TW201731968A - Compound, coloring composition, color filter, and display device being excellent in solvent resistance - Google Patents

Abstract

This invention aims to provide a color filter which is excellent in solvent resistance, a display device comprising the same, a compound capable of providing them, and a coloring composition. The compound of the present invention may be represented by formula (A-I).

Description

Compound, coloring composition, color filter and display device Field of invention

This invention relates to compounds and color forming compositions comprising the same.

Background of the invention

A coloring composition is used in the production of a color filter used in a display device such as a liquid crystal display device, an electroluminescence display device, and a plasma display. As such a coloring composition, a coloring composition containing a compound represented by the following formula or the like is known.

[Prior Art Literature] [Patent Literature]

Patent Document 1: WO2012/053211

Patent Document 2: JP-A-2015-38201

Summary of invention

In the conventionally known compounds described above, the absorbance and the voltage holding ratio are not sufficiently satisfactory, and a color filter formed of a colored composition containing the compound may not sufficiently satisfy the solvent resistance.

The invention includes the following invention.

[1] A compound represented by the formula (A-I).

In the formula (AI), R ⁴¹ to R ⁴⁴ each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a carbon number which may have a substituent The 7 to 30 aralkyl group, the aromatic hydrocarbon group and the aralkyl group may have a substituent of -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f , and the carbon number is 1 to 20 saturated. In the hydrocarbon group, the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a substituted or unsubstituted amino group or a halogen atom, and the methane group contained in the saturated hydrocarbon group may have a carbon number of 2 to 20 Can be replaced by an oxygen atom or -CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, the adjacent methylene group is not replaced with an oxygen atom at the same time, and the terminal methylene group is not replaced with an oxygen atom or -CO-. R ⁴¹ and R ⁴² may bond and form a ring together with the nitrogen atom to which they are bonded, and R ⁴³ and R ⁴⁴ may bond and form a ring together with the nitrogen atom to which they are bonded.

R ⁴⁷ to R ⁵⁴ each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, -SO ₃ ^- , -SO ₂ -N ^- -SO ₂ -R ^f or an alkyl group having 1 to 8 carbon atoms. The methylene group of the alkyl group may be replaced with an oxygen atom or -CO-, and R ⁴⁸ and R ⁵² may be bonded to each other to form -NH-, -S-, or -SO ₂ -. However, in the alkyl group, the adjacent methylene group is not replaced with an oxygen atom at the same time, and the terminal methylene group is not replaced with an oxygen atom or -CO-.

The ring T ¹ represents an aromatic heterocyclic ring having 3 to 10 carbon atoms, and the aromatic heterocyclic ring may have a saturated hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted amine group or a carbon number of 6 to 20 which may have a substituent. Aromatic hydrocarbon group. The substituent which the aromatic hydrocarbon group may have may be -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f .

M ^r+ represents a hydrogen ion, an r-valent metal ion or a substituted or unsubstituted ammonium ion.

k represents the sum of the number of -SO ₃ ^{- and} the number of -SO ₂ -N ^- -SO ₂ -R ^f of the compound represented by the formula (AI).

r represents an integer of 1 or more.

R ^f represents a fluoroalkyl group having 1 to 12 carbon atoms.

However, the compound represented by the formula (AI) has at least one -SO ₂ -N ^- -SO ₂ -R ^f . ]

[2] The compound according to [1], wherein M ^r+ is a metal ion.

[3] The compound according to the above [1], wherein the aromatic heterocyclic ring represented by the above T ^{1 is} a ring represented by the following formula (A-t1).

In the formula (A-t1), the ring T ² represents an aromatic heterocyclic ring having 3 to 10 carbon atoms.

R ⁴⁵ and R ⁴⁶ each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a carbon number which may have a substituent of 7~ In the case of the aralkyl group of 30, the carbon number of the saturated hydrocarbon group is 2 to 20, and the methylene group contained in the saturated hydrocarbon group may be replaced with an oxygen atom or -CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, the adjacent methylene group is not replaced with an oxygen atom at the same time, and the terminal methylene group is not replaced with an oxygen atom or -CO-. R ⁴⁵ and R ⁴⁶ may bond together with the nitrogen atom to which they are bound to form a ring.

R ⁵⁵ represents a saturated hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

K1 represents 0 or 1.

* indicates the bonding end with a carbocation. ]

[4] A coloring composition, which comprises the compound according to any one of [1] to [3].

[5] A color filter formed from the coloring composition according to [4].

[6] A display device comprising the color filter according to [5].

The compound of the present invention is excellent in absorbance and voltage holding ratio, and a coloring composition containing the compound can be used to form a color filter excellent in solvent resistance.

detailed description

The compound of the present invention is represented by the formula (A-I). Hereinafter, the compound represented by the formula (A-I) is also referred to as the compound (A-I). Also in the compounds of the invention Contains its tautomers, their salts.

In the formula (AI), R ⁴¹ to R ⁴⁴ each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a carbon number which may have a substituent The 7 to 30 aralkyl group, the aromatic hydrocarbon group and the aralkyl group may have a substituent of -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f , and the carbon number is 1 to 20 saturated. In the hydrocarbon group, the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a substituted or unsubstituted amino group or a halogen atom, and the methane group contained in the saturated hydrocarbon group may have a carbon number of 2 to 20 Can be replaced by an oxygen atom or -CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, the adjacent methylene group is not replaced with an oxygen atom at the same time, and the terminal methylene group is not replaced with an oxygen atom or -CO-. R ⁴¹ and R ⁴² may bond and form a ring together with the nitrogen atom to which they are bonded, and R ⁴³ and R ⁴⁴ may bond and form a ring together with the nitrogen atom to which they are bonded.

R ⁴⁷ to R ⁵⁴ each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, -SO ₃ ^- , -SO ₂ -N ^- -SO ₂ -R ^f or an alkyl group having 1 to 8 carbon atoms. The methylene group of the alkyl group may be replaced with an oxygen atom or -CO-, and R ⁴⁸ and R ