TW201441767A - Coloring composition, coloring cured film and display component - Google Patents

Abstract

The subject of the present invention is to provide a coloring composition suitable for forming a coloring cured film with high contrast. The solution of the present invention is a coloring composition, which comprises (A) a colorant made of at least one compound selected from a xanthene compound, a polymethine compound, a coumarin compound, and a perylene compound, (B) an adhesive resin, and (C) a polymerizable compound, in which the coloring composition further comprises (D) a transition metal compound (but except (A) component).

Description

Coloring composition, coloring cured film, and display element

The present invention relates to a coloring composition, a colored cured film, and a display element, and more particularly to a color liquid crystal display element, a solid-state imaging element, an organic EL display element, an electronic paper, or the like for forming a transmissive or reflective type. A colored composition of a colored cured film to be used, a colored cured film formed using the colored composition, and a display element including the colored cured film.

When a color filter is produced using a colored radiation-sensitive composition, it is known that a pigment-dispersed colored radiation-sensitive composition is coated on a substrate and dried, and then the dried coating film is irradiated with radiation according to a desired pattern shape (hereinafter It is called "exposure".) A method of obtaining pixels of each color by development (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 (see, for example, Patent Document 3). Further, a method of obtaining a pixel of each color by an inkjet method using a pigment-dispersed colored resin composition is also known (see, for example, Patent Document 4).

In order to achieve high luminance and high color purity of display elements, or high definition of solid-state imaging elements, it is known to use dyes as colorants, and it has been proposed to use, for example, A compound (see, for example, Patent Document 5) or a polymethine compound (see, for example, Patent Document 6).

Advanced technical literature Patent literature

Patent Document 1 JP-A-2-144502

Patent Document 2 Japanese Patent Publication No. 3-53201

Patent Document 3, JP-A-6-35188

Patent Document 4, JP-A-2000-310706

Patent Document 5, JP-A-2011-138094

Patent Document 6 JP-A-2009-235392

However, due to A compound which emits a fluorescent compound with a polymethine compound, and if it is used as a coloring agent, has a problem that the contrast is lowered. Therefore, there is a strong need to use even In the case where a dye such as a compound or a polymethine compound is used as a coloring agent, a coloring composition of a high contrast colored hardening film can also be formed.

Accordingly, an object of the present invention is to provide a coloring composition suitable for forming a colored cured film having a high contrast. A further object of the present invention is to provide a colored cured film formed using the colored composition and a display element provided therewith.

The results of the research by the inventor of the case, found that by using the inclusion The coloring agent and the specific compound of at least one compound selected from the group consisting of a compound, a polymethine compound, a coumarin compound, and an anthraquinone compound can solve the above problems.

That is, the present invention provides a coloring composition comprising (A) comprising a coloring agent of at least one compound selected from the group consisting of a compound, a polymethine compound, a coumarin compound, and an oxime compound, (B) a binder resin, and (C) a polymerizable compound, and further comprising (D) Transition metal compound (except for component (A)).

Moreover, the present invention provides a colored cured film formed using the above colored composition and a display element including the colored cured film. Here, the "stained cured film" means a color pixel, a black matrix, a black spacer, or the like used in a display element and a solid-state imaging element.

The colored cured film having a high contrast can be formed using the colored composition of the present invention.

Therefore, the coloring composition of the present invention can be suitably used for the production of solid-state imaging elements such as color liquid crystal display elements, organic EL display elements, display elements such as electronic paper, and CMOS image sensors.

[Formation of the Invention]

The invention is described in detail below.

Coloring composition

The constituent components of the colored composition of the present invention will be described in detail below.

- (A) colorant -

The colored composition of the present invention contains At least one compound selected from the group consisting of a compound, a polymethine compound, a coumarin compound, and an anthraquinone compound is used as the (A) colorant.

As the foregoing The compound is preferably a compound having a structure represented by the following formula (1).

In the formula (1), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or an aliphatic hydrocarbon group, and have a bond containing a carbon atom and an atom other than a hydrogen atom between CC bonds of the aliphatic hydrocarbon group. a base group, an alicyclic hydrocarbon group, a heterocyclic group, or an aromatic hydrocarbon group.

R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

R ⁷ are diagrams _{-SO 3 -, - SO 3 H} , -SO 3 M 1, -SO 3 R 8, -CO 2 -, - CO 2 H, -CO 2 M 1, -CO 2 R 9, -SO ₂ NHR ¹⁰ or -SO ₂ NR ¹¹ R ¹² .

r is an integer from 0 to 5, and in the case where r is an integer of 2 or more, a plurality of R ^{7 's} may be the same or different.

R ⁸ and R ⁹ each independently represent an aliphatic hydrocarbon group or a group having a linking group containing a carbon atom and an atom other than a hydrogen atom between CC bonds of the aliphatic hydrocarbon group.

R ¹⁰ , R ¹¹ and R ¹² each independently represent an aliphatic hydrocarbon group, a group having a linking group containing a carbon atom or an atom other than a hydrogen atom between CC bonds of an aliphatic hydrocarbon group, or an alicyclic hydrocarbon group, or R ¹¹ And a heterocyclic group formed by bonding R ^{12 to} each other.

The M ¹ system represents a sodium atom or a potassium atom. ]

The aliphatic hydrocarbon group may, for example, be an alkyl group, an alkenyl group or an alkynyl group. The carbon number of the aliphatic hydrocarbon group is preferably from 1 to 30, more preferably from 1 to 24, particularly preferably from 1 to 20. Further, these aliphatic hydrocarbon groups may be linear or branched. Specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a secondary butyl group, a tertiary butyl group, a hexyl group, a heptyl group, and an octyl group. , mercapto, fluorenyl, undecyl, 1-methylindenyl, dodecyl, 1-methylundecyl, 1-ethylindenyl, thirteenyl, tetradecyl, tertiary , fifteen base, 1-heptyloctyl, heptadecyl, octadecyl and the like. Examples of the alkenyl group include a vinyl group, a 1-propenyl group, a 2-propenyl group, a 1-butenyl group, a 2-butenyl group, a 1,3-butadienyl group, and a 1-pentenyl group. -pentenyl, 1-hexenyl, 2-ethyl-2-butenyl, 2-octenyl, (4-vinyl)-5-hexenyl, 2-decenyl and the like. Examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 1-butynyl group, a 1-pentynyl group, a 3-pentynyl group, a 1-hexynyl group, and a 2-ethyl-2- group. Butynyl, 2-octynyl, (4-ethynyl)-5-hexynyl, 2-decynyl and the like.

These aliphatic hydrocarbons may have a linking group containing a carbon atom and an atom other than a hydrogen atom based on the CC bond. Examples of the linking group containing an atom other than a carbon atom and a hydrogen atom include -O-, -S-, -CO-, -COO-, -CONH-, -SO ₂ - and the like.

The alicyclic hydrocarbon group is preferably an alicyclic hydrocarbon group having 3 to 30 carbon atoms. Specific examples of the alicyclic hydrocarbon group include a cycloalkyl group, a cycloalkenyl group, a condensed polycyclic hydrocarbon group, a crosslinked cyclic hydrocarbon group, a spirohydrocarbyl group, a cyclic terpene group, and the like. More specifically, a cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a tert-butylcyclohexyl group, a cyclobutyl group or a cyclooctyl group; a ring such as a 1-cyclohexenyl group; Alkenyl; condensed polycyclic hydrocarbon group such as tricyclodecyl, decahydro-2-naphthyl, adamantyl; tricyclo[5.2.1.0 ^2,6 ]non-8-yl, pentacyclopentadecyl, isoindole a bridged cyclic hydrocarbon group such as a bis-pentenyl group or a tricyclopentenyl group; a snail group such as a monovalent group obtained by removing one hydrogen atom from spiro[3.4]heptane or spiro[3.4]octane; A cyclic decyl group such as a monovalent group obtained by removing one hydrogen atom such as an alkane, a side arsenic or a hydrazine. The carbon number in the aforementioned cycloalkyl group and cycloalkenyl group is more preferably from 3 to 12.

Examples of the heterocyclic group include a monovalent monocyclic heterocyclic group having a 5- to 10-membered ring and a polycyclic heterocyclic group obtained by condensing the monocyclic heterocyclic group. The heterocyclic group may be either an unsaturated ring or a saturated ring, or may have two or more hetero atoms of the same or different kinds in the ring (for example, a nitrogen atom, an oxygen atom, or a sulfur atom). Specific examples thereof include pyrrolidinyl group and pyrazolinyl group. Olinyl group, sulfur Lolinyl, piperidinyl, N-hexahydropyridyl, piperazine Base a nitrogen-containing alicyclic heterocyclic group such as a tetrahydropyrimidinyl group, or a 1,3-di -2-yl and other alicyclic heterocyclic groups, pyridyl, pyridyl Base, pyrimidinyl, oxime Base, quinolyl, isoquinolyl, anthracene Base Lolinyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, thiazolyl, benzothiazolyl, Nitrogen-containing aromatic heterocyclic group such as azole group, mercapto group, carbazolyl group, benzimidazolyl group, quinone imine group, thienyl group, furyl group, pyridyl Other aromatic heterocyclic groups such as a thiol group and a fluorenyl group.

The aromatic hydrocarbon group is preferably a carbon number of 6 to 20, more preferably a carbon number of 6 to 10. Specific examples of the aromatic hydrocarbon group include an aryl group. Here, the "aryl group" in the present invention means a monocyclic to 3-cyclic aromatic hydrocarbon group, and specific examples thereof include a phenyl group, a benzyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, and a second group. Tolyl, naphthyl, anthracenyl, phenanthryl, anthracenyl, 9-fluorenyl and the like.

The alkyl group having 1 to 8 carbon atoms in R ⁵ and R ⁶ may be the same as the above.

R ¹¹ and R ¹² may be bonded to each other to form a heterocyclic group. Examples of the heterocyclic group formed by bonding R ¹¹ and R ^{12 to} each other include the above-mentioned nitrogen-containing alicyclic heterocyclic group and nitrogen-containing aromatic heterocyclic group.

The aliphatic hydrocarbon group, the alicyclic hydrocarbon group, the heterocyclic group, the aromatic hydrocarbon group, and the alkyl group having 1 to 8 carbon atoms in the formula (1) may further have a substituent without departing from the gist of the invention. The position and number of the substituent are arbitrary, and in the case of having two or more substituents, the substituents may be the same or different. Examples of such a substituent include a halogen atom, a hydroxyl group, a cyano group, a decyl group, a carboxyl group, a nitro group, an amine group, a dialkylamino group, a diarylamino group, an alkoxy group, an aryloxy group, and the like. Alkoxycarbonyl, alkylthio, arylthio, trialkylsulfonyl, decyl, allyl, alkylsulfonyl, alkylamine sulfonyl, aliphatic hydrocarbon, heterocyclic, aromatic hydrocarbon, and the like. These substituents may further have a substituent.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The dialkylamino group is preferably a di(C _1-6 alkyl)amino group, and examples thereof include a dimethylamino group and a diethylamino group. The diarylamino group is preferably a di(C _6-14 aryl)amino group, and examples thereof include a diphenylamino group. The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. The aryloxy group is preferably an aryloxy group having 6 to 14 carbon atoms, and examples thereof include a phenoxy group and a benzyloxy group. The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 10 carbon atoms, and examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, and a butoxycarbonyl group. The alkylthio group is preferably an alkylthio group having 1 to 6 carbon atoms, and examples thereof include a methylthio group and an ethylthio group. The arylthio group is preferably an arylthio group having 6 to 14 carbon atoms, and examples thereof include a phenylthio group. The trialkylsulfonyl group is preferably a tri(C _1-6 alkyl)fluorenyl group, and examples thereof include a trimethylsulfonyl group. The alkylsulfonyl group is preferably an alkylsulfonyl group having 1 to 6 carbon atoms, and examples thereof include a methylsulfonyl group, an ethylsulfonyl group, and a propylsulfonyl group. The alkylamine sulfonyl group is preferably an alkylamine sulfonyl group having 1 to 8 carbon atoms, and examples thereof include methylamine sulfonyl group, dimethylamine sulfonyl group, and ethylamine sulfonyl group. , 2-ethylhexylamine sulfonyl group and the like. The aliphatic hydrocarbon group, the heterocyclic group and the aromatic hydrocarbon group are the same as those described above.

A representative example of the structure represented by the above formula (1) is, for example, a structure represented by the following formula.

Again, as the foregoing The compound is preferably described in, for example, JP-A-2012-32754, JP-A-2012-46712, JP-A-2013-29760, and the like. The skeleton serves as a pigment multimer of a partial structure of the pigment site.

In the case where the structure represented by the formula (1) is cationic, it has the structure The compound becomes an electrically neutral anion. Examples of the anion include a halogen ion, a boron anion, a phosphate anion, a carboxylate anion, a sulfate anion, an organic sulfonate anion, a nitrogen anion, and a methyl anion.

In the case where the structure represented by the formula (1) is anionic, it has the structure The compound becomes an electrically neutral cation. Examples of the cation include a proton, a metal cation, a phosphonium cation, and the like. Examples of the metal cation include monovalent metal cations such as lithium ions, sodium ions, potassium ions, cesium ions, and cesium ions, and divalent metal cations such as magnesium ions, calcium ions, barium ions, and cesium ions. Examples of the phosphonium cation include an ammonium cation, a phosphonium cation, and the like.

The ammonium cation is, for example, a cation represented by the following formula (5).

In the formula (5), R ⁵¹ to R ⁵⁴ each independently represent a hydrogen atom or an organic group. However, at least one of R ⁵¹ to R ⁵⁴ is an organic group, and two of R ⁵¹ to R ⁵⁴ may be bonded to form a ring. ]

The organic group in R ⁵¹ to R ⁵⁴ may, for example, be a hydrocarbon group, and more specifically, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group or an aromatic hydrocarbon group. Specific examples of the aliphatic hydrocarbon group, the alicyclic hydrocarbon group and the aromatic hydrocarbon group are as described in the formula (1). Among them, the alkyl group having 1 to 20 carbon atoms is preferably an aryl group having 6 to 10 carbon atoms. Further, the organic group in R ⁵¹ to R ⁵⁴ may further have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, a cyano group, a decyl group, a carboxyl group, a nitro group, an amine group, and a dialkyl group. Amino, diarylamine, alkoxy, aryloxy, alkoxycarbonyl, alkylthio, arylthio, trialkylsulfonyl, decyl, allyl, alkylsulfonyl, alkylamine A sulfonyl group, an aliphatic hydrocarbon group, a heterocyclic group, an aromatic hydrocarbon group or the like. Specific examples are exemplified by the formula (1). Wherein, the positions and the number of the substituents are arbitrary, and in the case of having two or more substituents, the substituents may be the same or different.

Further, the organic groups in R ⁵¹ to R ⁵⁴ may be bonded to each other to form a ring, wherein R ⁵¹ and R ⁵² in the formula (5) are preferably bonded to each other to form a ring, and R ⁵³ and R ⁵⁴ do not form a ring. Aspect.

R ⁵¹ ~ R ^54, at least one organic group, from the viewpoint of easiness to obtain the stability of the coloring composition of the raw material and point of view, is preferably in the R ⁵¹ ~ R ⁵⁴ is an organic group of at least three, particularly preferably 4 All are organic.

Specific examples of the cation represented by the above formula (5) include tetramethylammonium, tetraethylammonium, monostearyltrimethylammonium, distearyldimethylammonium, and trisole. Stearyl monomethylammonium, cetyltrimethylammonium, trioctylmethylammonium, dioctyldimethylammonium, monolauryltrimethylammonium, dilauryldimethylammonium, trilauryl Methylammonium, triamylbenzylammonium, trihexylbenzylammonium, trioctylbenzylammonium, trilaurylbenzylammonium, benzyldimethyl stearyl ammonium, benzyl di Methyl octyl ammonium, di(C _14-18 alkyl) dimethyl ammonium, and the like.

Examples of the phosphonium cation include cations represented by the following formulas (6) and (7).

In the formula (6), R ⁶¹ to R ⁶⁴ each independently represent a hydrogen atom or an organic group. However, at least one of R ⁶¹ to R ⁶⁴ is an organic group, and two of R ⁶¹ to R ⁶⁴ may be bonded to form a ring. ]

In the formula (7), R ⁷¹ to R ⁷⁶ each independently represent a hydrogen atom or an organic group. However, two of R ⁷¹ to R ⁷⁶ may form a ring.

X represents a divalent linking group. ]

Examples of the organic group in R ⁶¹ to R ⁶⁴ and R ⁷¹ to R ⁷⁶ include a hydrocarbon group, a heterocyclic group, an acetonyl group, and a benzamidinemethyl group. Examples of the hydrocarbon group include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group, and specific examples thereof are as described in the formula (1). Among them, an alkyl group having 1 to 20 carbon atoms and an aryl group having 6 to 10 carbon atoms are preferable, and an alkyl group having 4 to 20 carbon atoms and an aryl group having 6 to 10 carbon atoms are more preferable. Further, the heterocyclic group is preferably a monovalent monocyclic heterocyclic group having 5 to 10 membered rings, and specific examples thereof can be exemplified by the formula (1).

The organic group in R ⁶¹ to R ⁶⁴ and R ⁷¹ to R ⁷⁶ may further have a substituent in the range not departing from the gist of the invention. The substituent is the same as the substituent of the organic group in the above R ⁵¹ to R ⁵⁴ as a substituent. Here, the position and the number of the substituent are arbitrary, and in the case of having two or more substituents, the substituents may be the same or different.

Further, the organic groups in R ⁶¹ to R ⁶⁴ and R ⁷¹ to R ⁷⁶ may be bonded to each other to form a ring, and preferably, R ⁶¹ and R ⁶² in the formula (6) are bonded to each other to form a ring. R ⁶³ and R ⁶⁴ do not form a ring, and R ⁷¹ and R ⁷² in the formula (7) are bonded to each other to form a ring, and R ⁷³ to R ⁷⁶ do not form a ring.

At least one of R ⁶¹ to R ⁶⁴ is an organic group, and from the viewpoint of stability of the coloring composition and ease of obtaining raw materials, at least three of R ⁶¹ to R ⁶⁴ are preferably an organic group, and particularly preferably All four are organic.

As R ⁷¹ ~ R ⁷⁶ is an organic group, to obtain a coloring material and stability of the composition in view of easiness, R ⁷¹ ~ R ⁷³ in at least two of the organic groups, and preferably R ⁷⁴ ~ R At least two of ⁷⁶ are organic groups, and particularly preferably all of R ⁷¹ to R ⁷⁶ are organic groups.

Examples of the divalent linking group in X include an alkanediyl group, an alkenediyl group, a 1,4-phenylene biscyclodiyl group, an oxy group, an oxyalkyldiyloxy group, and an alkanediyloxy group. Alkanediyl and the like.

As the alkanediyl group, a carbon number of 1 to 10 is preferred. Specific examples thereof include methylene, ethyl, ethyl-1,1-diyl, propan-1,1-diyl, propyl-1,2-diyl and propyl-1,3-diyl. , C-2,2-diyl, D-1,2- Dibasic, butyl-1,3-diyl, butane-1,4-diyl, pent-1,4-diyl, pent-1,5-diyl, hex-1,5-diyl, hexyl- 1,6-diyl, octane-1,8-diyl, indole-1,10-diyl and the like. Among them, an alkanediyl group having 1 to 8 carbon atoms is preferred, and an alkanediyl group having 1 to 6 carbon atoms is more preferred, and a methylene group, an exoethyl group, a propane-1,3-diyl group, and a butyl group are particularly preferred. -1,4-diyl, pent-1,5-diyl, hex-1,6-diyl.

The olefinic group is preferably a carbon number of 2 to 10, and specifically includes an ethylene-1,1-diyl group, an ethylene-1,2-diyl group, a propylene-1,2-diyl group, and a propylene group. -1,3-diyl, propylene-2,3-diyl, 1-butene-1,2-diyl, 1-butene-1,3-diyl, 1-butene-1,4- Diyl, 2-pentene-1,5-diyl, 3-hexene-1,6-diyl and the like.

The 1,4-phenylene bisanediyl group is bonded to the alkanediyl group at both terminals of the 1,4-phenylene group, and the total carbon number of the 1,4-phenylene bisanediyl group is preferably 8 ~10. Specific examples thereof include a 1,4-phenylene bismethylene group and a 1,4-phenylene diexylethyl group.

The oxyalkyldiyloxy group is a group in which an oxygen atom is bonded to both ends of the alkanediyl group, and the total carbon number of the oxyalkyldioxy group is preferably from 1 to 10. Specific examples thereof include an oxymethyleneoxy group, an oxyethyloxy group, an oxytrimethyleneoxy group, an oxypropane-1,2-diyloxy group, and an oxytetramethyleneoxy group. Base.

The alkanediyloxyalkane group is bonded to the two alkanediyl groups through an oxygen atom, and the total carbon number of the alkanediyloxyalkyldiyl group is preferably from 2 to 20. Specific examples thereof include a methyleneoxymethylene group, an ethylideneoxyethyl group, a trimethyleneoxytrimethylene group, a methyloxytrimethylene group, and a propionyl-1,2-diyl group. Oxypropan-1,2-diyl, exoethyloxypropane-1,2-diyl, tetramethyleneoxytetramethylene, and the like.

Specific examples of the cation represented by the above formula (6) include cations represented by the following compound groups α to γ.

The invention Among the compounds, a combination of a structure represented by the formula (1) and a cation which is anionic is exemplified by a compound shown by the following compound group δ.

Also, as the invention The compound can also be used as described in the specification of Japanese Patent No. 4492760.

The polymethine compound is preferably a compound having a structure represented by the following formula (2).

[In the formula (2), the ring Z ¹ and the ring Z ² each independently represent a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted aromatic hydrocarbon group, and 1 represents an integer of 0 to 3, and m represents 0 or 1.

But l and m are not 0 at the same time. ]

The heterocyclic group in the ring Z ¹ and the ring Z ² may be a monocyclic heterocyclic group or a polycyclic heterocyclic group. The heterocyclic group is the same as the heterocyclic group of the formula (1), and among them, a nitrogen-containing aromatic heterocyclic group is preferred, and a fluorenyl group is more preferred. The substituent of the heterocyclic group in the ring Z ¹ and the ring Z ² may be the same as those described in the formula (1), and among them, an aliphatic hydrocarbon group is preferred, and a carbon number of 1 to 6 is more preferred. alkyl. Here, the hydrogen atom of the substituent of the heterocyclic group may be further substituted with a halogen atom, an alkoxy group, a phenoxy group, an aryloxy group, an aromatic hydrocarbon group, a carboxyl group, a cyano group, a nitro group or the like. Specific examples of the substituents include the same as described above.

The aromatic hydrocarbon group in the ring Z ¹ and the ring Z ² may be the same as those described in the formula (1). In addition, the substituent of the aromatic hydrocarbon group in the ring Z ¹ and the ring Z ² may be the same as those described in the formula (1), and the hydrogen atom of the substituent of the aromatic hydrocarbon group may further be A halogen atom, an alkyl group, a substituted or unsubstituted amino group, a cyano group, an alkoxy group or the like is substituted. The substituent of the amine group may, for example, be a substituted or unsubstituted alkyl group, and the alkyl group preferably has 1 to 4 carbon atoms. Examples of the substituent of the alkyl group include a halogen atom, a cyano group, an ammonium group, and a -NR ₃ ⁺ group (R represents an alkyl group having 1 to 4 carbon atoms). Specific examples of the alkyl group include the same as described above.

l and m are preferably 1.

Specific examples of the compound having a structure represented by the above formula (2) include a compound having a structure represented by the following formula (3).

In the case where the compound having the structure represented by the formula (2) is cationic, it has an anion which makes the compound electrically neutral. The anion may be the same as those described in the formula (1).

In the case where the compound having the structure represented by the formula (2) is anionic, it has a cation which makes the compound electrically neutral. The cation is the same as the one described in the formula (1).

Examples of the compound having the structure represented by the above formula (2) include basic red 12, basic red 13, basic red 14, basic violet 7, basic violet 18, and basic yellow 11 . Wait.

The coumarin compound may, for example, be Solvent Yellow 160:1, Basic Yellow 40 or the like.

Examples of the hydrazine compound include solvent orange 55 and the like.

As the coloring agent of the present invention, it is At least one compound selected from the group consisting of a compound, a polymethine compound, a coumarin compound, and an anthracene compound can also be used as a lake pigment. The lake pigment refers to a pigment which is made into a poorly soluble pigment by a precipitating agent, and examples of the precipitating agent include barium chloride, calcium chloride, ammonium sulfate, aluminum chloride, aluminum acetate, lead acetate, and single. Nitrate, Katanol, Tamol, complex heteropolyacid called phosphotungstic acid, phosphomolybdic acid, phosphotungstic acid, samarium tungsten molybdate, samarium tungstic acid , bismuth molybdate, phosphotungstic acid, phosphotungstic acid, phosphomolybdic acid, etc.

The colored composition of the present invention can also be mixed A coloring agent other than at least one compound selected from the group consisting of a compound, a polymethine compound, a coumarin compound, and an anthraquinone compound is used. As other coloring agents, it is not particularly limited, and colors and materials can be appropriately selected depending on the application. As other colorants, it can be cited A pigment, a dye, or a natural pigment other than the compound, the polymethine compound, the coumarin compound, and the quinone compound, and other colorants may be used alone or in combination of two or more. Among them, from the viewpoint of obtaining pixels having high brightness, contrast, and coloring power, the pigment is preferably an organic pigment, and the dye is preferably an organic dye.

As the organic pigment, for example, a compound classified as a pigment in a color index (C.I.; issued by The Society of Dyers and Colourists), that is, a color index (C.I.) number as given below can be cited.

CI Pigment Red 166, CI Pigment Red 177, CI Pigment Red 224, CI Pigment Red 242, CI Pigment Red 254, CI Pigment Red 264; CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58; CI Pigment Blue 15: 6. CI Pigment Blue 16, CI Pigment Blue 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, CI Pigment Yellow 215; CI Pigment Orange 38; CI Pigment Violet 23.

Others, which are described in JP-A-2001-081348, JP-A-2010-026334, JP-A-2010-237384, JP-A-2010-237569, JP-A-2011-006602, JP-A-2011- A lake pigment such as No. 145346.

Further, as the above dye, a triarylmethane dye, an anthraquinone dye, an azo dye or the like is preferable. More specifically, it is described in Japanese Laid-Open Patent Publication No. 10/123,071, JP-A-2011-116803, JP-A-2011-117995, JP-A-2011-133844, and JP-A-2011-174987 Organic dyes such as bulletins.

In the present invention, any other pigment which is optionally mixed may be purified by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof. Moreover, these pigments may also be modified with a resin to re-use the surface of the particles. The resin of the surface of the particle of the modified pigment is, for example, a carrier resin described in JP-A-2001-108817, or a commercially available resin for pigment dispersion. For example, the method of the resin coating method of the surface of the carbon black is disclosed, for example, in JP-A-H09-71733, JP-A-9-95625, and JP-A-9-124969. Further, the organic pigment may be micronized and reused by so-called salt milling. As a method of salt milling, for example, the method disclosed in Japanese Laid-Open Patent Publication No. Hei 08-179111 can be employed.

Further, in the present invention, other coloring agents which are arbitrarily mixed may be contained, and further known dispersing agents and dispersing aids. As a widely known dispersing agent, for example, a urethane dispersing agent, a polyethyleneimine dispersing agent, a polyoxyethylene alkyl ether dispersing agent, and a polyoxyethylene alkyl phenyl ether can be mentioned. Dispersing agent, polyethylene glycol diester dispersion A dissolving agent, a sorbitan fatty acid ester dispersing agent, a polyester dispersing agent, an acrylic dispersing agent, etc., and a dispersing aid may, for example, be a pigment derivative.

Such a dispersing agent can be obtained commercially, and examples thereof include an acrylic dispersing agent: Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, and BYK-LPN21324 (the above is BYK Chemie (BYK)). ); as a urethane dispersant, Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above BYK Chemie (BYK)) , Solsperse 76500 (manufactured by Lubrizol Co., Ltd.), etc.; as a polyethyleneimine-based dispersing agent, Solsperse 24000 (manufactured by Lubrizol Co., Ltd.); and as a polyester-based dispersing agent: AJISPER PB821, AJISPER PB822, AJISPER PB880, AJISPER PB881 (above is Ajinomoto Fine-Techno Co., Ltd.) and the like.

Further, specific examples of the pigment derivative include copper phthalocyanine, diketopyrrolopyrrole, and sulfonic acid derivatives of quinoline yellow.

The other coloring agents in the present invention may be used alone or in combination of two or more.

The content ratio of the other coloring agent is preferably 70% by mass or less, and more preferably 50 parts by mass or less based on the total content of the coloring agent. The lower limit value is not particularly limited, and may be 0.01% by mass or more.

(A) The content ratio of the coloring agent is such that it is excellent in heat resistance, a pixel having excellent color purity, or a black base having excellent light-shielding properties. The point of the mass and the black spacer is usually 5 to 70% by mass, preferably 5 to 60% by mass, based on the solid content of the coloring composition. Here, the solid content is a component other than the solvent described later.

- (B) Adhesive Resin -

The (B) binder resin in the present invention 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 (hereinafter also referred to as a "carboxyl group-containing polymer") is preferably an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter also referred to as "unsaturated single". Copolymer of (b1)") and other copolymerizable ethylenically unsaturated monomer (hereinafter also referred to as "unsaturated monomer (b2)").

Examples of the unsaturated monomer (b1) include (meth)acrylic acid, maleic acid, maleic anhydride, and succinic acid mono [2-(methyl)acryloxyethyl ester. ], ω-carboxypolycaprolactone mono(meth)acrylate, p-vinylbenzoic acid, and the like.

These unsaturated monomers (b1) may be used alone or in combination of two or more.

Further, as the unsaturated monomer (b2), for example, an N-position-substituted maleene such as N-phenylbutyleneimine or N-cyclohexylmethyleneimine may be mentioned. Diquinone imine; such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyloxypropyl ether, vinyl naphthalene aromatic vinyl a compound; such as methyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate Ester, benzyl (meth)acrylate, polyethylene glycol (degree of polymerization 2~10) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization 2~10) methyl ether (meth) acrylate , polyethylene glycol (degree of polymerization 2~10) mono (meth) acrylate, polypropylene glycol (degree of polymerization 2~10) mono (meth) acrylate, cyclohexyl (meth) acrylate, (methyl) Isodecyl acrylate, tricyclo [5.1.02 ^2,6 ] 癸-8-ester, dicyclopentenyl (meth) acrylate, glycerol mono(meth) acrylate, (methyl) ) 4-hydroxyphenyl acrylate, ethylene oxide modification of p-cumylphenol ( Acrylate, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3-[(meth)acryloxymethyl]oxocyclobutane, a (meth) acrylate of 3-[(meth)acryloxymethyl]-3-ethylcyclocyclobutane; such as cyclohexyl vinyl ether, isodecyl vinyl ether, tricyclo [5.2. 1.0 ^2,6 ]癸-8-yl vinyl ether, pentacyclopentadecyl vinyl ether, vinyl ether of 3-(vinyloxymethyl)-3-ethyloxycyclobutane; such as polyphenylene Ethylene, polymethyl (meth) acrylate, poly-n-butyl acrylate (meth) acrylate, polysiloxane, macromolecular monomer having a mono (meth) acrylonitrile group at the end of the polymer molecular chain .

These unsaturated monomers (b2) may be used alone or in combination of two or more.

In the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2), the copolymerization ratio of the unsaturated monomer (b1) in the copolymer is preferably from 5 to 50% by mass, more preferably from 10 to 40%. quality%. By copolymerizing the unsaturated monomer (b1) in such a range, a colored composition excellent in alkali developability and storage stability can be obtained.

Specific examples of the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2), for example, JP-A-7-140654, JP-A-8-259876, and JP-A 10-31308 Copolymers disclosed in, for example, Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei.

In the present invention, for example, Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. In general, as disclosed in JP-A-2008-181095, a carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) acrylonitrile group in a side chain can be used as the binder resin.

In the binder resin of the present invention, the weight average molecular weight (Mw) in terms of polystyrene by gel permeation chromatography (hereinafter referred to as GPC) (flushing solvent: tetrahydrofuran) is usually 1,000 to 100,000, preferably 3,000. ~50,000. By forming such a state, the residual film ratio, pattern shape, heat resistance, electrical characteristics, and resolution of the film can be further improved, and generation of dry impurities during coating can be suppressed at a high level.

Further, the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the binder resin in the present invention is preferably 1.0 to 5.0, more preferably 1.0 to 3.0. Here, Mn refers to a number average molecular weight in terms of polystyrene measured by GPC (flushing solvent: tetrahydrofuran).

The binder resin in the present invention can be produced by a well-known method, for example, by the special publication 2003-222717, The method disclosed in the publication No. 2006-259680, International Publication No. 07/029871, and the like can also control the structure and Mw, Mw/Mn.

In the present invention, the binder resin may be used alone or in combination of two or more.

In the present invention, the content of the binder resin is usually 10 to 1,000 parts by mass, preferably 20 to 500 parts by mass, per 100 parts by mass of the (A) colorant. By forming such an aspect, the alkali developability, the storage stability of the colored composition, and the chromaticity characteristics can be further improved.

- (C) Polymeric Compound -

The polymerizable compound in the present invention means a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, and an N-alkoxymethylamino group. In the present invention, the polymerizable compound is preferably a compound having two or more (meth)acryl fluorenyl groups or a compound having two or more N-alkoxymethylamino groups.

Specific examples of the compound having two or more (meth) acrylonitrile groups include polyfunctional (meth) acrylates obtained by reacting an aliphatic polyhydroxy compound with (meth)acrylic acid. Multifunctional amine group obtained by reacting ester-modified polyfunctional (meth) acrylate, alkylene oxide modified polyfunctional (meth) acrylate, hydroxyl group (meth) acrylate with polyfunctional isocyanate A polyfunctional (meth) acrylate having a carboxyl group obtained by reacting a formate (meth) acrylate, a hydroxyl group-containing (meth) acrylate, and an acid anhydride.

Here, as the aliphatic polyhydroxy compound, for example, a valence of, for example, ethylene glycol, propylene glycol, polyethylene glycol, or polypropylene glycol is exemplified. An aliphatic polyhydroxy compound; a trivalent or higher aliphatic polyhydroxy compound such as glycerol, trimethylolpropane, neopentyl alcohol, or dipentaerythritol. Examples of the (meth) acrylate having the above hydroxyl group include 2-hydroxyethyl (meth)acrylate, trimethylolpropane di(meth)acrylate, and pentaerythritol tri(methyl). Acrylate, dipentaerythritol penta (meth) acrylate, glycerin dimethacrylate, and the like. The polyfunctional isocyanate may, for example, be benzylidene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate or isophorone diisocyanate. Examples of the acid anhydride include anhydrides of dibasic acids such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, and hexahydrophthalic anhydride, and pyromellitic acid II. A tetrabasic acid dianhydride such as an anhydride, a biphenyltetracarboxylic dianhydride or a benzophenone tetracarboxylic dianhydride.

In addition, the polyfunctional (meth) acrylate which is modified by the caprolactone, for example, is a compound of the paragraphs [0015] to [0018] described in JP-A-11-44955. The polyfunctional (meth) acrylate modified with the above alkylene oxide may, for example, be bisphenol A (methyl) modified with at least one selected from the group consisting of ethylene oxide and propylene oxide. An acrylate, at least one modified isocyanuric acid tri(meth)acrylate selected from ethylene oxide and propylene oxide, selected from ethylene oxide and propylene oxide At least one modified trimethylolpropane tri(meth)acrylate, at least one modified pentaerythritol tri(meth)acrylate selected from ethylene oxide and propylene oxide At least one modified pentaerythritol tetra(meth)acrylate selected from ethylene oxide and propylene oxide, and at least one selected from ethylene oxide and propylene oxide Modified dipentaerythritol penta (meth) acrylate, after passing from epoxy B At least one modified dipentaerythritol hexa(meth)acrylate selected from the group consisting of an alkane and a propylene oxide.

Further, examples of the compound having two or more N-alkoxymethylamino groups include a melamine structure and a benzoquinone. Structure, compound having a urea structure, and the like. Among them, melamine structure, benzoquinone Structure means having more than one three Ring or phenyl substituted three The ring is used as the chemical structure of the basic skeleton, and also contains melamine and benzoquinone. Or the concept of its 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)acetylene urea, and the like.

Among these polymerizable compounds, a polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound having a trivalent or higher value with (meth)acrylic acid or a polyfunctional group modified by caprolactone is preferred. Acrylate, polyfunctional urethane (meth) acrylate, polyfunctional (meth) acrylate having carboxyl group, N, N, N', N', N", N"-hexa Oxymethyl) melamine, N, N, N', N'-tetrakis(alkoxymethyl)phenylhydrazine . On the other hand, in the case where the strength of the colored layer is high, the surface smoothness of the colored layer is excellent, and the trivalent or higher aliphatic polyhydroxy compound and the point are not likely to cause scum or film residue on the substrate of the unexposed portion and the light shielding layer. Among the polyfunctional (meth) acrylates obtained by the reaction of (meth)acrylic acid, particularly preferred are trimethylolpropane triacrylate, neopentyl alcohol triacrylate, dipentaerythritol pentaacrylate, and new Pentaerythritol hexaacrylate, a polyfunctional (meth) acrylate having a carboxyl group, particularly preferably a compound obtained by reacting pentaerythritol triacrylate with succinic anhydride, dipentaerythritol pentaacrylate and A compound obtained by the reaction of succinic anhydride.

In the present invention, the (C) polymerizable compound may be used singly or in combination of two or more kinds.

In the present invention, the content of the (C) polymerizable compound is preferably 10 to 1,000 parts by mass, more preferably 20 to 700 parts by mass, even more preferably 100 to 500 parts by mass per 100 parts by mass of the (A) coloring agent. Share. By forming such a state, the curability and the alkali developability are further improved, and scum, film residue, and the like can be suppressed from occurring on the substrate of the unexposed portion or the light shielding layer at a high level.

-(D) transition metal compound -

The coloring composition of the present invention contains the component (D) (except for the component (A) described above). The component (D) in the present invention has A compound composed of a skeleton, a polymethine skeleton, a coumarin skeleton, and a skeleton other than the fluorene skeleton and a transition metal. The component (D) in the present invention is preferably one which is dissolved in an organic solvent.

Examples of the transition metal include cerium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), and nickel (Ni). Copper (Cu), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), niobium (Tc), ruthenium (Ru), rhenium (Rh), palladium (Pd), silver (Ag),镧 (La), 铈 (Ce), 鐠 (Pr), 钕 (Nd), 鉕 (Pm), 钐 (Sm), 铕 (Eu), 釓 (Gd), 鋱 (Tb), 镝 (Dy),鈥 (Ho), 铒 (Er), 銩 (Tm), 镱 (Yb), 镏 (Lu), 铪 (Hf), 钽 (Ta), tungsten (W), 铼 (Re), 锇 (Os), Ir (Ir), platinum (Pt), gold (Au), and the like. Among them, a transition metal belonging to the fourth cycle is preferred, and more preferably samarium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co). , nickel (Ni), copper (Cu).

Examples of the (D) transition metal compound in the present invention include a non-electrolyte-type transition metal complex (hereinafter also referred to as "compound (d1)") and an electrolyte-type transition metal complex (hereinafter also referred to as "Compound (d2)".). Among them, the compound (d2) is preferred from the viewpoint that a color-curable film having a high contrast can be formed. In the present invention, the transition metal complex in the compound (d1) and the compound (d2) is centered on a transition metal or a transition metal ion, and is coordinated from a monodentate ligand and a multidentate ligand. At least one selected, single tooth ligand and multidentate coordination system have A compound of a skeleton other than a skeleton, a polymethine skeleton, a coumarin skeleton, and an anthracene skeleton. Further, the non-electrolyte type transition metal complex means that the complex itself constitutes a complex of a complex ligand, and the electrolyte type transition metal complex means having a coordination cation or a coordination anion as a misalignment. A complex of complexed radicals.

Examples of the ligand in the compound (d1) include fluorine, chlorine, bromine, iodine, hydroxyl, water, tetrahydrofuran, ethylene glycol dimethyl ether, acetonitrile, benzonitrile, pendant oxy group, and peroxygen. Base, carbonyl, carbonate, oxalate, acetate, ethanol, 1-butanethiol, thiophenolate, 2,2'-thiobis(4-t-octyl)phenolate, acetoacetate, 2,2,6,6-tetramethyl-3,5-pimelate, trifluoroacetamidine, hexafluoroacetamone, ethyl acetonide, thiocyanate, isothiocyanate, Diethyldithiocarbamate, di-n-butyldithiocarbamate, cyanide, amine, dimethylamine, diethylamine, tetraethylammonium, piperidine, N-methylaniline, pyridine, 2 -Phenylpyridine, ethylenediamine, N,N,N',N'-tetramethylethylenediamine, 1,2-diaminocyclohexane, 2,2'-bipyridine, 1,10-morphine Porphyrin, ethylenediaminetetraacetate, 1,4,8,11-tetraazacyclotetradecane, ginseng (2-aminoethyl)amine, sulfate, nitro, nitrite, Phosphate, diisopropyldithiophosphate, diethyldithiophosphate, triethylphosphine, tributylphosphine, tricyclohexylphosphine, dimethylphenylphosphine, triphenylphosphine, two Phenylphosphine, tricyclohexylphosphine, cyclopentadiene, pentamethylcyclopentadiene, cyclooctene, 1,5-cyclooctadiene, bicyclo[2.2.1]pent-2,5-diene, 4-dimethylaminodithiobenzyl, benzene, naphthalene, allyl, and the like.

Specific examples of the compound (d1) include those exemplified in paragraphs [0102] to [0116] of JP-A-2004-295116. Among them, it is preferred to have acetate, acetoacetate, hexafluoroacetamone, thiocyanate, diethyldithiocarbamate, di-n-butyldithiocarbamate, sulfate, 4- Dimethylaminodithiobenzyl is used as a transition metal complex of the ligand. Specific examples thereof include: chromium (III) ammonium sulfate 12 hydrate, acetamidine acetone vanadium (III), acetonitrile acetone chromium (III), acetamidine acetone manganese (III), acetamidine acetone iron (III), and B.醯Acetone cobalt (II), acetonitrile acetone nickel (II), acetonitrile acetone copper (II), chromium (III) acetate monohydrate, manganese (II) diacetate tetrahydrate, iron (II) diacetate, two Cobalt (II) acetate tetrahydrate, nickel (II) diacetate tetrahydrate, copper (II) acetate, bis(4-dimethylaminodithiobenzyl) nickel (II), and the like.

As the compound (d2), it is preferred to have A compound of a skeleton other than a skeleton, a polymethine skeleton, a coumarin skeleton, and an anthracene skeleton is used as a transition metal complex anion of a ligand, and a salt of a cation selected from a metal cation and a phosphonium cation.

The compound (d2) is not particularly limited, and is preferably a transition metal complex anion having an azo compound in the ligand, and a salt of a cation selected from the metal cation and the phosphonium cation. In the case where the transition metal complex is a polyvalent anion, it has the same number of cations as the electrically neutral and the anion, but they may be the same or different.

Here, the azo compound contains a compound having an azo group. The ligand represented by the following formula (a) is exemplified as such a ligand.

[In the formula (a), the ring Z ³ represents a substituted or unsubstituted heterocyclic group independently of each other, and the ring Z ⁴ independently represents a substituted or unsubstituted aromatic hydrocarbon group, and t ¹ and t ² are independently of each other. Indicates 0 or 1. ]

Specific examples of the anion having a transition metal complex of the azo compound in the ligand include an anion represented by the following formula (4).

[In the formula (4), the ring Z ³ represents a substituted or unsubstituted heterocyclic group independently of each other, the ring Z ⁴ independently represents a substituted or unsubstituted aromatic hydrocarbon group, and the M system represents a transition metal, t ¹ and The t ² series independently represents 0 or 1. ]

The heterocyclic group in the ring Z ³ may be a monocyclic heterocyclic group or a polycyclic heterocyclic group. The heterocyclic group is exemplified by the formula (1), and among them, a nitrogen-containing aromatic heterocyclic group, a pyridyl group or a pyrazolyl group is preferred. The substituent of the heterocyclic group may be exemplified by the formula (1), and among them, a hydroxyl group, a cyano group, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an aliphatic hydrocarbon group and an aromatic hydrocarbon group may be further used. Has a substituent. Among them, specific examples of the aliphatic hydrocarbon group and the aromatic hydrocarbon group are as described in the formula (1).

The aromatic hydrocarbon group in the ring Z ⁴ may be exemplified by the formula (1), and among them, a phenyl group is preferred. Examples of the substituent of the aromatic hydrocarbon group include, in addition to those exemplified in the formula (1), a sulfo group, an aminesulfonyl group, an alkylguanamine group, and two alkylguanamine groups. a base formed by the alkyl group of one alkyl guanamine group bonded to the amine group of another alkyl guanamine group (hereinafter referred to as "the base of two alkyl amide groups""). Among them, preferred are a halogen atom, a hydroxyl group, a cyano group, a nitro group, an alkoxy group, a sulfo group, an alkylsulfonyl group, an aminesulfonyl group, an alkylaminesulfonyl group, an alkylguanamine group, and two alkane groups. A group based on an amine bond, an aliphatic hydrocarbon group. The alkyl moiety of the alkylsulfonyl group, the amine sulfonyl group, and the alkylamine sulfonyl group, and the aliphatic hydrocarbon group may further have a substituent.

The anion represented by the following formula (4) is preferably an anion represented by the following formula (4-1) or (4-2).

In the formula (4-1), R ²¹ each independently represents a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, and R ²² independently represents an alkyl group having 1 to 8 carbon atoms, a halogen atom, and a nitrate. a group, -SO ₃ H, -SO ₂ R ²⁴ , -SO ₂ NH ₂ , -SO ₂ NHR ²⁵ , -NHCO-R ²⁶ -NHCOR ²⁷ , R ²³ independently of each other represents a nitro group, -SO ₃ H, - SO ₂ NH ₂ , -SO ₂ NHR ²⁸ , R ²⁴ , R ²⁵ , R ²⁷ and R ²⁸ each independently represent a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, and R ²⁶ represents a carbon number of 1 to 6 The alkanediyl group, the M ² system represents a transition metal, and the p and q systems independently represent an integer of 0 to 2, and t ² represents 0 or 1 independently of each other. ]

In the formula (4-2), R ³¹ each independently represents a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, and R ³² each independently represents an alkyl group having 1 to 8 carbon atoms and a carbon number of 1 to 8; Alkoxy group of 8, a halogen atom, a hydroxyl group, a cyano group, a nitro group, a sulfo group, -SO ₂ NHR ³⁴ , -NHCOR ³⁵ , and R ³³ each independently represent an alkyl group or a cyano group having 1 to 8 carbon atoms, R ³⁴ and R ³⁵ each independently represent an alkyl group having 1 to 8 carbon atoms, M ³ represents a transition metal, and x and y each independently represent an integer of 0 to 2, and t ² represents 0 or 1 independently of each other. ]

The alkyl group having 1 to 8 carbon atoms in R ²¹ , R ²² , R ²⁴ , R ²⁵ , R ²⁷ , R ²⁸ , R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ is a straight chain or a branched chain. However, as a specific example, it can be exemplified by the formula (1).

Examples of the substituent of the alkyl group in R ²¹ include a hydroxyl group and -COOR ²⁹ . R ²⁹ is an alkyl group having 1 to 8 carbon atoms and may be either a straight chain or a branched chain.

Further, examples of the substituent of the alkyl group in R ²⁴ , R ²⁵ , R ²⁷ and R ²⁸ include an alkoxy group having 1 to 6 carbon atoms.

Further, examples of the substituent of the alkyl group in R ³¹ include a hydroxyl group, -COOR ³⁶ , -OCOR ³⁶ , -CO-R ³⁷ -OH, -COR ³⁶ and -CONHR ³⁸ . R ³⁶ and R ³⁸ are each independently an alkyl group having 1 to 8 carbon atoms or a phenyl group, and the alkyl group may be a straight chain or a branched chain. R ³⁷ is an alkanediyl group having 1 to 6 carbon atoms and may be a straight chain or a branched chain. Specific examples of the alkanediyl group having 1 to 6 carbon atoms are exemplified by the formula (7).

The alkanediyl group having 1 to 6 carbon atoms in R ²⁶ may be a straight chain or a branched chain.

The transition metal in M ² is preferably cobalt, chromium, iron, nickel or copper, more preferably cobalt, chromium, iron or nickel, still more preferably cobalt, chromium or iron, particularly preferably cobalt or chromium.

As the transition metal in M ³ , preferably cobalt, chromium, iron, nickel, copper, more preferably cobalt, chromium, iron, nickel, more preferably cobalt, chromium, iron, and even more preferably cobalt. , chromium, especially good for chromium.

p is preferably 0 or 1.

q is preferably 1 or 2.

x is preferably 0 or 1.

y is preferably 2, and in this case, the two R ³³ on the hetero ring may be the same or different.

The metal cation in the compound (d2) is the same as the above.

The phosphonium cation in the compound (d2) may, for example, be a phosphonium cation or an ammonium cation. Preferred examples of the phosphonium cation include the cations represented by the above formulas (6) and (7), and the specific structures thereof are as described above. Further, a polymer having a structural unit represented by the following formula (8) can also be preferably used as the above phosphonium cation.

In the formula (8), R ⁸¹ represents a hydrogen atom or a methyl group.

R ⁸² to R ⁸⁴ each independently represent a hydrogen atom or a hydrocarbon group. However, at least one of R ⁸² to R ⁸⁴ is a hydrocarbon group, and two of R ⁸² to R ⁸⁴ may be bonded to form a ring.

Q ¹ represents a single bond or a divalent group. ]

The ammonium cation in the compound (d2) is preferably a cation represented by the above formula (5), and the specific structure thereof is as described above. Further, as the ammonium cation, a polymer having a structural unit represented by the following formula (9) and a polymer having a structural unit represented by the formula (10) can be preferably used.

In the formula (9), R ⁹¹ represents a hydrogen atom or a methyl group.

R ⁹² to R ⁹⁴ each independently represent a hydrogen atom or a hydrocarbon group, and two of R ⁹² to R ⁹⁴ may be bonded to form a ring.

Q ² represents a single bond or a divalent group. ]

[In the formula (10), the ring Z system represents a nitrogen-containing hetero ring.

R ¹⁰¹ represents a hydrogen atom or a methyl group.

R ¹⁰² represents a hydrogen atom or a hydrocarbon group.

The Q ³ system represents a single bond or a divalent group. ]

The hydrocarbon group in R ⁸² to R ⁸⁴ , R ⁹² to R ⁹⁴ and R ¹⁰² may be the same as the hydrocarbon group in R ⁵¹ to R ⁵⁴ , and the preferred embodiment is also the same.

Examples of the divalent group in Q ¹ , Q ² and Q ³ include a divalent hydrocarbon group, a group in which a divalent hydrocarbon group is bonded to a linking group containing a carbon atom or an atom other than a hydrogen atom, or a halogen group. An atom is a group formed by substituting a part of hydrogen atoms of the group. Wherein Q ³ may be bonded to any carbon atom on the nitrogen-containing heterocycle.

The divalent hydrocarbon group may, for example, be a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, a divalent aromatic hydrocarbon group, or a combination thereof. The divalent aliphatic hydrocarbon group may be either a straight chain or a branched chain, and the divalent aliphatic hydrocarbon group and the divalent alicyclic hydrocarbon group may be saturated or unsaturated.

The divalent aliphatic hydrocarbon group is preferably an alkanediyl group having 1 to 10 carbon atoms, more preferably an alkanediyl group having 2 to 6 carbon atoms. As a specific example, the same as the above is mentioned.

The divalent alicyclic hydrocarbon group is preferably a cycloalkyl group having 3 to 20 carbon atoms, more preferably a cycloalkyl group having 5 to 10 carbon atoms. Specific examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

The divalent aromatic hydrocarbon group may, for example, be an arylene group, and among them, a monocyclic to 3-ring arylene group having 6 to 14 carbon atoms is preferred. Specific examples thereof include a phenylene group, a naphthylene group, a biphenylylene group, and a fluorenyl group.

As a group in which a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group are combined, it is preferably an alkylene alkanediyl group having 7 to 20 carbon atoms, more preferably an alkylene alkane having 2 to 15 carbon atoms. base. Specific examples thereof include a phenylene methylene group, a phenylene dimethylene group, a phenylene trimethylene group, a phenylenetetramethylene group, a phenylene pentamethylene group, and a phenylene hexaylene group. A phenylene C _1-6 alkanediyl group such as methyl. Among them, the arylene alkanediyl group has an ortho, a meta-substrate and a para-substrate, and from the viewpoint of having few steric hindrance, a para-substrate is preferred.

Examples of the combination of a divalent hydrocarbon group and a linking group containing a carbon atom and an atom other than a hydrogen atom include, for example, an alkanediyl group having 1 to 10 carbon atoms and a ring having a carbon number of 3 to 10. At least one selected from the group consisting of an alkyl group, an arylene group having 6 to 14 carbon atoms, and an arylene group having 7 to 20 carbon atoms, and -O-, -S-, -COO-, -CONR '-(R' represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms) and a combination of at least one selected from -SO ₂ -. Among them, at least one selected from the group consisting of an alkanediyl group having 1 to 10 carbon atoms and an arylene group having 6 to 20 carbon atoms is preferable from the group consisting of -O-, -COO-, and -SO ₂ - At least one selected combination is selected.

In the polymer having a structural unit represented by the formula (10), the nitrogen-containing heterocyclic ring constituting the ring Z may be monocyclic or polycyclic, and may be either an unsaturated ring or a saturated ring. Specific examples thereof include a nitrogen-containing alicyclic heterocyclic ring and a nitrogen-containing aromatic heterocyclic ring. Among them, a nitrogen-containing aromatic heterocyclic ring is preferred, and examples thereof include a pyridine ring, a pyrazole ring, and a pyridyl group. Ring, pyrimidine ring, anthracene Monocyclic nitrogen-containing aromatic heterocyclic ring, imidazole ring, quinoline ring, isoquinoline ring, benzimidazole ring, quin Phytoline ring, quinazoline ring, hydrazine A cyclic heterocyclic nitrogen-containing aromatic heterocyclic ring. Further, the nitrogen-containing aromatic heterocyclic ring may have a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a halogen atom, a carboxyl group, an alkoxycarbonyl group, an alkoxy group, a hydroxyl group, and an amine group. , amidino group, sulfhydryl group, thioether group and the like.

The polymer having a structural unit represented by the formula (9) can be obtained, for example, by reacting a polymer having a structural unit represented by the following formula (11) with a halogenated hydrocarbon to form a quaternary ammonium salt. In addition, the polymer having a structural unit represented by the formula (10) can be obtained, for example, by reacting a polymer having a structural unit represented by the following formula (12) with a halogenated hydrocarbon to form a quaternary ammonium salt. Here, the formation reaction of the quaternary ammonium salt can be carried out by a well-known method, and all the amine groups in the polymer having the structural unit represented by the following formula (11) or have the formula (12) The entire imine group in the polymer of the structural unit does not necessarily need to be a quaternary ammonium salt.

In the formula (11), R ¹¹¹ represents a hydrogen atom or a methyl group.

R ¹¹² and R ¹¹³ each independently represent a hydrogen atom or a hydrocarbon group, and R ¹¹² and R ¹¹³ may be bonded to each other to form a ring.

Q ⁴ represents a single bond or a divalent group. ]

[In the formula (12), the ring Z system is synonymous with the ring Z in the formula (10).

R ¹²¹ represents a hydrogen atom or a methyl group.

Q ⁵ represents a single bond or a divalent group. ]

The hydrocarbon group in R ¹¹² and R ¹¹³ may be the same as the hydrocarbon group in R ⁵¹ to R ⁵⁴ , and the preferred embodiment is also the same.

The divalent group in Q ⁴ and Q ⁵ may be the same as the divalent group in Q ¹ , Q ² and Q ³ .

The monomer to which the structural unit represented by the formula (8) is given may, for example, be allyltriphenylphosphonium bromide or 4-allylphenyltributylphosphonium chloride. They may be used alone or in combination of two or more.

The monomer to which the structural unit represented by the formula (9) is given may, for example, be chlorinated (meth) acrylamidopropyltrimethylammonium chloride or chloro(meth) propylene oxyloxy group. Ethyltrimethylammonium, (meth)acryloyloxyethyltriethylammonium chloride, brominated (meth)acryloxyethyl (4-benzylidenebenzyl)dimethyl (meth)acryloyl fluorenyl group, such as ammonium, chlorinated (meth) propylene methoxyethyl benzyl dimethyl ammonium, chlorinated (meth) propylene methoxy ethyl benzyl diethyl ammonium Ammonium salt. They may be used alone or in combination of two or more.

