which is formed by pre-doping with a polyacid or a heteropoly acid as a precipitating agent is preferred, and a heteropoly acid is used as a precipitating agent to form a precipitant. Lake pigment. A lake pigment obtained by laking with a polyacid or a heteropoly acid as a precipitating agent can be produced, for example, by the method described in JP-A-2011-186043.

Further, as the above dye, it can be mentioned Dyes, triaryl methane dyes, cyanine dyes, anthraquinone dyes, azo dyes, phthalocyanine dyes, quinone imine dyes, quinoline dyes, nitro dyes, methine dyes Etc., among them, preferably Dyes, triaryl methane dyes, cyanine dyes, anthraquinone dyes, azo dyes, and the like. More specifically, JP-A-2010-32999, JP-A-2010-254964, JP-A-2011-138094, International Publication No. 10/123071, and JP-A-2011- An organic dye described in, for example, JP-A-2011-174987, JP-A-2011-174987, and JP-A-2011-174987.

In the present invention, the pigment and the dye may be used alone or in combination of two or more.

In the present invention, it may also be a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a group of these methods. The pigment is refined and used. Further, the pigment may be used after modifying the surface of the particles with a resin as needed. For example, a vehicle resin described in JP-A-2001-108817 or a commercially available resin for dispersing various pigments is used as the resin for modifying the surface of the particles of the pigment. As a method of coating the surface of the carbon black, for example, a method described in JP-A-H09-71733, JP-A-H09-95625, JP-A-9-124969, and the like can be employed. Further, the organic pigment may be used after the primary particles are refined by a so-called salt milling method. As a method of the salt milling method, for example, a method disclosed in Japanese Laid-Open Patent Publication No. Hei 08-179111 can be employed.

Further, in the present invention, a well-known dispersing agent and a dispersing aid may be added together with the pigment. Examples of the known dispersant include a polyurethane dispersant, a polyethyleneimine dispersant, a polyoxyethylene alkyl ether dispersant, a polyoxyethylene alkylphenyl ether dispersant, and a polydispersant. The ethylene glycol diester dispersing agent, the sorbitan fatty acid ester dispersing agent, the polyester dispersing agent, the acrylic dispersing agent, etc., and a dispersing adjuvant, a pigment derivative etc. are mentioned.

Such a dispersant can be obtained by commercial purchase, and for example, Disperbyk-2000, Disperbyk-2001, BYK-LPN 6919, BYK-LPN 21116, BYK-LPN 21324, which are acrylic dispersants, respectively (the above is BYK) Chemical (BYK) company, etc., Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 as a polyurethane dispersant (above BYK (BYK) )), Solsperse 76500 (Lubricol), etc., as a polyethylene imine dispersant, Solsperse-24000 (manufactured by Lubrizol), Ajisper-PB821, Ajisper-PB822, which is a polyester dispersant. Ajisper-PB880, Ajisper-PB881 (above, Ajinomoto Fine-Techno Co., Ltd.), and the like.

In addition, specific examples of the pigment derivative include copper phthalocyanine, diketopyrrolopyrrole, and a sulfonic acid derivative of quinacridone.

From the viewpoint of forming a pixel having high luminance and excellent color purity or a black matrix having excellent light-shielding properties, the content ratio of the (A) coloring agent is usually 5 to 70% by mass, preferably 5, in the solid content of the colored composition. ~60% by mass. The solid component referred to herein means a component other than the solvent (C) to be described later.

- (B) polymer -

The colored composition of the present invention contains the above-mentioned (B1) specific polymer or (B2) specific polymer, and these polymers function as a binder resin and also function as a curing component. In the present specification, the (B1) specific polymer and the (B2) specific polymer are collectively referred to as (B) polymer.

(B2) The polymer obtained by reacting at least a compound represented by the following formula (2) with a tetravalent acid dianhydride (hereinafter also referred to as "(B2') polymer") has an oxygen saturation. A step of a heterocyclic group (meth) acrylate compound is obtained.

In the formula (2), the ring Z ¹ and the ring Z ² independently of each other represent a monocyclic or condensed polycyclic hydrocarbon ring.

R ^1a and R ^1b independently of each other represent a hydrogen atom or an alkyl group.

R ^2a and R ^2b independently of each other represent a hydrocarbon group, an alkoxy group, a decyl group, an alkoxycarbonyl group, a halogen atom, a nitro group or a cyano group.

R ^3a and R ^3b independently of each other represent a hydrogen atom or a methyl group.

K1 and k2 represent an integer of 0 to 4 independently of each other.

M1 and m2 represent an integer of 0 to 3 independently of each other.

N1 and n2 represent an integer of 0 to 10 independently of each other.

P1 and p2 represent an integer of 1 to 4 independently of each other. ]

First, the compound represented by the formula (2) will be described.

The ring Z ¹ and the ring Z ² each independently represent a monocyclic or condensed polycyclic hydrocarbon ring, and examples of the monocyclic hydrocarbon group include a monocyclic hydrocarbon such as benzene. Examples of the condensed polycyclic hydrocarbon include a condensed bicyclic hydrocarbon having 8 to 20 carbon atoms such as anthracene or naphthalene; a condensed polycyclic hydrocarbon having a tricyclic or higher formula such as anthracene or phenanthrene; and the like. The condensed polycyclic hydrocarbon is preferably a condensed bicyclic hydrocarbon having 10 to 16 carbon atoms. Among them, benzene, naphthalene and anthracene are preferred. Ring Z ¹ and ring Z ² may be the same or different.

R ^1a and R ^1b each independently represent a hydrogen atom or an alkyl group, and as the alkyl group, an alkyl group having 1 to 6 carbon atoms is preferable, and specific examples thereof include a methyl group, an ethyl group, a propyl group and an isopropyl group. Base, butyl, secondary butyl, tert-butyl, pentyl, isopentyl, hexyl and the like. Among them, an alkyl group having 1 to 4 carbon atoms is preferred, and a methyl group is more preferred. R ^1a and R ^1b may be the same or different.

K1 and k2 represent an integer of 0 to 4 independently of each other, but are preferably 0 or 1, more preferably 0. Further, when k1 and k2 are 2 or more, a plurality of R ^1a and R ^1b existing may be the same or different.

The substitution position of R ^1a and R ^1b is not particularly limited, and may be substituted on any carbon atom on the benzene ring constituting the anthracene skeleton.

R ^2a and R ^2b independently of each other represent a hydrocarbon group, an alkoxy group, a decyl group, an alkoxycarbonyl group, a halogen atom, a nitro group or a cyano group, and examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group. Wait.

The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms. Specifically, in addition to the alkyl group exemplified as R ^1a and R ^1b , a heptyl group, an octyl group, a decyl group, and ten Dialkyl and the like. Among these alkyl groups, an alkyl group having 1 to 8 carbon atoms is more preferable, and an alkyl group having 1 to 6 carbon atoms is particularly preferable.

The cycloalkyl group is preferably a cycloalkyl group having 5 to 10 carbon atoms, and specific examples thereof include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Among these, a cycloalkyl group having 5 to 8 carbon atoms is preferred, and a cycloalkyl group having 5 or 6 carbon atoms is more preferred.

The aryl group is preferably an aryl group having 6 to 10 carbon atoms, and specific examples thereof include a phenyl group and an alkylphenyl group. Examples of the alkylphenyl group include a methylphenyl group and a dimethylphenyl group. More preferably among these aryl groups It is an aryl group having a carbon number of 6 to 8, and particularly preferably a phenyl group. Examples of the methylphenyl group include an o-tolyl group, a m-tolyl group, and a p-tolyl group. Examples of the dimethylphenyl group include a xylyl group and the like.

The aralkyl group is preferably an aralkyl group having 7 to 14 carbon atoms, and specific examples thereof include an alkyl group having 1 to 4 carbon atoms bonded to an aryl group having 6 to 10 carbon atoms. More specifically, a benzyl group, a phenethyl group, etc. are mentioned. Among these, a group in which an alkyl group having 1 to 2 carbon atoms is bonded to an aryl group having 6 to 8 carbon atoms is more preferable.

The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, and specific examples thereof include a methoxy group, an ethoxy group, and a butoxy group.

The fluorenyl group having 1 to 6 carbon atoms is preferable as the fluorenyl group, and specific examples thereof include an acetyl group and the like.

The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 1 to 4 carbon atoms, and specific examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, and a butoxycarbonyl group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

In the above, R ^2a and R ^{2b are} preferably an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkoxy group, more preferably an alkyl group having 1 to 6 carbon atoms, and a carbon number of 5~. a cycloalkyl group of 8 , an aryl group having 6 to 10 carbon atoms, a group having an alkyl group having 1 to 2 carbon atoms bonded to an aryl group having 6 to 8 carbon atoms, and an alkyl group having 1 to 4 carbon atoms; The oxy group is particularly preferably an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 8 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms. R ^2a and R ^2b may be the same or different.

M1 and m2 independently represent an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0. Further, when m1 and m2 are 2 or more, a plurality of R ^2a and R ^2b present may be the same or different.

The position of substitution of R ^2a and R ^2b is not particularly limited, and substitution may be carried out on any carbon atom on ring Z ¹ and ring Z ² .

R ^3a and R ^3b independently of each other represent a hydrogen atom or a methyl group. When a plurality of R ^3a and R ^3b are present, they may be the same or different.

P1 and p2 are independently from each other in the range of 1 to 4, but are preferably an integer of 1 to 3, more preferably 1 or 2. Further, the position of substitution of the group having a hydroxyl group is not particularly limited, and substitution may be carried out on any carbon atom on the ring Z ¹ and the ring Z ² .

N1 and n2 independently represent an integer of 0 to 10, preferably an integer of 0 to 4, and more preferably an integer of 0 to 2. Further, when n1 and n2 are 2 or more, the (poly)alkylene oxide group may be composed of the same alkoxy group or may be composed of a different type of alkoxy group. Examples of the combination of different kinds of alkoxy groups include an ethoxy group and a 1,2-epoxypropane group.

Among the compounds represented by the above formula (2), a compound represented by the following formula (4) and formula (5) can be listed as a more suitable example.

[In the formula (4), R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , k1 , k2 , m1 , m2 , n1 , n2 , p1 and p2 have the same meanings as described above. However, m1+p1 is an integer of 4 or less, and m2+p2 is an integer of 4 or less. ]

[In the formula (5), R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , k1 , k2 , m1 , m2 , n1 , n2 , p1 and p2 have the same meanings as described above. However, m1+p1 is an integer of 5 or less, and m2+p2 is an integer of 5 or less. ]

The compound represented by the formula (4) is preferably a 9,9-bis(hydroxyalkoxynaphthyl)anthracene or a 9,9-bis(hydroxypolyalkoxynaphthyl)anthracene.

Examples of the 9,9-bis(hydroxyalkoxynaphthyl)anthracene include 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)anthracene and 9,9-double. (6-(2-hydroxypropoxy)-2-naphthyl)anthracene, 9,9-bis[5-(2-hydroxyethoxy)-1-naphthyl]anthracene, 9,9-bis[5 -(2-Hydroxypropoxy)-1-naphthyl]anthracene.

As the 9,9-bis(hydroxypolyalkoxynaphthyl)anthracene, a 9,9-bis(hydroxydialkoxynaphthyl)anthracene is preferable, and specifically, 9,9-double is exemplified. {6-[2-(2-Hydroxyethoxy)ethoxy]-2-naphthyl}anthracene, 9,9-bis{6-[2-(2-hydroxypropoxy)propoxy]- 2-naphthyl}anthracene, 9,9-bis{5-[2-(2-hydroxyethoxy)ethoxy]-1-naphthalenyl}anthracene, 9,9-double {5-[2-( 9,9-bis(hydroxydiC _2-4 alkoxynaphthyl)anthracene or the like such as 2-hydroxypropoxy)propoxy]-1-naphthyl}anthracene.

The compound represented by the formula (5) is preferably 9,9-bis(hydroxyalkoxyphenyl)anthracene, 9,9-bis(hydroxypolyalkoxydialkylphenyl)anthracene, 9, 9-bis(hydroxyalkoxyarylphenyl)anthracene, 9,9-bis(hydroxypolyalkoxyarylphenyl)anthracene.

Examples of the 9,9-bis(hydroxyalkoxyphenyl)anthracene include 9,9-bis[4-(2-hydroxyethoxy)phenyl]anthracene, 9,9-bis[4- (2-hydroxypropoxy)phenyl]anthracene, 9,9-bis[4-(2-hydroxyethoxy)-3-methylphenyl]anthracene, 9,9-bis[4-(2- Hydroxypropoxy)-3-methylphenyl]anthracene, 9,9-bis[4-(2-hydroxyethoxy)-3,5-dimethylphenyl]anthracene, 9,9-double [ 4-(2-hydroxyethoxy)phenoxyethanol]anthracene, 9,9-bis[4-(2-hydroxypropoxy)phenoxyethanol]anthracene, 9,9-bis[4-(2 -hydroxyethoxy)-3-methylphenyl]anthracene, 9,9-bis[4-(2-hydroxypropoxy)-3-methylphenyl]anthracene, 9,9-bis[4- (2-hydroxyethoxy)-2,5-dimethylphenyl]anthracene, 9,9-bis[4-(2-hydroxypropoxy)-2,5-dimethylphenyl]anthracene, 9,9-bis[4-(2-hydroxyethoxy)-3,6-dimethylphenyl]anthracene, 9,9-bis[4-(2-hydroxypropoxy)-2,6- Dimethylphenyl]anthracene, 9,9-bis[4-(2-hydroxyethoxy)-2,4-dimethylphenyl]anthracene, 9,9-bis[3-(2-hydroxypropane) Oxy)-2,4-dimethylphenyl]anthracene, 9,9-bis[4-(2-hydroxyethoxy)-3,4-dimethylphenyl]anthracene, 9,9-double 9,9-bis(hydroxyalkoxyalkylphenyl) [2-(2-hydroxypropoxy)-3,4-dimethylphenyl]anthracene Class.

As the 9,9-bis(hydroxypolyalkoxyphenyl)anthracene, a 9,9-bis(hydroxydialkoxyphenyl)anthracene is preferable. As a specific example thereof, 9,9-bis[4-(2-hydroxydiethoxy)phenyl]anthracene, 9,9-bis[4-(2-hydroxydipropoxy)phenyl]茀,9,9-bis[4-(2-hydroxydiethoxy)-3- Methylphenyl]anthracene, 9,9-bis[4-(2-hydroxydipropoxy)-3-methylphenyl]anthracene, 9,9-bis[4-(2-hydroxydiethoxyl) -3,5-Dimethylphenyl]anthracene, 9,9-bis[4-(2-hydroxydiethoxy)-2,5-dimethylphenyl]anthracene, 9,9-double [ 4-(2-hydroxydipropoxy)-2,5-dimethylphenyl]anthracene, 9,9-bis[4-(2-hydroxydiethoxy)-3,6-dimethylbenzene茀, 9,9-bis[4-(2-hydroxydipropoxy)-2,6-dimethylphenyl]anthracene, 9,9-bis[4-(2-hydroxydiethoxyl) )-2,4-dimethylphenyl]anthracene, 9,9-bis[3-(2-hydroxydipropoxy)-2,4-dimethylphenyl]anthracene, 9,9-double [ 4-(2-hydroxydiethoxy)-3,4-dimethylphenyl]anthracene, 9,9-bis[2-(2-hydroxydipropoxy)-3,4-dimethylbenzene Base] 茀 and so on.

Examples of the 9,9-bis(hydroxyalkoxyarylphenyl)anthracene include 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]anthracene, 9. 9-bis[4-(2-hydroxypropoxy)-3-phenylphenyl]anthracene, 9,9-bis[4-(2-hydroxypropoxy)-3-tolylphenyl]anthracene, etc. 9,9-bis(hydroxyalkoxyarylphenyl)anthracene, preferably 9,9-bis(2-hydroxyethoxyarylphenyl)anthracene or the like.

The 9,9-bis(hydroxypolyalkoxyarylphenyl)anthracene is preferably a 9,9-bis(hydroxydialkoxyarylphenyl)anthracene, specifically, 9 9,9-bis(hydroxydialkoxyarylphenyl)anthracene of 9-bis{4-[2-(2-hydroxyethoxy)ethoxy]-3-phenylphenyl}anthracene The class is preferably 9,9-bis[2-(2-hydroxyethoxy)ethoxyarylphenyl]anthracene or the like.

In the present invention, as the compound represented by the above formula (2), a compound produced by a usual method can be used, but commercially available products such as BPEF, BOPPEF, and BNFEO (above, Osaka Gas Chemical Co., Ltd.) can also be used.

Next, the tetravalent acid dianhydride will be described.

Examples of the tetravalent acid dianhydride include butane tetracarboxylic dianhydride, pentane tetracarboxylic dianhydride, hexane tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, and cyclopentane tetracarboxylic acid. Dihydride, cyclohexane tetracarboxylic dianhydride, cycloheptane tetracarboxylic dianhydride, lower Alkane tetracarboxylic dianhydride, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, 5-(2,5-dione Tetrahydro-3-furanyl-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 4-(2,5-dionetetrahydrofuran-3-yl)-1,2, 3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,4'-(hexafluoroisopropene) dicarboxylic anhydride, 3,4, 9,10-decanetetracarboxylic dianhydride, 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride, and the like. These compounds may be used singly or in combination of two or more. Among them, pyromellitic dianhydride and 5-(2,5-dionetetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride are preferred. Benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride.

Next, the reaction of the (B2') polymer with a (meth) acrylate compound having an oxygen-containing saturated heterocyclic group will be described.

The (meth) acrylate compound having an oxygen-containing saturated heterocyclic group is not particularly limited as long as it is a compound having one or more oxygen-containing saturated heterocyclic groups and one or more (meth) acrylonitrile groups in the molecule. can. Here, the "oxygen-containing saturated heterocyclic group" means a saturated heterocyclic group having an oxygen atom as a hetero atom constituting a hetero ring. Further, the bonding position of the oxygen-containing saturated heterocyclic group and the (meth)acryl fluorenyl group in the (meth) acrylate compound having an oxygen-saturated heterocyclic group is not limited.

The oxygen-containing saturated heterocyclic group in the present invention is preferably a cyclic ether group having 3 to 7 atoms in the ring, and specific examples thereof include an oxiranyl group and an oxetanyl group. 3,4-epoxycyclohexyl, tetrahydrofuranyl and the like. Among them, from the viewpoint of reactivity, it is preferably epoxy B. Alkyl, oxetanyl, 3,4-epoxycyclohexyl.

The (meth) acrylate compound having an oxygen-containing saturated heterocyclic group, for example, a compound represented by the following formula (3-1), formula (3-2), or formula (3-3) can be exemplified.

In (3-1), formula (3-2), and formula (3-3), R ⁴ represents a hydrogen atom or a methyl group.

R ⁵ represents a single bond or a group represented by the following formula (6).

R ⁶ represents an alkyl group having 1 to 6 carbon atoms. ]

In the formula (6), q, r, and s represent an integer of 0 to 9 independently of each other.

However, q, r, and s are not 0 at the same time, and the -C ₂ H ₄ O- group, the -C ₃ H ₆ O- group, and the -C ₄ H ₈ O- group may be bonded in any order. ]

In the formula (6), the -C ₂ H ₄ O- group means a linking group containing an ethyl group and an ethane-1,1-diyl group, and the -C ₃ H ₆ O- group means a propane-1,1 group. a linking group of a diyl group, a propane-1,2-diyl group, a propane-1,3-diyl group, and a propane-2,2-diyl group. Further, -C ₄ H ₈ O-group means including butane-1,2-diyl, butane-1,3-diyl, butane-1,4-diyl, butane-2,2- A linking group of a diradical, butane-2,3-diyl or the like.

R ^{6 is} preferably an alkyl group having 1 to 4 carbon atoms, and specific examples thereof include the same groups as described above.

Examples of the compound represented by the above formula (3-1) include glycidyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate glycidyl ether, and 2-hydroxypropyl (meth)acrylate. (meth) acrylate glycidyl ether, 3-hydroxypropyl (meth) acrylate glycidyl ether, 4-hydroxybutyl (meth) acrylate glycidyl ether, polyethylene glycol polypropylene glycol (methyl) Acrylate glycidyl ether and the like.

In addition, examples of the compound represented by the above formula (3-2) include 3,4-epoxycyclohexylmethyl (meth)acrylate.

In addition, examples of the compound represented by the above formula (3-3) include 3-(methacryloxymethyl)-3-methyloxetane and 3-(methacryloxyloxy group). Methyl)-3-ethyloxetane, 3-(acryloxymethyl)-3-methyloxetane, 3-(acryloxymethyl)-3-ethyl Oxetane and the like.

The polymer obtained by reacting the (B2') polymer with the (meth) acrylate compound having an oxygen-containing saturated heterocyclic group may be used as the (B2) specific polymer as it is, or a part of the residual carboxyl group may be used. The glycidyl ether or the like is sealed and used as the (B2) specific polymer. By blocking a part of the carboxyl group, the acid value of the (B2) specific polymer can be suppressed.

The (B2) specific polymer of the present invention is preferably a polymer having a structural unit represented by the following formula (1).

[In the formula (1), the ring Z ¹ , the ring Z ² , R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , k1 , k2 , m1 , m2 , n1 and n 2 have the same meanings as described above.

Y represents a residue obtained by removing four carboxyl groups from an organic compound having four carboxyl groups.

R ^a represents a group having a (meth)acryloxy group.

R ^b represents a group having a hydrogen atom or a (meth) propylene fluorenyloxy group.

t and u represent an integer of 0 to 3 independently of each other. ]

Y represents a residue obtained by removing four carboxyl groups from an organic compound having four carboxyl groups, and specific examples thereof include residues obtained by removing four carboxyl groups from a tetravalent acid corresponding to the tetravalent acid dianhydride.

In the formula (1), R ^a represents a group having a (meth) acryloxy group, and examples thereof include a group derived from the (meth) acrylate compound having an oxygen-containing saturated heterocyclic group.

R ^b represents a hydrogen atom or a (meth) propylene fluorenyloxy group.

t and u independently represent an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, more preferably 0.

Ring Z ¹ , ring Z ² , R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , k1 , k2 , m1 , m2 , n1 and n 2 in formula (1) and in formula (2) Ring Z ¹ , ring Z ² , R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , k1 , k2 , m1 , m2 , n1 and n2 are synonymous, and preferred embodiments are also the same.

Among the polymers having the structural unit represented by the formula (1), structural units represented by the following formulas (1-A) and (1-B) can be exemplified as more suitable examples.

[In the formula (1-A), R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , R ^a , R ^b , Y, k1, k2, m1, m2, n1, n2, t and u Synonymous with the foregoing. ]

[In the formula (1-B), R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , R ^a , R ^b , Y, k1, k2, m1, m2, n1, n2, t and u Same as the foregoing. ]

In the present invention, the molecular weight of the (B) polymer is not particularly limited, but is preferably from 1,000 to 200,000, more preferably from 2,500 to 50,000, from the viewpoint of coating film strength, coatability or developability. Further, in the present specification, the molecular weight of the (B) polymer is a weight average molecular weight (Mw) converted to polystyrene as measured by gel permeation chromatography (hereinafter abbreviated as GPC) (solution solvent: tetrahydrofuran).

In the present invention, the acid value of the (B) polymer is preferably from 30 to 150 mgKOH/g, more preferably from 30 to 130 mgKOH/g, and particularly preferably from 50 to 100 mgKOH/g from the viewpoint of developability. If the acid value is too low, the development speed is lowered, and a necessary pattern may not be obtained. On the other hand, when the acid value is too high, the development is excessive, and the pattern may be easily peeled off. The "acid value" in the present specification means the number of mg of KOH required to neutralize 1 g of the nonvolatile component after removing the solvent of the polymer solution.

In the present invention, as the binder resin, (B) may be added. Other resins other than polymers (hereinafter also referred to as "(b) other polymers"). Thereby, the adhesion to the substrate, the alkali developability, and the storage stability can be improved. The polymer is not particularly limited, but is preferably a resin having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. In particular, a polymer having a carboxyl group is preferably an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter also referred to as "unsaturated monomer (b-1)"). A copolymer of an ethylenically unsaturated monomer (hereinafter also referred to as "unsaturated monomer (b-2)").

Specific examples of the copolymer of the unsaturated monomer (b-1) and the unsaturated monomer (b-2), for example, JP-A-7-140654, JP-A-8-259876, Japanese Laid-Open Patent Publication No. H10-31308, Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. The copolymer disclosed in Japanese Patent Publication No. 101728 or the like.

In the present invention, (b) the other polymers may be used singly or in combination of two or more.

In the present invention, the content of the component (B) is preferably from 10 to 1,000 parts by mass, particularly preferably from 20 to 500 parts by mass, per 100 parts by mass of the (A) colorant. In this case, when the content of the component (B) is too small, for example, the alkali developability is lowered, and the storage stability of the obtained colored composition is lowered. On the other hand, when the content of the component (B) is too large, the concentration of the colorant is relatively lowered, and it is difficult to achieve the target color density as a film.

Further, when (b) other polymers are used in combination, the content of the (B) polymer is preferably 10% by mass or more, and more preferably 15% by mass based on the total amount of the binder resin. The amount is at least %, and particularly preferably 20% by mass or more.

-(C) solvent -

The colored composition of the present invention contains at least one solvent selected from the group consisting of alcohols and ketones (hereinafter also referred to as "solvent c1"), which accounts for 3 to 50% by mass based on the total amount of the solvent. Thereby, a coloring composition excellent in storage stability can be obtained.

Examples of the alcohols include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, and diethylene glycol. Monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether , propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether (poly) olefin group II Alcohol monoalkyl ethers; methanol, ethanol, propanol, butanol, isopropanol, isobutanol, tertiary butanol, 3-methoxybutanol, octanol, 2-ethylhexanol, cyclohexyl (cyclo)alkyl alcohols such as alcohol; alkyl lactates such as methyl lactate and ethyl lactate; and ketone alcohols such as diacetone alcohol.

Among these alcohols, preferred are (poly)olefin diol monoalkyl ethers, (cyclo)alkyl alcohols, particularly preferably ethylene glycol mono-n-butyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol single Methyl ether, propylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monoethyl ether, ethanol, 3-methoxybutanol. The alcohols may be used alone or in combination of two or more.

Further, examples of the ketones include methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone. Among them, cyclohexanone is preferred. The ketones may be used singly or in combination of two or more.

In addition, examples of the solvent other than (c1) (hereinafter also referred to as "solvent (c2)") include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and diethylene glycol single Methyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate (poly) olefinic diol monoalkyl ether acetates such as 3-methyl-3-methoxybutyl acetate; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether , other ethers such as diethylene glycol diethyl ether and tetrahydrofuran; diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, and 1,6-hexanediol diacetate; Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl Alkoxycarboxylates such as -3-methoxybutylpropionate; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate , isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate , isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate, ethyl 2-oxobutyrate, etc. Other esters; aromatic hydrocarbons such as toluene and xylene; decylamine or guanidine such as N,N-dimethylformamide, N,N-dimethylacetamide or N-methylpyrrolidone Amines, etc.

Among these solvents (c2), preferred are (poly)olefin-based diol monoalkyl ether acetates, ethers, diacetates, alkoxycarboxylates, and particularly preferably ethylene glycol monomethyl ether. Acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, dipropylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol Alcohol methyl ethyl ether, 1,3-butanediol diacetate, 1,6-hexanediol diacetate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate , 3-ethoxypropionic acid ethyl ester. The solvent (c2) may be used singly or in combination of two or more.