Examples of the monomer to which the structural unit represented by the formula (11) is given include, for example, dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, and (methyl). Dimethylaminobutyl acrylate, diethylaminoethyl (meth)acrylate, diethylaminopropyl (meth)acrylate, diethylaminobutyl (meth)acrylate, (meth)acrylic acid Methylaminoethoxyethyl ester, dimethylaminoethoxypropyl (meth)acrylate, diethylaminobutoxybutyl (meth)acrylate, and the like. They may be used alone or in combination of two or more.

The monomer to which the structural unit represented by the formula (12) is given may, for example, be 2-vinylpyridine or 4-vinylpyridine. They may be used alone or in combination of two or more.

The polymer having a structural unit represented by the formula (8), the formula (9) or the formula (10) may have a structural unit other than the structural unit which is necessary. Examples of such a structural unit include, for example, a structural unit derived from an ethylenically unsaturated monomer having one or more carboxyl groups, a structural unit derived from an N-substituted maleimide, and a source. a structural unit derived from an aromatic vinyl compound, a structural unit derived from (meth) acrylate, a structural unit derived from a vinyl ether, and a mono(meth)acryl fluorenyl group derived from a terminal having a molecular chain of a polymer A structural unit of a macromonomer. As a specific example, the same as the above is mentioned. Among them, from the viewpoint of dispersibility, as other structural units, it is preferred to have a structural unit derived from (meth) acrylate. As the (meth) acrylate, preferably methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, etc. Base) C _1-10 alkyl acrylate.

The content of the structural unit represented by the formula (8), the formula (9) or the formula (10) is preferably 3% by mass or more, more preferably 5% by mass or more, based on the total structural unit of the polymer. More preferably, it is 8 mass% or more. In addition, the upper limit of the content is not particularly limited, and can be appropriately selected depending on the type of the polymer, and is preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less.

A polymer having a structural unit represented by the formula (8), the formula (9) or the formula (10) can be supplied together with other monomers as desired by a monomer corresponding to each of the structural units respectively required It is produced by a polymerization reaction which is the same as the above-mentioned binder resin.

The polymer having a structural unit represented by the formula (8), the formula (9) or the formula (10), which has a weight average molecular weight (Mw) in terms of polystyrene measured by GPC, is usually 1,000 to 50,000, preferably It is 3,000~30,000.

The cation in the compound (d2) is preferably a phosphonium cation, more preferably at least one selected from the group consisting of phosphonium cations and ammonium cations.

The cation which is a ruthenium cation in the compound (d2) is preferably a cation represented by the above formula (6) and formula (7), and more preferably a formula (6). Indicates the cation.

The ammonium cation in the compound (d2) is preferably a polymer having a cation represented by the above formula (5) and a structural unit represented by the formula (9), from the viewpoint of easiness of obtaining a raw material. More preferably, it is a cation represented by the formula (5).

In the present invention, the (D) transition metal compound may be used singly or in combination of two or more kinds.

In the present invention, the total content of the (D) transition metal compound is relative to The total content of at least one compound selected from the group consisting of the compound, the polymethine compound, the coumarin compound, and the hydrazine compound is 100 parts by mass, preferably 0.01 to 90 parts by mass, more preferably 0.1 to 70. The mass part is preferably 1 to 50 parts by mass, more preferably 2 to 35 parts by mass, and particularly preferably 3 to 25 parts by mass.

The content of the (D) transition metal compound is preferably 0.01 to 60 parts by mass, more preferably 0.1 to 45 parts by mass, even more preferably 0.5 to 35 parts by mass based on 100 parts by mass of the total of the (A) coloring agent. It is preferably 1 to 25 parts by mass, and particularly preferably 1.5 to 15 parts by mass.

By forming such a state, a comparatively high color hardening film can be obtained.

-Photopolymerization initiator -

A photopolymerization initiator may be included in the color composition of the present invention. Thereby, the coloring composition can be imparted with radiation sensitivity. The photopolymerization initiator used in the present invention is a compound which emits an active species capable of starting polymerization of the above polymerizable compound by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam or X-ray.

Such a photopolymerization initiator can be exemplified by, for example, 9-oxosulfur Compound, acetophenone compound, biimidazole compound, three A compound, an O-mercaptopurine compound, an onium salt compound, a benzoin compound, a benzophenone compound, an α-diketone compound, a polynuclear hydrazine compound, a diazo compound, an imidosulfonate compound, or the like.

In the present invention, the photopolymerization initiators may be used alone or in combination of two or more. As a photopolymerization initiator, preferably from 9-oxosulfur Compound, acetophenone compound, biimidazole compound, three At least one selected from the group consisting of a compound and an O-mercaptopurine compound.

Among the preferred photopolymerization initiators of the present invention, 9-oxosulfur Specific examples of the compound include 9-oxosulfur 2-chloro 9-oxosulfur 2-methyl-9-oxosulfur 2-isopropyl-9-oxosulfur 4-isopropyl-9-oxosulfur 2,4-dichloro-9-oxosulfur 2,4-dimethyl-9-oxosulfur 2,4-diethyl-9-oxosulfur 2,4-diisopropyl-9-oxosulfur Wait.

Further, specific examples of the acetophenone compound include 2-methyl-1-[4-(methylthio)phenyl]-2- Phenylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4- Phenylphenyl)butan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4- Phenylphenyl)butan-1-one and the like.

Further, specific examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-linked. Imidazole, 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.

Among them, in the case where a biimidazole compound is used as a photopolymerization initiator, and a hydrogen donor is used to improve the sensitivity, it is preferable. The term "hydrogen donor" as used herein means a compound capable of supplying a hydrogen atom to a radical generated from a biimidazole compound by exposure. Examples of the hydrogen donor include 2-mercaptobenzothiazole and 2-mercaptobenzoene. An amine hydrogen donor such as a thiol hydrogen donor such as azole or 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. It is preferred to use one or more thiol hydrogen donors in combination with one or more amine hydrogen donors to further improve the sensitivity. of.

Again, as the above three Specific examples of the compound include: 2,4,6-gin (trichloromethyl) symmetry three 2-methyl-4,6-bis(trichloromethyl) symmetry three , 2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl) symmetric three 2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl) symmetric three 2-[2-(4-Diethylamino-2-methylphenyl)vinyl]-4,6-bis(trichloromethyl)symmetric three 2-[2-(3,4-Dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)symmetric three 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl) symmetry three 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)symmetric three 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)symmetric three Three of the halomethyl groups Compound.

Further, specific examples of the O-indenyl hydrazine compound include 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzylidene).肟), ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(O-ethylindenyl), B Ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylmethoxybenzylidene)-9H-indazol-3-yl]-, 1-(O-ethenyl)肟), ethyl ketone, 1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-di) Methoxybenzopyridinyl}-9H-indazol-3-yl]-, 1-(O-ethylindenyl) and the like. As a commercial product of an O-indenyl compound, NCI-831, NCI-930 (above, ADEKA Co., Ltd.), DFI-020, DFI-091 (manufactured by DAITO CHEMIX Co., Ltd.), etc. can also be used. .

In the present invention, in the case of using a photopolymerization initiator other than the biimidazole compound such as an acetophenone compound, a sensitizer may be used in combination. As such a sensitizer, for example, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4-diethyl Aminoacetophenone, 4-dimethylaminopropiophenone, ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis(4-di Ethylbenzylidenemethyl)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzimidyl)coumarin, 4-(diethylamino)chalcone, and the like.

In the present invention, the content of the photopolymerization initiator is preferably 0.01 to 120 parts by mass, particularly preferably 1 to 100 parts by mass, per 100 parts by mass of the (C) polymerizable compound. By forming such an aspect, the hardenability and film properties can be further improved.

- solvent -

The coloring composition of the present invention contains the above components (A) to (D) and any other components added arbitrarily, and is usually prepared by mixing a solvent to prepare a liquid composition.

As the solvent, if the components (A) to (D) constituting the colored composition are dispersed or dissolved, and they do not react with these components and have moderate volatility, they can be appropriately selected and used. .

Examples of such a solvent 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 diethyl ether. 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 single positive Propylene 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, etc. Glycol monoalkyl ethers; alkyl lactate such as methyl lactate or ethyl lactate; methanol, ethanol, propanol, butanol, isopropanol, isobutanol, tertiary butanol, octanol, 2- (cyclo)alkyl alcohols such as ethylhexanol and cyclohexanol; ketone alcohols such as diacetone alcohol; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl Ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, acetic acid 3-A Butyl ester, 3-methyl-3-methoxybutyl acetate, etc. (poly)alkylene glycol monoalkyl ether acetate; diethylene glycol dimethyl ether, diethylene glycol methyl ether, diethyl Other ethers such as diol diethyl ether and tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone; Diacetate such as propylene glycol diacetate, 1,3-butanediol diacetate or 1,6-hexanediol diacetate; methyl 3-methoxypropionate, 3-methoxy Alkoxy groups such as ethyl propionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutyl propionate Carboxylic esters; 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, 2-sided oxygen Other esters such as ethyl butyrate; aromatic hydrocarbons such as toluene and xylene; N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc. Amine or indoleamines, etc.

Among these solvents, from the viewpoints of solubility, pigment dispersibility, coatability, and the like, (poly)alkylene glycol monoalkyl ethers, alkyl lactates, (poly)alkylene glycols are preferred. Alkyl ether acetates, other ethers, ketones, diacetates, alkoxycarboxylates, other esters, particularly preferably propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether Acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-glycol Ketone, 3-heptanone, 1,3-butanediol diacetate, 1,6-hexanediol diacetate, ethyl lactate, ethyl 3-methoxypropionate, 3-ethoxyl Methyl propionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutyl propionate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, N-butyl propionate, ethyl butyrate, isopropyl butyrate, n-butyl butyrate, ethyl pyruvate.

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

The content of the solvent is not particularly limited, and the total concentration of each component excluding the solvent of the coloring composition is preferably 5 to 50% by mass, and more preferably 10 to 40% by mass. By forming such a form, a colorant dispersion having good dispersibility and stability, and a coloring composition excellent in coatability and stability can be obtained.

-additive-

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

Examples of the additive include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly(fluorinated alkyl acrylate); surfactants such as fluorine surfactants and polyfluorene surfactants; ; vinyl trimethoxy decane, vinyl triethoxy decane, vinyl ginseng (2-methoxyethoxy) decane, N-(2-aminoethyl)-3-aminopropylmethyl Dimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethyl Oxydecane, 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxy a adhesion promoter such as decane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane; 2,2-thiobis (4-methyl-6-tertiary butyl phenol), 2,6-di-tertiary butyl phenol, neopentyl pentoxide [3-(3,5-bis-tertiary butyl-4-hydroxyphenyl) Propionate], 3,9-bis[2-[3-(3-tri-butyl-4-hydroxy-5-methylphenyl)propanoxy]-1,1-dimethylethyl Base]-2 , 4, 8, 10 - four An antioxidant such as spiro[5.5]undecane or thiodiglycol bis[3-(3,5-bistris-butyl-4-hydroxyphenyl)propionate; 2-(3-tertiary butyl) Ultraviolet absorbers such as 5-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole and alkoxybenzophenone; anti-agglomerating agents such as sodium polyacrylate; malonic acid and adipic acid , itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino- Residue improver such as 1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol; succinic acid mono[2-(methyl)acryloxyl A developer improving agent such as ester], phthalic acid mono [2-(methyl) propylene methoxyethyl ester], ω-carboxy polycaprolactone mono (meth) acrylate, or the like.