In the present invention, the content of the solvent (c1) is preferably from 5 to 50% by mass, more preferably from 10 to 40% by mass, even more preferably from 15 to 35% by mass based on the total amount of the solvent. When the content ratio of the solvent (c1) is less than 3% by mass, foreign matter is likely to be generated in the colored composition or in the cured film. On the other hand, when the content ratio of the solvent (c1) exceeds 50% by mass, the viscosity of the colored composition tends to increase with time.

The content of the solvent (C) is not particularly limited, but the total concentration of each component after removing the solvent of the coloring composition is preferably from 5 to 50% by mass, particularly preferably from 10 to 40% by mass. According to this aspect, a colored composition having good dispersibility, coatability, and stability can be obtained.

-crosslinker -

In the present invention, the curability can be further improved by adding a crosslinking agent. The crosslinking agent means a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an epoxy group, an oxetanyl group, and an N-alkoxymethylamino group. In the present invention, as the crosslinking agent, a compound having two or more (meth) acryloxy groups (excluding the above component (B)) or having two or more N-alkoxymethyl groups is preferable. Amine based compounds.

Specific examples of the compound having two or more (meth)acryloxycarbonyl groups (excluding the component (B)) include polyfunctional compounds obtained by reacting an aliphatic polyhydroxy compound with (meth)acrylic acid. (Meth) acrylate, caprolactone-modified polyfunctional (meth) acrylate, alkylene oxide-modified polyfunctional (meth) acrylate, (meth) acrylate having hydroxyl group, and polyfunctional A polyfunctional polyurethane (meth) acrylate obtained by reacting an isocyanate, a polyfunctional (meth) acrylate having a carboxyl group obtained by reacting a (meth) acrylate having a hydroxyl group, and an acid anhydride.

Here, examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; glycerin, trimethylolpropane, and pentaerythritol. A trivalent or higher aliphatic polyhydroxy compound such as dipentaerythritol. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, trimethylolpropane di(meth)acrylate, and pentaerythritol tri(meth)acrylic acid. Ester, dipentaerythritol penta (meth) acrylate, glycerin dimethacrylate, and the like. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of the acid anhydride include acid anhydrides of dibasic acids such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, and hexahydrophthalic anhydride, and the aforementioned tetravalent acid II. anhydride.

In addition, polyfunctional (methyl) modified as the above caprolactone The acrylate is, for example, a compound described in paragraphs [0015] to [0018] of JP-A-11-44955. The polyfunctional (meth) acrylate modified with the above alkylene oxide may be exemplified by at least one modified bisphenol A di(meth)acrylate selected from the group consisting of ethylene oxide and propylene oxide. At least one modified isocyanuric acid tri(meth)acrylate selected from the group consisting of ethylene oxide and propylene oxide, modified with at least one selected from the group consisting of ethylene oxide and propylene oxide Trimethylolpropane tri(meth)acrylate, modified with at least one selected from the group consisting of ethylene oxide and propylene oxide, neopentyl alcohol tri(meth)acrylate, selected from the group consisting of epoxy At least one modified neopentyltetrakis(meth)acrylate of an alkane and propylene oxide, and at least one modified dipentaerythritol selected from the group consisting of ethylene oxide and propylene oxide (Meth) acrylate, at least one modified dipentaerythritol hexa(meth)acrylate selected from the group consisting of ethylene oxide and propylene oxide.

Further, examples of the compound having two or more N-alkoxymethylamino groups include a melamine structure and a benzoquinone structure. Structure, compound of urea structure, and the like. Among them, melamine structure, benzoquinone Structure means having more than one three Ring or phenyl substituted three The chemical structure of the ring as a basic skeleton also includes melamine and benzoquinone. Or the concept of their condensate. Specific examples of the compound having two or more N-alkoxymethylamino groups include N, N, N', N', N", N"-hexa(alkoxymethyl) melamine, N,N,N',N'-tetrakis(alkoxymethyl)benzoquinone , N, N, N', N'-tetrakis(alkoxymethyl) glycoluril, and the like.

Among these crosslinking agents, a polyfunctional (meth) acrylate obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid, or a polyfunctional (methyl) modified by caprolactone is preferred. Acrylate, polyfunctional polyurethane (meth) acrylate, polyfunctional (meth) acrylate having carboxyl group, N, N, N', N', N", N"-hexa (alkoxy) Methyl)melamine, N,N,N',N'-tetrakis(alkoxymethyl)benzoquinone . The trivalent or higher aliphatic polyhydroxy compound is used from the viewpoint of high strength of the colored layer, excellent surface smoothness of the colored layer, and difficulty in occurrence of stains and film residues on the substrate on the unexposed portion and on the light shielding layer. Among the polyfunctional (meth) acrylates obtained by the reaction of (meth)acrylic acid, trimethylolpropane triacrylate, neopentyl alcohol triacrylate, dipentaerythritol pentaacrylate, and new are particularly preferred. Pentaerythritol hexaacrylate, in a polyfunctional (meth) acrylate having a carboxyl group, particularly preferably a compound obtained by reacting pentaerythritol triacrylate with succinic anhydride, and dipentaerythritol pentaacrylate A compound obtained by reacting with succinic anhydride.

In the present invention, the crosslinking agents may be used singly or in combination of two or more.

The content of the crosslinking agent in the present invention is preferably from 10 to 1,000 parts by mass, particularly preferably from 20 to 500 parts by mass, per 100 parts by mass of the (A) colorant. At this time, if the content of the crosslinking agent is too small, sufficient curability may not be obtained. On the other hand, when the content of the crosslinking agent is too large, when the alkali developability is imparted to the colored composition of the present invention, the alkali developability is lowered, and stains and film sticking tend to occur on the substrate or the light-shielding layer of the unexposed portion. .

-Photopolymerization initiator -

A photopolymerization initiator may be added to the colored composition of the present invention. by Thereby, the coloring composition can be imparted with radiation linearity. The photopolymerization initiator used in the present invention is an activity of generating a polymerization capable of starting the component (B) and optionally adding a crosslinking agent by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam or X-ray. Kind of compound.

As such a polymerization initiator, for example, a thiophene can be mentioned. Ketones, acetophenones, biimidazoles, three Compounds, O-mercaptopurines, phosphonium salts, benzoin compounds, benzophenones, α-diketones, polynuclear terpenoids, diazo compounds, sulfhydrazines An acid ester compound, a phosphonium salt compound, or the like.

In the present invention, the photopolymerization initiators may be used singly or in combination of two or more. As the photopolymerization initiator, it preferably contains a selected from the group consisting of thiophene Ketones, acetophenones, biimidazoles, three At least one of the compound-like compound and the O-indenyl hydrazine compound is particularly preferably an O-mercapto fluorene-based compound from the viewpoint of good compatibility with the (B) polymer and difficulty in occurrence of foreign matter.

In the preferred photopolymerization initiator of the present invention, as a thiophene Specific examples of the ketone compound include thiophene Ketone, 2-chlorothiazide Ketone, 2-methylthiazide Ketone, 2-isopropylthiophene Ketone, 4-isopropylthiophene Ketone, 2,4-dichlorothiazide Ketone, 2,4-dimethylthiophene Ketone, 2,4-diethylthio Ketone, 2,4-diisopropylthio Ketones, etc.

Further, specific examples of the above acetophenone-based compound include 2-methyl-1-[4-(methylthio)phenyl]-2- Olinone propan-1-one, 2-benzyl-2-dimethylamino-1-(4- Oleinophenyl)butan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4- Olefinophenyl) butan-1-one and the like.

Further, as a specific example of the above biimidazole compound, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole can be exemplified. , 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4 , 6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, and the like.

Further, when a biimidazole compound is used as a photopolymerization initiator, it is preferred to use a hydrogen donor in combination from the viewpoint of improving sensitivity. The "hydrogen donor" as used herein refers to a compound capable of supplying a hydrogen atom to a radical generated by a biimidazole compound by exposure. Examples of the hydrogen donor include 2-mercaptobenzothiazole and 2-mercaptobenzoene. Thiol-like hydrogen donor such as azole; amine hydrogen donor such as 4,4'-bis(dimethylamino)benzophenone or 4,4'-bis(diethylamino)benzophenone . In the present invention, the hydrogen donor may be used singly or in combination of two or more kinds, and from the viewpoint of further improving the sensitivity, it is preferred to combine one or more thiol-based hydrogen donors and one or more amine-based hydrogen donors. use.

In addition, as the above three Specific examples of the compound-like compound include, for example, 2,4,6-tris(trichloromethyl)-all. 2-methyl-4,6-bis(trichloromethyl)-all three , 2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-three , 2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl) are all three 2-[2-(4-Diethylamino-2-methylphenyl)vinyl]-4,6-bis(trichloromethyl)-all 2-[2-(3,4-Dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-three , 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-three , 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl) are all three , 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-three Three with a halogenated methyl group Class of compounds.

Further, as a specific example of the O-indenyl quinone compound, 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzylidene fluorenyl) can be exemplified. ), Ethyl Ketone, 1-[9-Ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(O-ethylindenyl), Ethyl Ketone ,1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylmethoxybenzylidene)-9H-indazol-3-yl]-,1-(O-ethylindenyl) Ethylketone, 1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzylidene] -9H-carbazol-3-yl]-, 1-(O-ethylindenyl) and the like. As a commercial item of the O-indenyl quinone compound, NCI-831, NCI-930 (above, ADEKA Co., Ltd.), etc. can be used. Among these compounds, from the viewpoint of the sensitivity of the coloring composition, ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylmethoxybenzylidene)-9H is preferred. -oxazol-3-yl]-, 1-(O-ethylindenyl), NCI-831, NCI-930.