The coloring composition of the present invention can be prepared by a suitable method, and the method of the present invention can be exemplified, for example, in the method disclosed in JP-A-2008-58642 and JP-A-2010-132874. In the case where both the dye and the pigment are used as the coloring agent, as disclosed in Japanese Laid-Open Patent Publication No. 2010-132874, the dye solution passing through the first filter and the other may be used after passing the dye solution through the first filter. A method in which the prepared pigment dispersion liquid or the like is mixed, and the obtained coloring composition is passed through a second filter. Further, the dye, the components (B) to (D), and other components as needed may be dissolved in a solvent, and the obtained solution may be passed through the first filter, and then the solution passing through the first filter may be used. Further, the prepared pigment dispersion was mixed, and the obtained colored composition was prepared by passing through a second filter. Further, by passing the dye solution through the first filter, the dye solution passing through the first filter may be mixed with the components (B) to (D) and other components as needed, and then dissolved. Passing the resulting solution through the second filter, followed by the solution through the second filter and the additionally prepared pigment The dispersion is mixed, and the obtained colored composition is passed through a third filter to prepare a method.

Colored cured film and method of producing the same

The colored cured film of the present invention is formed using the colored composition of the present invention, and specifically means a color pixel, a black matrix, a black spacer, or the like used for a color filter.

Hereinafter, a colored cured film used for a color filter and a method of forming the same will be described.

As a method of manufacturing a color filter, the first method is as follows. First, a light shielding layer (black matrix) for partitioning a portion where a pixel is formed is formed on the surface of the substrate as needed. Next, a liquid composition of, for example, a red radiation-sensitive coloring composition of the present invention is applied onto the substrate, and then pre-baked to evaporate the solvent to form a coating film. Next, the coating film was exposed through 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 a red pixel pattern (colored cured film) is arranged in a predetermined arrangement is formed.

Next, each of the radiation-sensitive coloring compositions of green or blue is applied in the same manner as described above, and coating, prebaking, exposure, development, and post-baking of each radiation-sensitive coloring composition are performed on the same substrate. A green pixel array and a blue pixel array are sequentially formed. Thereby, a color filter in which three primary color pixel arrays of blue, green, and red 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.

Further, the black matrix can be formed by a photolithography method to form a metal film such as chromium which is formed by sputtering or vapor deposition into a desired pattern. A radiation-sensitive coloring composition in which a black pigment is dispersed can be used in the same manner as in the case of forming a pixel as described above.

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

Further, such substrates may be subjected to appropriate pretreatment such as drug treatment, plasma treatment, ion plating, sputtering, gas phase reaction, vacuum vapor deposition, etc., such as a decane coupling agent.

When the radiation-sensitive coloring composition is applied onto a substrate, a suitable coating method such as a spray method, a roll coating method, a rotary coating method (spin coating method), a slit die coating method (slit coating method), or a bar coating method may be employed. In particular, a spin coating method or a slit die coating method is preferred.

Prebaking is usually carried out by combining vacuum drying and heat drying. Drying under reduced pressure usually proceeds until it reaches 50 to 200 Pa. Further, the conditions for heating and drying are usually 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 after drying.

The light source used for forming the radiation used in at least one selected from the pixel and the black matrix may, for example, be a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, or a metal halide. Lamps such as object lamps, medium-pressure mercury lamps, low-pressure mercury lamps, and other laser sources such as argon ion laser, YAG laser, XeCl excimer laser, and nitrogen laser. As an 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 generally preferably from 10 to 10,000 J/m ² .

Further, as the above alkaline developing solution, for example, sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diguanidine bicyclo-[5.4 is preferable. .0] An aqueous solution such as 7-undecene or 1,5-dioxabicyclo-[4.3.0]-5-nonene.

A water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the alkaline developer in an appropriate amount. Further, after alkaline development, water washing is usually performed.

As the development treatment method, a shower development method, a spray development method, a dip development method, a mixed development method, or the like can be applied. The development conditions are preferably 5 to 300 seconds at normal temperature.

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

The film thickness of the pixel formed in this manner is usually 0.5 to 5 μm, preferably 1.0 to 3 μm.

Moreover, as a second method of producing a color filter, a method of obtaining pixels of respective colors by an inkjet method can be employed as disclosed in JP-A-H07-318723, JP-A-2000-310706, and the like. In this method, first, a partition wall having a shading function is formed on the surface of the substrate. Next, in the formed partition, for example, a liquid composition of the blue thermosetting coloring composition of the present invention is ejected by an inkjet device, and then prebaked to evaporate the solvent. Next, the coating film is exposed as needed, and then cured by post-baking to form a blue pixel pattern.

Next, each of the thermosetting coloring compositions of green or red is used in the same manner as described above, and sequentially formed on the same substrate. Green pixel pattern and red pixel pattern. Thereby, a color filter in which three primary color pixel patterns of blue, green, and red 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.

Among them, the partition wall functions not only as a shading function, but also functions to prevent the thermosetting coloring composition of the respective colors ejected into the compartment from being mixed, and the film thickness is thicker than that of the black matrix used in the first method. . Therefore, the partition walls are usually formed using a black radiation-sensitive composition.

The light source of the substrate and the radiation used in forming the color filter, and the methods and conditions for prebaking and postbaking are the same as the first method described above. In this manner, the film thickness of the pixel formed by the ink jet method is approximately the same as the height of the partition walls.

On the pixel pattern thus obtained, a protective film is formed as needed, and then a transparent conductive film is formed by sputtering. It is also possible to form a color filter by further forming a spacer after the transparent conductive film is formed. The spacers are usually formed using a radiation-sensitive composition, but spacers having a light-shielding property (black spacers) may also be used. In this case, a colored radiation-sensitive composition in which a black colorant is dispersed is used, and the coloring composition of the present invention is also suitable for forming such a black spacer.

The colored composition of the present invention can also be suitably used for forming a colored cured film which is used for any of the color pixels, the black matrix, the black spacer, and the like of the above color filter.

The color filter including the color hardened film of the present invention thus formed is formed by a color liquid crystal display because of high brightness and coloring power. Components, color camera tubes, color sensors, organic EL display elements, electronic paper, etc. are extremely useful. Among them, the display element to be described later may have at least one or more colored cured films formed using the colored composition of the present invention.

Display component

The display element of the present invention is provided with the colored cured film 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 colored cured film of the present invention may be of a transmissive type or a reflective type, and an appropriate structure may be employed. For example, a color filter may be formed on a substrate different from a driving substrate on which a thin film transistor (TFT) is disposed, and a substrate on which the color filter is formed may be opposed to a liquid crystal layer. Further, a substrate on which a color filter is formed on a surface of a driving substrate on which a thin film transistor (TFT) is disposed, and an ITO (tin-doped indium oxide) electrode or IZO (indium oxide and oxidation) may be used. The mixture of zinc) the substrate of the electrode passes through the opposite structure of the liquid crystal layer. The structure of the latter can significantly increase the aperture ratio, and has the advantage of being able to obtain a bright and high-definition liquid crystal display element. In the case where the latter structure is employed, the black matrix and the black spacer may be formed on either the substrate side on which the color filter is formed and the substrate side on which the ITO electrode or the IZO electrode is formed.

A color liquid crystal display element having the colored cured film of the present invention may include a backlight element using a white LED as a light source in addition to a cold cathode fluorescent tube (CCFL: Cold Cathode Fluorescent Lamp). As a white LED, for example, by using a red LED, a green LED, and a blue LED Combine and mix colors to obtain a white light white LED, and combine a blue LED, a red LED and a green phosphor to mix and color to obtain a white light white LED, a blue LED, a red light emitting phosphor and a green light emitting fluorescent light. The light body is combined and mixed to obtain a white light white LED, and a white LED is obtained by mixing the blue LED and the YAG phosphor, and the blue LED, the orange light emitting phosphor and the green light emitting fluorescent light are obtained. The body is combined and mixed to obtain a white light white LED, and an ultraviolet LED, a red luminescent phosphor, a green luminescent phosphor, and a blue luminescent phosphor are combined and mixed to obtain a white light white LED or the like.

A TN (twisted nematic) type, an STN (super twisted nematic) type, an IPS (in-plane switching) type, a VA (vertical alignment) type, and an OCB (optical) can be applied to the color liquid crystal display element having the colored cured film of the present invention. Appropriate liquid crystal mode such as compensation for birefringence).

In addition, the organic EL display device having the colored cured film of the present invention can be configured as appropriate, and the structure disclosed in Japanese Laid-Open Patent Publication No. Hei 11-307242, for example.

Further, the electronic paper having the colored cured film of the present invention can have an appropriate structure, and a structure disclosed in, for example, JP-A-2007-41169 can be cited.

[Examples]

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

<Synthesis of Adhesive Resin> Synthesis Example 1

To a flask equipped with a cooling tube and a stirrer, 100 parts by mass of propylene glycol monomethyl ether acetate was added and nitrogen substitution was carried out. Heating to 80 ° C, at the same temperature, 100 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 styrene methacrylate for 1 hour. Ester, 15 parts by mass of 2-hydroxyethyl methacrylate, 23 parts by mass of 2-ethylhexyl methacrylate, 12 parts by mass of N-phenyl maleimide, 15 parts by mass of D A mixed solution of diacid mono(2-propenyloxyethyl ester) and 6 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) was dropped, maintained at this temperature and polymerized for 2 hours. . Thereafter, the temperature of the reaction solution was raised to 100 ° C, and further polymerization was carried out for 1 hour to obtain a binder resin solution (solid content concentration: 33% by mass). The obtained binder resin had an Mw of 12,200 and an Mn of 6,500. This binder resin is referred to as "binder resin (B1)".

<(D) Synthesis of Transition Metal Compounds> Synthesis Example 2

According to the method of paragraphs [0155] to [0162] described in JP-A-2011-148994, a compound represented by the following formula (d-1) is synthesized. Next, after adding 0.1 part by mass of N-methylpyrrolidone to 1.1 parts by mass of the compound represented by formula (d-1) to dissolve it, 0.5 part by mass of tributylhexadecylphosphonium chloride is added. Stir for about 2 hours. This solution was poured into 250 parts by mass of water, and the solid obtained by filtration was dried at 60 ° C under reduced pressure to obtain 1.3 parts by mass of a compound represented by the following formula (D-1). The obtained compound was designated as the compound (D-1).

Synthesis Example 3

Into a 4-neck separable flask equipped with a thermometer, a stirrer, a distillation tube, and a cooler, 67.3 parts by mass of methyl ethyl ketone was added, and the temperature was raised to 75 ° C under a nitrogen stream. Further, 34.0 parts by mass of methyl methacrylate, 28.0 parts by mass of n-butyl methacrylate, 28.0 parts by mass of 2-ethylhexyl methacrylate, and 10.0 parts by mass of dimethylaminoethyl methacrylate The ester, 6.5 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile), and 25.1 parts by mass of methyl ethyl ketone were uniformly mixed, and then added to a dropping funnel and attached to a 4-neck separable flask. It took 2 hours to drip in. Two hours after the completion of the dropwise addition, the polymerization yield was 98% or more from the viewpoint of the solid content, and the weight average molecular weight (Mw) was confirmed to be 6830, and was cooled to 50 °C. Add 3.2 parts by mass of methyl chloride and 22.0 parts by mass of ethanol to react at 50 ° C for 2 small After the time, the temperature was raised to 80 ° C over 1 hour, and further, the dimethylamino group derived from dimethylaminoethyl methacrylate was changed to a quaternary ammonium salt by the reaction for 2 hours. In this manner, a resin 1 solution having a cationic group in the side chain (resin component: 47% by mass) was obtained.