In the present invention, when a photopolymerization initiator other than the biimidazole compound such as an acetophenone compound is used, a sensitizer may be used in combination. As such a sensitizer, for example, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4-di Ethylaminoacetophenone, 4-dimethylaminopropiophenone, ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5- Bis(4-diethylaminobenzylidene)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzimidyl)coumarin, 4-(diethyl Amino) chalcone and the like. Further, in the present invention, the sensitivity of the coloring composition can be improved by the addition of a polyfunctional thiol which acts as a chain transfer agent. Examples of such a chain transfer agent include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), and 2,4,6-tridecyl group. three , 2-(N,N-dibutylamino)-4,6-diindenyl Wait.

In the present invention, the content of the photopolymerization initiator is preferably 0.01 to 120 parts by mass, more preferably 1 to 100 parts by mass, based on 100 parts by mass of the total of the component (B) and the arbitrarily added crosslinking agent. It is preferably 7 to 50 parts by mass, and particularly preferably 10 to 30 parts by mass. In this case, when the content of the photopolymerization initiator is too small, the curing due to exposure is insufficient. On the other hand, if the content is too large, the formed coloring layer tends to fall off from the substrate during development.

-additive-

The composition of the present invention may contain various additives as needed.

Examples of the additive include a filler such as glass or alumina; a polymer compound such as polyvinyl alcohol or poly(fluoroalkyl acrylate); and a surfactant such as a fluorine-based surfactant or a quinone surfactant; Agent; vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tris(2-methoxyethoxy) decane, N-(2-aminoethyl)-3-aminopropyl Dimethoxyoxane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethyl Oxydecane, 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxy a adhesion promoter of decane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, etc.; 2,2-thiobis An antioxidant such as (4-methyl-6-tertiary butylphenol) or 2,6-ditributylphenol; 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl) )-5-chlorobenzotriazole, alkoxybenzophenone, etc. UV absorber; anti-flocculant such as sodium polyacrylate; malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1- Residues of propanol, 5-amino-1-pentanol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, etc. Improver; succinic acid mono [2-(methyl) propylene methoxyethyl] ester, phthalic acid mono [2-(methyl) propylene methoxyethyl] ester, ω-carboxy polycaprolactone single A developability improving agent such as (meth) acrylate or the like.

The colored composition of the present invention can be prepared by a suitable method, and the preparation method can be prepared, for example, by mixing the components (A) to (B) with (C) a solvent and optionally adding other components. When a pigment is used as the (A) coloring agent, it is preferred to use a pigment in the solvent (C) in the presence of a dispersing agent, and, depending on the case, a part of the component (B), for example, using a bead mill or a roll mill. A method of preparing a pigment dispersion liquid by mixing and dispersing, and then adding a component (B), a solvent or other component which is further added as needed, to the pigment dispersion liquid, and mixing them. When both the dye and the pigment are used as the (A) coloring agent, it is possible to use a dye solution to be further prepared by the first screening method as disclosed in Japanese Laid-Open Patent Publication No. 2010-132874. A method in which a dispersion or the like is mixed, and the obtained colored composition is prepared by a second screening program. Further, the dye and the component (B) and other components used as needed may be dissolved in a solvent, and the obtained solution may be mixed with a separately prepared pigment dispersion liquid by a first screening test, and then The obtained coloring composition is prepared by a second screening program. Further, after the dye solution is subjected to the first screening test, it may be mixed with the component (B) and other components used as needed, and dissolved. The obtained solution was mixed with a separately prepared pigment dispersion by a second screening procedure, and the resulting colored composition was prepared by a third screening procedure.

Color filter and manufacturing method thereof

The color filter of the present invention comprises a coloring layer formed using the colored composition of the present invention.

As a method of manufacturing a color filter, the first method is as follows. First, a light shielding layer (black matrix) is formed on the surface of the substrate as needed, and a portion where the pixels are formed is partitioned. Next, a liquid composition of the radiation sensitive coloring composition of the present invention in which a red pigment is dispersed is applied onto the substrate, and then prebaked to evaporate the solvent to form a coating film. Next, the coating film was exposed by a photomask, and then developed with an alkali developing solution to dissolve and remove the unexposed portion of the coating film. Thereafter, by post-baking, a pixel array in which red pixel patterns are arranged in a predetermined array is formed.

Next, coating, prebaking, exposing, developing, and post-baking the respective radiation-sensitive coloring compositions are performed using the green or blue respective radiation-sensitive coloring compositions, and green pixels are sequentially formed on the same substrate. Array and blue pixel array. Thereby, a color filter in which pixel arrays of three primary colors of red, green, and blue are disposed on the substrate can be obtained. However, in the present invention, the order in which the pixels of the respective colors are formed is not limited to the above order. Further, in the first method of manufacturing a color filter, any one or more of the arrays of the red, green, and blue pixel arrays described above may be a coloring layer formed using the colored composition of the present invention.

Further, the black matrix can be formed by forming a metal thin film such as chromium which is formed by sputtering or vapor deposition into a desired pattern by photolithography, but a radiation-sensitive coloring composition in which a black pigment is dispersed may also be used. It is formed in the same manner as when the above-described pixels are formed.

Examples of the substrate used for forming the color filter include glass, ruthenium, polycarbonate, polyester, aromatic polyamide, polyamidimide, and polyimine.

Further, as appropriate, these substrates may be subjected to a suitable pretreatment such as chemical treatment such as a decane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, or vacuum vapor deposition.

When the radiation sensitive composition is applied onto a substrate, a suitable coating method such as a spray coating method, a roll coating method, a spin coating method (spin coating method), a slit coating method, or a bar coating method may be employed, and it is particularly preferable to use a spinning method. Coating method, slit coating method.

Prebaking is usually carried out by combining reduced pressure drying with heat drying. Drying under reduced pressure is usually carried out until it reaches 50 to 200 Pa. The conditions of heat drying are usually dried at 70 to 110 ° C for about 1 to 10 minutes.

The coating thickness is usually 0.6 to 8 μm, preferably 1.2 to 5 μm, as the film thickness after drying.

Examples of the light source for radiation used in forming the pixel and/or the black matrix include a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, and the like. Laser source, argon ion laser, YAG laser, XeCl excimer laser, nitrogen laser and other laser sources. As the exposure light source, an ultraviolet LED can also be used. Radiation having a wavelength in the range of 190 to 450 nm is preferred.

The exposure amount of the radiation is usually preferably from 10 to 10,000 J/m ² .

Further, as the above alkali developing solution, for example, sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo-[5.4.0]-7-ten An aqueous solution of monoene, 1,5-diazabicyclo-[4.3.0]-5-nonene or the like.

In the above alkali developing solution, a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like may be added in an appropriate amount. Further, after alkali development, water washing is usually carried out.

As the development treatment method, a shower development method, a spray development method, a dip development method, a dipping type (liquid coating) development method, or the like can be used. The developing conditions are preferably carried out at room temperature for 5 to 300 seconds.

The post-baking conditions are usually baked at 180-280 ° C for about 10 to 60 minutes.

The film thickness of the pixel thus formed is usually 0.5 to 5 μm, preferably 1 to 3 μm.

In addition, as a second method of producing a color filter, a method of obtaining pixels of respective colors by inkjet disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. In this method, first, a partition wall having a light blocking function is formed on the surface of the substrate. Next, after the liquid composition of the thermosetting coloring composition of the present invention in which, for example, a red pigment is dispersed, is sprayed into the formed partition walls by an inkjet device, prebaking is performed to evaporate the solvent. Next, after exposing the coating film as needed, it is cured by post-baking to form a red pixel pattern.

Next, using a green or blue thermosetting composition, a green pixel pattern and a blue pixel pattern are sequentially formed on the same substrate as described above. Thereby, a color filter in which pixel patterns of three primary colors of red, green, and blue are arranged on the substrate is obtained. However, in the present invention, the order in which the pixels of the respective colors are formed is not limited to the above order. Further, in the second method of manufacturing the color filter, any one or more of the above-described red, green, and blue pixel arrays may be a coloring layer formed using the coloring composition of the present invention.

Further, the partition walls not only serve as a light-shielding effect, but also serve to prevent the coloring composition of each color sprayed into the division from mixing, so that the film is thicker than the black matrix used in the first method. . Therefore, the partition walls are usually formed using a black sensitizing radioactive composition.

The substrate used for forming the color filter, the light source of the radiation, and the method and conditions for prebaking and postbaking are the same as those of the first method described above. Thereby, the film thickness of the pixel formed by the inkjet method is the same as the height of the partition wall.

After forming a protective film as needed on the pixel pattern thus obtained, a transparent conductive film is formed by sputtering. After the transparent conductive film is formed, a spacer can be further formed to produce a color filter. The spacer is usually formed using a radiation-sensitive composition, but a spacer having a light-shielding property (black spacer) may also be used. At this time, a radiation-sensitive composition in which a black colorant is dispersed may be used, but the coloring composition of the present invention can also be suitably used for the formation of the black spacer.

The brightness and color purity of the color filter of the present invention thus obtained Therefore, it is extremely useful for a color liquid crystal display element, a color image sensor element, a color sensor, an organic EL element, an electronic paper, or the like.

Display component

The display element of the present invention includes the color filter of the present invention. Examples of the display element include a color liquid crystal display element, an organic EL display element, and electronic paper.

The color liquid crystal display element having the color filter of the present invention may be of a transmissive type or a reflective type, and may have an appropriate structure. For example, the color filter may be formed on a substrate different from the driving substrate on which the thin film transistor (TFT) is disposed, and the driving substrate and the substrate on which the color filter is formed may have a structure opposed to each other by the liquid crystal layer. Further, a color filter may be formed on the surface of the driving substrate on which the thin film transistor (TFT) is disposed, and the substrate and the substrate on which the ITO (tin-doped indium oxide) electrode is formed are formed by the liquid crystal layer. And the relative structure. The latter structure has the advantage of being able to increase the aperture ratio particularly, resulting in a bright, high-definition liquid crystal display element.

The color liquid crystal display element including the color filter of the present invention may include a backlight unit using a white LED as a light source in addition to a CCFL (Cold Cathode Fluorescent Lamp). Examples of the white LED include a combination of a red LED, a green LED, and a blue LED, and a white LED obtained by color mixing; a combination of a blue LED, a red LED, and a green phosphor; and a white LED obtained by color mixing. a combination of a blue LED, a red illuminating phosphor and a green illuminating phosphor, a white LED obtained by color mixing; a white LED obtained by mixing a blue LED and a YAG phosphor; Combination blue LED, orange a color-emitting phosphor and a green-emitting phosphor, a white LED that obtains white light by color mixing; a combination of an ultraviolet LED, a red-emitting phosphor, a green-emitting phosphor, and a blue-emitting phosphor, by color mixing A white LED or the like that obtains white light.

The color liquid crystal display element having the color filter of the present invention can be TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, IPS (Transverse Electric Field Switching, In-Planes Switching). A suitable liquid crystal mode such as a type, a VA (Vertical Alignment) type, or an OCB (Optically Compensated Birefringence) type.

In addition, the organic EL display element having the color filter of the present invention can have a suitable structure. For example, the structure disclosed in Japanese Laid-Open Patent Publication No. Hei 11-307242 can be employed.

Further, the electronic paper having the color filter of the present invention can adopt a suitable structure, and for example, a structure disclosed in, for example, Japanese Laid-Open Patent Publication No. 2007-41169 can be employed.

[Examples]

Hereinafter, embodiments of the present invention will be specifically described by way of examples. However, the invention is not limited to the following embodiments.

<Measurement of acid value>

The acid value of the (B) polymer obtained in each of the following Synthesis Examples was measured in the following manner. The polymer solution was accurately weighed to 0.5 g, accurate to 1 mg unit, and dispensed into a glass container. After diluting to 50 ml with propylene glycol monomethyl ether acetate, phenolphthalein was added, and titration was carried out with a 0.1 N aqueous solution of potassium hydroxide, and the point of discoloration into a pink color was used as an end point. In the same way Blank test. The acid value (unit: mgKOH/g) was calculated from the dropwise addition amount of the (B) polymer and the 0.1 N aqueous solution of potassium hydroxide in the blank test.

<Synthesis of Polymer>

Synthesis Example 1 (Synthesis of (B) Polymer)

To a 1000 mL flask equipped with a stirrer and a cooling tube, biphenyltetracarboxylic dianhydride (manufactured by Ube Industries, Ltd.: trade name BPDA) 90 g, 9,9-bis[4-(2-hydroxyethoxy)phenyl group was added. 110 g of 茀 (produced by Osaka Gas Chemical Co., Ltd.: trade name BPEF), 1 g of 4-dimethylaminopyridine, and 134 g of propylene glycol monomethyl ether acetate were heated in a 155 ° C oil bath for 4 hours while stirring under a nitrogen stream. Next, after cooling to 120 ° C, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (manufactured by Adeka Co., Ltd.: trade name: ADK STAB LA-7RD) 0.04 was added as a polymerization inhibitor. g, 80 g of 4-hydroxybutyl acrylate glycidyl ether (manufactured by Nippon Kasei Co., Ltd.: trade name: 4HBAGE) was further added, and the mixture was stirred at 120 ° C for 4 hours. Subsequently, the mixture was cooled to room temperature, and propylene glycol monomethyl ether acetate was added to give a nonvolatile content of 50% by mass to obtain a pale yellow transparent viscous polymer solution. The GPC of the obtained polymer had a polystyrene-equivalent weight average molecular weight of 4,920 and an acid value of 61 mgKOH/g. This polymer was referred to as "polymer (B-1)".

Synthesis Example 2 ((b) Synthesis of other polymers)

100 parts by mass of propylene glycol monomethyl ether acetate was placed in a flask equipped with a stirrer and a cooling tube, and nitrogen substitution was performed. Heating to 80 ° C, 100 parts by mass of propylene glycol monomethyl ether acetate, 15 parts by mass of methacrylic acid, 12 parts by mass of styrene, 41 parts by mass of benzyl methacrylate, and 15 parts by mass of 2-hydroxyethyl methacrylate 2 parts by mass of n-butyl methacrylate, 15 parts by mass of N-phenylmaleimide and 0.5 parts by mass of 2,2'-azobisbutyronitrile A mixed solution of dinonpentaerythritol tetrakis(2-mercaptopropionate) 2 parts by mass was kept at 80 ° C and polymerized at the same temperature for 4 hours. Thereafter, the temperature of the reaction solution was raised to 100 ° C, and polymerization was further carried out for 1 hour, whereby a polymer solution (solid content concentration = 40% by mass) was obtained. The obtained polymer had Mw = 24,000, Mn = 14,800, Mw / Mn = 1.60, and an acid value of 98 mg KOH / g. This polymer was referred to as "polymer (B-2)".

Synthesis Example 3 ((b) Synthesis of other polymers)

100 parts by mass of propylene glycol monomethyl ether acetate was placed in a flask equipped with a stirrer and a cooling tube, and nitrogen substitution was performed. The mixture was heated to 80 ° C, and 50 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, 10 parts by mass of styrene, 5 parts by mass of benzyl methacrylate, and methyl group were added dropwise at the same temperature for 1 hour. 15 parts by mass of 2-hydroxyethyl acrylate, 23 parts by mass of 2-ethylhexyl methacrylate, 12 parts by mass of N-phenylmaleimide, and mono(2-propenyloxyethyl) succinate A mixed solution of 15 parts by mass and 6 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) was maintained at this temperature for 2 hours. Thereafter, the temperature of the reaction solution was raised to 90 ° C, and further polymerization was carried out for 1 hour, whereby a polymer solution (solid content concentration = 40% by mass) was obtained. The obtained polymer had Mw = 11,000, Mn = 6000, Mw / Mn = 1.83, and an acid value of 130 mg KOH / g. This polymer was referred to as "polymer (B-3)".

<Preparation of Pigment Dispersion>

Modulation example 1

As the (A) coloring agent, 15.0 parts by mass of a mixture of CI Pigment Green 58/CI Pigment Yellow 138=60/40 (mass ratio) was used, and as a dispersing agent, BYK-LPN 21116 (BYK Corporation, BYK) was used. Solvent ratio (quality %): propylene glycol monomethyl ether acetate / ethylene glycol mono-n-butyl ether / ethanol = 48.7 / 50 / 1.3) 11.1 parts by weight (solid content concentration of 40% by mass), as (b) other polymers, using polymerization 13.8 parts by mass of the solution (B-3) (solid content concentration: 40% by mass), and propylene glycol monomethyl ether acetate was used as a solvent to have a solid content concentration of 25%, which was mixed and dispersed by bead milling for 12 hours. Prepared as a pigment dispersion (A-1).

Modulation example 2

As the (A) coloring agent, 15.0 parts by mass of a mixture of CI Pigment Red 254/CI Pigment Red 177=60/40 (mass ratio) was used, and 11.1 parts by weight of BYK-LPN 21116 (solid content concentration of 40 was used as a dispersing agent). (% by mass), as the (b) other polymer, 13.8 parts by mass of the polymer (B-3) solution (solid content concentration: 40% by mass), and propylene glycol monomethyl ether acetate as a solvent to adjust the solid content concentration The pigment dispersion liquid (A-2) was prepared by mixing and dispersing for 2 hours by a bead milling method at 25%.

Modulation example 3

As a coloring agent, 15.0 parts by mass of a mixture of CI Pigment Blue 15:6/CI Basic Blue 7=60/40 (mass ratio) was used, and 11.1 parts by mass of BYK-LPN 21116 (solid content concentration of 40 was used as a dispersing agent). 5% by mass, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether were used as a solvent, and the content ratio of propylene glycol monoethyl ether in the total amount of the solvent was 20%, and the solid content concentration was 25%, and then the bead milling method was used. The mixture was mixed and dispersed for 12 hours to prepare a pigment dye mixture (A-3).

<Modulation and evaluation of coloring composition>

Example 1

Modulation of coloring radiation-linear coloring composition

As the (A) colorant, 210 parts by mass of the pigment dispersion liquid (A-1) was selected, and as the (B) polymer, 11.1 parts by mass (solid content concentration = 50% by mass) of the polymer (B-1) solution was selected as For the crosslinking agent, 36 parts by mass of KAYARAD MAX-3510 (a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) manufactured by Nippon Kayaku Co., Ltd. was selected as a photopolymerization initiator, and 2 was selected. -benzyl-2-dimethylamino-1-(4- 851 parts by mass of phenyl phenyl)butan-1-one and ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 2.0 parts by mass of 1-(O-ethinylhydrazine), as a fluorine-based surfactant, 0.2 parts by mass of MEGAFAC F-554 produced by DIC Co., Ltd. was selected as a solvent (C-1), and propylene glycol monomethyl ether B was selected. In the solvent (C-4), propylene glycol monoethyl ether was selected and mixed, and the content ratio of the solvent (C-4) in the total amount of the solvent was 30% by mass to prepare a green radiation having a solid concentration of 15% by mass. Sexual coloring composition (S-1).