Then, 51 parts by mass of the resin 1 solution was added to 2000 parts by mass of water, and the mixture was sufficiently stirred and mixed, and then heated to 60 °C. On the other hand, 10 parts by mass of an aqueous solution obtained by dissolving 10 parts by mass of the compound represented by the formula (d-1) in 90 parts by mass of water is prepared and dropped into the resin solution little by little. After the dropwise addition, the mixture was stirred at 60 ° C for 120 minutes to carry out a sufficient reaction. A small amount of the reaction was dropped on the filter paper, and the time at which the filter paper was not leaked was judged to be the end of the reaction. After cooling to room temperature with stirring, the mixture was vacuum filtered, and after washing with water, the moisture of the salt-forming compound remaining on the filter paper was removed by a dryer and dried to obtain an anion portion containing the compound represented by the formula (d-1). Compound (D-2) which is a salt with a cationic portion of the resin 1.

Synthesis Example 4

The compound represented by the following formula (d-3) was synthesized by referring to Synthesis Example H11 of JP-A-08-500912. In the same manner as in Synthesis Example 2, except that the compound represented by the formula (d-3) was used instead of the compound represented by the formula (d-1) in Synthesis Example 2, the following formula (D-) was obtained. 3) The compound represented. The obtained compound was designated as the compound (D-3).

Synthesis Example 5

According to Production Example 1 of the specification of Japanese Patent No. 4795981, a compound represented by the following formula (d-4) was synthesized. Next, in the same manner as in Synthesis Example 2 except that the compound represented by the formula (d-4) was used instead of the compound represented by the formula (d-1), the following formula (D) was obtained. -4) The compound represented. The obtained compound was designated as the compound (D-4).

Synthesis Example 6

According to the synthesis example of paragraphs [0045] to [0046] of JP-A-2003-213178, a nickel chelate compound represented by the following formula (d-5) is synthesized. The obtained compound was designated as the compound (d-5).

Synthesis Example 7

According to the synthesis example of the paragraph [0051] of JP-A-2003-213178, a copper chelate compound represented by the following formula (d-6) is synthesized. The obtained compound was designated as the compound (d-6).

<Synthesis of coloring agent> Synthesis Example 8

The compound represented by the following formula (A-1) was synthesized by the method of JP-A-2012-108469. The obtained compound was used as a coloring agent (A-1).

Synthesis Example 9

The compound represented by the following formula (A-2) was synthesized by the method of JP-A-2012-108469. The obtained compound was used as a coloring agent (A-2).

Synthesis Example 10

According to Synthesis Example 1 of JP-A-2013-190776, a compound represented by the following formula (A-3) is synthesized. The obtained compound was used as a coloring agent (A-3).

Synthesis Example 11

It is carried out in the same manner as in Synthesis Example 1 of JP-A-2013-190776, except that tetrabutylphosphonium bromide is used in place of the tributylhexadecyl bromide in Synthesis Example 1 of JP-A-2013-190776. A compound represented by the following formula (A-4) is synthesized. The obtained compound was used as a coloring agent (A-4).

Synthesis Example 12

According to the synthesis example of paragraph [0105] of JP-A-2012-032754, it is synthesized The skeleton serves as a pigment multimer of a partial structure of the pigment site. The obtained compound was used as a coloring agent (A-5).

Comparative Synthesis Example 1

According to Example 2 of JP-A-2011-148995, a compound represented by the following formula (A-6) was synthesized. The obtained compound was used as a coloring agent (A-6).

Comparative Synthesis Example 2

According to Example 3 of JP-A-2012-214718, a compound represented by the following formula (A-7) is synthesized. The obtained compound was used as a coloring agent (A-7).

Solubility test Modulation example 1

10 parts by mass of the compound (D-1) and 90 parts by mass of propylene glycol monomethyl ether were mixed, and the mixture was stirred for 1 hour with a web rotor, and the solubility was visually confirmed. If there is no insoluble matter, it is rated as "○", and if there is insoluble matter, it is rated as "X". The evaluation results are shown in Table 1.

Modulation example 2~4

The solubility was confirmed in the same manner as in Preparation Example 1 except that the compound (D-2) to (D-4) was used instead of the compound (D-1) in Preparation Example 1. The evaluation results are shown in Table 1.

Modulation example 5~6

The solubility was confirmed in the same manner as in Preparation Example 1 except that the coloring agents (A-6) to (A-7) were used instead of the compound (D-1) in Preparation Example 1. The evaluation results are shown in Table 1.

Modulation example 7

The solubility was confirmed in the same manner as in Preparation Example 1 except that the compound (D-1) in the preparation example 1 was replaced with ginseng (2,4-pentanedione) iron (III). The evaluation results are shown in Table 1.

<Preparation of Transition Metal Compound Solution> Modulation example 8

15 parts by mass of the compound (D-1) and 85 parts by mass of cyclohexanone were mixed to prepare a compound solution (D-1).

Modulation example 9

15 parts by mass of the compound (D-2) and 85 parts by mass of cyclohexanone were mixed to prepare a compound solution (D-2).

Modulation example 10~11

The compound solution (D-3) to (D-) was prepared in the same manner as in Preparation Example 9 except that the compound (D-3) to (D-4) was used instead of the compound (D-2) in Preparation Example 9. 4).

Modulation example 12

15 parts by mass of the compound (d-1) and 85 parts by mass of cyclohexanone were mixed to prepare a compound solution (d-1).

Modulation example 13~16

The compound solution (d-3) to (d-) was prepared in the same manner as in Preparation Example 12 except that the compound (d-3) to (d-6) were used instead of the compound (d-1) in Preparation Example 12. 6).

Modulation example 17

15 parts by mass of ginseng (2,4-pentanedione) iron (III) and 85 parts by mass of cyclohexanone were mixed to prepare a compound solution (d-7).

<Modulation of Dye Solution> Modulation example 18

15 parts by mass of the color former (A-1) and 85 parts by mass of cyclohexanone were mixed to prepare a dye solution (A-1).

Modulation example 19~24

A dye solution (A-2)~ was prepared in the same manner as in Preparation Example 18, except that the coloring agents (A-2) to (A-7) were used instead of the coloring agent (A-1) in Preparation Example 18. A-7).

Modulation example 25

15 parts by mass of a compound represented by the following formula (A-8) (Orasol Red G; manufactured by Ciba Specialty Chemicals Co., Ltd.) and 85 parts by mass of cyclohexanone were mixed to prepare a dye solution (A-8). .

<Preparation of Pigment Dispersion> Modulation example 26

15 parts by mass of CI Pigment Red 177 as a coloring agent, 12.5 parts by mass of BYK-LPN21116 (manufactured by BYK Chemie (BYK) Co., Ltd.), and 72.5 parts by mass of propylene glycol monomethyl ether B as a solvent The acid ester was treated with a bead mill to prepare a pigment dispersion (A-9).

Modulation example 27

A pigment dispersion liquid (A-10) was prepared in the same manner as in Preparation Example 1 except that C.I. Pigment Red 254 was used instead of C.I. Pigment Red 177 as a colorant.

<Modulation and evaluation of coloring composition> Modulation of coloring composition Example 1

13.5 parts by mass of the dye solution (A-1) as the (A) colorant, 1.0 part by mass of the compound solution (d-1) as the (D) transition metal compound, and (B) the binder resin 26.3 parts by mass of the binder resin (B1) solution, 9.9 parts by mass of the (C) polymerizable compound, a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (Nippon Chemical Co., Ltd.) Ltd., trade name KAYARAD DPHA), 1.8 parts by mass of 2-benzyl-2-dimethylamino-1-(4-) as a photopolymerization initiator Phenylphenyl)butan-1-one (trade name: Irgacure 369, manufactured by Ciba Specialty Chemicals Co., Ltd.), 0.1 part by mass of NCI-930 (made by ADEKA Co., Ltd.), and 0.05 parts by mass of MEGAFAC as a fluorine-based surfactant F-554 (manufactured by DIC Corporation) and propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a coloring composition (S-1) having a solid content concentration of 20% by mass.

Comparison evaluation

The obtained coloring composition was applied onto a glass substrate using a spin coater, and then prebaked on a hot plate at 80 ° C for 10 minutes to form a coating film. The rotation speed of the spin coater was changed to form three coating films having different film thicknesses by the same operation.

Next, after the substrates were cooled to room temperature, radiation containing wavelengths of 365 nm, 405 nm, and 436 nm was exposed to the respective coating films at a light exposure of 2,000 J/m ² using a high pressure mercury lamp. Thereafter, a developing solution composed of a 0.04% by mass aqueous potassium hydroxide solution at 23 ° C was sprayed at a developing pressure of 1 kgf/cm ² (nozzle diameter: 1 mm) for the substrate, and subjected to shower development for 90 seconds. Thereafter, the substrate was washed with ultrapure water, air-dried, and further post-baked in a clean oven at 200 ° C for 30 minutes to form a cured film for evaluation.

The substrate on which the cured film is formed is sandwiched between two polarizing plates, and is irradiated from the back side by a fluorescent lamp (wavelength range of 380 to 780 nm), and the polarizing plate on the front side is rotated by a luminance meter LS-100 (manufactured by MINOLTA Co., Ltd.) The maximum and minimum values of the transmitted light intensity are determined. Then, the value obtained by dividing the maximum value by the minimum value is taken as the contrast ratio of each of the cured films. From the measurement results, the contrast ratio at the chromaticity coordinate value y = 0.080 was obtained. The evaluation results are shown in Table 2. Among them, the larger the contrast ratio value means the better.

Evaluation of foreign bodies

The substrate on which the cured film was formed was visually confirmed, and if it was confirmed that the foreign matter was confirmed, it was evaluated as "x", and if it was not confirmed, it was evaluated as "○". The evaluation results are shown in Table 2.

Examples 2 to 22 and Comparative Examples 1 to 9

The coloring composition was prepared in the same manner as in Example 1 except that the type and amount of the coloring agent and the component (D) in the first embodiment were changed as shown in Table 2. Subsequently, the same procedure as in Example 1 was carried out, and the obtained colored composition was evaluated. The evaluation results are shown in Table 2.

Claims (7)

A colored composition comprising (A) comprising a coloring agent for at least one compound selected from the group consisting of a compound, a polymethine compound, a coumarin compound, and an oxime compound, (B) a binder resin, and (C) a polymerizable compound, which further comprises (D) Transition metal compound (except for component (A)). The colored composition of claim 1, wherein the (D) transition metal compound is an electrolyte type transition metal complex. The colored composition of claim 2, wherein the electrolyte-type transition metal complex comprises a salt of the following ions: A compound of a skeleton other than a skeleton, a polymethine skeleton, a coumarin skeleton, and an anthracene skeleton is used as a transition metal complex anion of a ligand, and a cation selected from a metal cation and a phosphonium cation. The colored composition of claim 3, wherein the transition metal complex anion has an azo compound as a ligand. The colored composition of claim 3, wherein the sulfonium cation is at least one selected from the group consisting of a phosphonium cation and an ammonium cation. A colored hardening film formed using the coloring composition according to any one of claims 1 to 5. A display element comprising the colored cured film of claim 6.