Sensitivity evaluation

The colored composition (S-1) was applied onto a soda glass substrate having a SiO ₂ film on which sodium ions were eluted on the surface by a slit coater, and then prebaked on a hot plate at 90 ° C for 4 minutes. Six pre-baked coating films having a film thickness of 2.5 μm were formed.

Then, after cooling the substrates to room temperature, the radiation of each wavelength including 365 nm, 405 nm, and 436 nm is exposed at 100, 200, 300, 500, 800, or 1000 J/m ² by using a high pressure mercury lamp. The amount of the coating film is exposed. Thereafter, a developing solution composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C was sprayed on the substrate at a developing pressure of 1 kgf/cm ² (nozzle diameter: 1 mm) to carry out shower development, and then further at 220 ° C. After baking in a minute, a dot pattern of 200 μm × 200 μm was formed on the substrate.

The spot pattern on each of the substrates on which the pattern was formed at each exposure amount was observed by a scanning electron microscope, and the pattern formation was good, and the residual film ratio calculated as the film thickness ratio before and after development (film thickness after development × 100 / development) When the film thickness before the film is 90% or more, it is evaluated as "○", and when the pattern formation is good, the residual film ratio is less than 90%, or a part of the pattern is missing, it is evaluated as "Δ", and when the pattern is not formed, it is evaluated as "x". The evaluation results are shown in Table 3.

Heat resistance evaluation

The colored composition (S-1) was applied onto a soda glass substrate having a SiO ₂ film on which sodium ions were eluted on the surface by a slit coater, and then prebaked on a hot plate at 90 ° C for 4 minutes. Two coating films having a film thickness of 2.5 μm after prebaking were formed.

Next, after the substrate was cooled to room temperature, the coating film was exposed to a radiation amount of each of 365 nm, 405 nm, and 436 nm by an exposure amount of 1000 J/m ² using a high pressure mercury lamp. Thereafter, a developing solution composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C was sprayed on the substrate at a developing pressure of 1 kgf/cm ² (nozzle diameter: 1 mm) to carry out shower development, and then further at 220 ° C. After baking in a minute, a dot pattern of 200 μm × 200 μm was formed on the substrate.

The obtained two substrates were additionally baked at 230 ° C and 250 ° C for 60 minutes, and the pattern after the additional baking was observed with an optical microscope. No foreign matter was observed under any additional baking at 230 ° C and 250 ° C. In the case of "○", no foreign matter was generated at 230 °C additional baking, and foreign matter was observed under additional baking at 250 °C, and it was recorded as "△", and added at 230 °C. When foreign matter is observed under baking, it is marked as "X". The evaluation results are shown in Table 3.

Further, as the storage stability evaluation of the colored composition (S-1), the following foreign matter evaluation and viscosity stability evaluation were carried out.

Foreign body evaluation

The colored composition (S-1) which was allowed to stand at 5 ° C for 3 days was applied to a 10 cm × 10 cm soda glass substrate having a SiO ₂ film on the surface where sodium ions were eluted by a slit coater, and then The hot plate at 90 ° C was prebaked for 4 minutes to form a coating film having a film thickness of 2.5 μm after prebaking. When the obtained substrate was observed with an optical microscope, and no foreign matter was observed on the coating film, it was indicated as "○", and the number of foreign matter on the coating film was one or more and 10 or less, and it was indicated as "Δ", and the observed coating film was observed. If the number of foreign bodies generated is 11 or more, it is marked as "X". The evaluation results are shown in Table 3.

Viscosity stability evaluation

The viscosity of the freshly prepared coloring composition (S-1) was measured with an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd.). Then, the colored composition (S-1) was placed in a light-shielding glass container, and after standing at 23 ° C for 14 days in a sealed state, the viscosity was measured again using an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd.). Then, the increase rate of the viscosity after the storage for 14 days was calculated as "○" when the increase rate was less than 5%, and "△" when the increase rate was less than 5%, and "△" when it was less than 10%, and 10% or more. The evaluation is "X". The evaluation results are shown in Table 3.

Examples 2 to 30 and Comparative Examples 1 to 14

The type and amount of the pigment dispersion liquid, the polymer solution, the crosslinking agent, and the photopolymerization initiator in Example 1 were changed as shown in Table 1, and the type and amount of the solvent were changed to form a coloring composition. Alcohols and The content ratio (unit: mass%) of the ketone to the total amount of the solvent was adjusted to a colored composition (S-2) to (S-44) as shown in Table 2. Next, the colored compositions (S-2) to (S-44) were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.

In Table 2, the solvents (C-12) and (C-13) are used in the BYK-LPN 21116 used to prepare the pigment dispersions (A-1) to (A-2) and the pigment dye mixture (A-3). Ingredients.

In Table 1, each component is as follows.

D-1: a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (trade name: MAX-3510, manufactured by Nippon Kayaku Co., Ltd.)

E-1: 2-benzyl-2-dimethylamino-1-(4- Olefinophenyl)-butan-1-one (trade name IRGACURE 369, manufactured by Ciba Specialty Chemicals)

E-2: ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(O-ethylindenyl) ( Trade name IRGACURE OXE02, manufactured by Ciba Specialty Chemicals)

E-3: NCI-930 (trade name: NCI-930, manufactured by ADEKA)

In Table 2, each component is as follows. Among them, the solvents (C-1) to (C-3) correspond to the solvent (c2), and the solvents (C-4) to (C-13) correspond to the solvent (c1).

C-1: propylene glycol monomethyl ether acetate

C-2: ethyl 3-ethoxypropionate

C-3: 3-methoxybutyl acetate

C-4: propylene glycol monoethyl ether

C-5: propylene glycol monomethyl ether

C-6: 3-methoxybutanol

C-7: dipropylene glycol monomethyl ether

C-8: dipropylene glycol mono-n-propyl ether

C-9: dipropylene glycol mono-n-butyl ether

C-10: Diethylene glycol monoethyl ether

C-11: cyclohexanone

C-12: ethylene glycol mono-n-butyl ether

C-13: Ethanol

<Preparation and Evaluation of Colored Compositions Containing Lake Pigments>

Synthesis Example 4 ((b) Synthesis of other polymers)

To a flask equipped with a cooling tube and a stirrer, 0.5 parts by mass of 2,2'-azobisisobutyronitrile and 200 parts by mass of propylene glycol monomethyl ether acetate were added, and 15 parts by mass of methacrylic acid and N-phenyl horse were further added. 20 parts by mass of hydrazine, 55 parts by mass of benzyl methacrylate, 10 parts by mass of styrene, and pentaerythritol tetrakis(3-mercaptopropionate) as a molecular weight modifier (product name: 堺Chemical Industries, Ltd.: trade name PEMPII-20P) 2 parts by mass, nitrogen substitution. Thereafter, the mixture was slowly stirred, the temperature of the reaction solution was raised to 80 ° C, and the temperature was maintained for 5 hours to carry out polymerization to obtain a polymer solution (solid content concentration = 33.3 mass%). The obtained polymer had Mw = 25,000 and Mn = 12,000. This polymer is referred to as "polymer (B-4)".

Modulation example 4

7.5 parts by mass of a triarylmethane-based lake pigment (wherein x=1 to 2) represented by the following formula (7) as a coloring agent, and 7.5 parts by mass of Pigment Blue 15:6 as (meth)acrylic acid BYK-LPN 6919 (nonvolatile content = 60%, amine value: 72 mgKOH/g, manufactured by BYK Chemical Co., Ltd.), 11 parts by mass of the dispersant, and 10.2 parts by mass of the polymer (B-4) solution, as a solvent A mixed solvent of propylene glycol monomethyl ether acetate/propylene glycol monoethyl ether = 90/10 (mass ratio) was mixed to have a solid content concentration of 20%, which was mixed and dispersed by a bead mill for 12 hours to prepare a pigment dispersion liquid ( A-4).

Modulation example 5

As the coloring agent, 1.5 parts by mass of Pigment Red 254, 10.5 parts by mass of Pigment Red 177, and 3 parts by mass of Pigment Red 81:2 (pigmented with hydrazine molybdate) were used. As a (meth)acrylic dispersant, BYK-LPN 21116 (nonvolatile content = 40%, amine value: 29 mgKOH/g, manufactured by BYK Chemical Co., Ltd.), 11 parts by mass, and polymerization were used. 16.8 parts by mass of the solution of the substance (B-4), and a mixed solvent of propylene glycol monomethyl ether acetate / propylene glycol monoethyl ether = 90/10 (mass ratio) was used as a solvent to have a solid concentration of 20% by bead milling. The mixture was mixed and dispersed for 12 hours to prepare a pigment dispersion liquid (A-5).

Modulation example 6

7.5 parts by mass of a triarylmethane-based lake pigment (wherein x=1 to 2) represented by the above formula (7) as a coloring agent, and 7.5 parts by mass of Pigment Blue 15:6 as a (meth)acrylic acid Dispersing agent BYK-LPN 6919 (nonvolatile content = 60%, amine value: 72 mgKOH/g, manufactured by BYK Chemical Co., Ltd.) 11 parts by mass and polymer (B-3) solution 10.2 parts by mass, propylene glycol as a solvent Mixing solvent of monomethyl ether acetate/propylene glycol monoethyl ether = 90/10 (mass ratio) to make a solid content concentration of 20%, mixed by a bead mill The mixture was dispersed for 12 hours to prepare a pigment dispersion (A-6).

Modulation example 7

7.5 parts by mass of Pigment Blue 61 (triarylmethane-based lake pigment) as a colorant, and 7.5 parts by mass of Pigment Blue 15:6, BYK-LPN 6919 as a (meth)acrylic dispersant (nonvolatile content = 60%, an amine value of 72 mgKOH/g, 11 parts by mass of BYK Chemical Co., Ltd., and 10.2 parts by mass of a polymer (B-3) solution, and propylene glycol monomethyl ether acetate/propylene glycol monoethyl ether as a solvent = 90 The mixed solvent of /10 (mass ratio) was mixed to have a solid content concentration of 20%, and the mixture was mixed and dispersed by a bead mill for 12 hours to prepare a pigment dispersion liquid (A-7).

Example 31

150 parts by mass of a pigment dispersion liquid (A-4) as a coloring agent, 31.8 parts by mass of a polymer (B-1) solution as a (B) polymer, and M-402 manufactured by Toagosei Co., Ltd. as a crosslinking agent (mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) 40 parts by mass of 2-benzyl-2-dimethylamino-1-(4-) as a photopolymerization initiator 4 parts by mass of Molecular phenyl)-butan-1-one (manufactured by Ciba Specialty Chemicals Co., Ltd., trade name IRGACURE 369), and 0.1 parts by mass of MEGAFAC F-554 (manufactured by DIC Corporation) as a fluorine-based surfactant The propylene glycol monomethyl ether acetate and the propylene glycol monomethyl ether as a solvent have a solid content concentration of 20% by mass and a content ratio of propylene glycol monoethyl ether to the total amount of the solvent of 20% by mass to prepare a colored composition (S-45). ).

Using the obtained coloring composition (S-45), a dot pattern was formed in the same manner as in Example 1, and sensitivity evaluation and heat resistance evaluation were performed, and the results were all good. Further, the coloring composition (S-45) was the same as in Example 1. Method evaluation The foreign body evaluation and the viscosity stability evaluation all showed good results.

Examples 32~34

In Example 31, except that the type and amount of the pigment dispersion liquid and the polymer solution were changed to those shown in Table 4, a coloring composition (S-46) to (S-) was prepared in the same manner as in Example 31. 48).

Next, in Example 31, evaluation was carried out in the same manner as in Example 31 except that the colored composition (S-46) to (S-48) was used instead of the colored composition (S-45), and as a result, sensitivity was obtained. Evaluation, heat resistance evaluation, foreign matter evaluation, and viscosity stability evaluation all showed good results.

Comparative Example 15~18

The coloring composition (S-49) to (S-52) was prepared in the same manner as in Example 31 except that the kind and amount of the pigment dispersion liquid and the polymer solution in Example 31 were changed to those shown in Table 4. ).

Then, evaluation was carried out in the same manner as in Example 31 except that the colored composition (S-49) to (S-52) was used instead of the colored composition (S-45) in Example 13, and as a result, foreign matter evaluation was performed. Both the viscosity stability evaluation showed good results, but the sensitivity and heat resistance were inferior to those of Examples 31 to 34.

In Table 4, each component is as follows.

D-2: M-402 (a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) manufactured by Toagos Corporation

E-1: 2-benzyl-2dimethylamino-1-(4- Olefinophenyl)-butan-1-one (manufactured by Ciba Specialty Chemicals, trade name IRGACURE 369)

<Solvent resistance evaluation>

The substrate having the dot pattern formed in Examples 1 to 34 was immersed in N-methylpyrrolidone at 25 ° C for 30 minutes, and the dot pattern before and after the immersion was observed with a scanning electron microscope. As a result, each of the substrates maintained a good edge shape after immersion, and the film thickness ratio before and after the immersion (film thickness after immersion × 100 / film thickness before immersion) was 95% or more.

In the same manner, the substrate having the dot pattern formed in Comparative Examples 1 to 15 was evaluated for solvent resistance in the same manner as described above. As a result, Comparative Examples 1 to 4 and 9 to 12 maintained a good edge shape after immersion. The film thickness ratio before and after the immersion (film thickness after immersion × 100 / film thickness before immersion) was 95% or more, and the film thickness ratios of Comparative Examples 5 to 8 and 13 to 18 before and after immersion were less than 95%, and light appeared. A case where a part of the dot pattern is missing or a case where the dot pattern after immersion is all peeled off from the substrate.

Claims (12)

A coloring composition comprising the following components (A), (B1), and (C): (A) a colorant, (B1) a polymer having a structural unit represented by the following formula (1), and ( C) a solvent containing (c1) an alcohol selected from at least one of a (poly)olefin-based diol monoalkyl ether and a (cyclo)alkyl alcohol, wherein the content of the alcohol is 3 ~50% by mass, [In the formula (1), the ring Z ¹ and the ring Z ² each independently represent a monocyclic or condensed polycyclic hydrocarbon ring, and Y represents a residue obtained by removing four carboxyl groups from an organic compound having four carboxyl groups, R ^1a and R ^1b independently of each other represent a hydrogen atom or an alkyl group, and R ^2a and R ^2b independently of each other represent a hydrocarbon group, an alkoxy group, a decyl group, an alkoxycarbonyl group, a halogen atom, a nitro group or a cyano group, and R ^3a and R ^3b Each of them independently represents a hydrogen atom or a methyl group, R ^a represents a group having a (meth)acryloxy group, and R ^b represents a group having a hydrogen atom or a (meth)acryloxy group, and k1 and k2 are independently represented by each other. An integer of 0 to 4, m1 and m2 represent an integer of 0 to 3 independently of each other, and n1 and n2 independently represent an integer of 0 to 10, and t and u independently represent an integer of 0 to 3]. A coloring composition comprising the following components (A), (B2), and (C): (A) a colorant, and (B2) at least a compound represented by the following formula (2) and a tetravalent acid dianhydride a polymer obtained by the step of adding a (meth) acrylate compound having an oxygen-saturated heterocyclic group to the polymer obtained by the reaction, and (C) containing (c1) a polyalkylene group selected from (poly)alkylene glycol a solvent of an alcohol of at least one of an ether and a (cyclo)alkyl alcohol, wherein the content of the alcohol is from 3 to 50% by mass based on the total amount of the solvent; [In the formula (2), the ring Z ¹ and the ring Z ² independently of each other represent a monocyclic or condensed polycyclic hydrocarbon ring, and R ^1a and R ^1b independently of each other represent a hydrogen atom or an alkyl group, and R ^2a and R ^2b are mutually Independently represents a hydrocarbon group, an alkoxy group, a decyl group, an alkoxycarbonyl group, a halogen atom, a nitro group or a cyano group, and R ^3a and R ^3b independently represent a hydrogen atom or a methyl group, and k1 and k2 independently represent 0 to 4; The integers, m1 and m2, represent an integer of 0 to 3 independently of each other, and n1 and n2 independently represent an integer of 0 to 10, and p1 and p2 independently represent an integer of 1 to 4]. The coloring composition of the second aspect of the invention, wherein the (meth) acrylate compound having an oxygen-containing saturated heterocyclic group is the following formula (3-1), formula (3-2), and formula (3) -3) a compound represented by any one of In the formula (3-1), the formula (3-2) and the formula (3-3), R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ represents a single bond or a group represented by the following formula (6), and R ⁶ An alkyl group having a carbon number of 1 to 4, In the formula (6), q, r, and s independently represent an integer of 0 to 9, but q, r, and s are not 0, -C ₂ H ₄ O-group, -C ₃ H ₆ O-group, and -C ₄ H ₈ O- groups can be combined in any order]. The coloring composition of the formula (2), wherein the compound represented by the formula (2) is a compound represented by the following formula (4), [In the formula (4), R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , k1 , k2 , m1 , m2 , n1 , n2 , p1 and p2 are synonymous with the above, but m1+p1 is 4 The following integer, m2+p2 is an integer of 4 or less]. The coloring composition of the formula (2), wherein the compound represented by the formula (2) is a compound represented by the following formula (5), [In the formula (5), R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , k1 , k2 , m1 , m2 , n1 , n2 , p1 and p2 are synonymous with the above, but m1+p1 is 5 The following integer, m2+p2 is an integer of 5 or less]. The colored composition according to any one of claims 1 to 3, wherein the coloring agent contains a pigment. The colored composition of claim 6, wherein the coloring agent contains a lake pigment. The colored composition according to any one of claims 1 to 3, further comprising an O-indenyl quinone compound as a photopolymerization initiator. The coloring composition of the first or second aspect of the invention, wherein the (C) solvent further comprises (c2) a (poly)alkylene glycol monoalkyl ether acetate, an ether, a diacetate. At least one of alkoxycarboxylic acid esters. The coloring composition of the first or second aspect of the invention, wherein the content ratio of the (A) coloring agent is 5 to 70% by mass based on the solid content of the coloring composition. A color filter having a coloring layer formed using the coloring composition of any one of claims 1 to 3. A display element having a color filter as in claim 11 of the patent application.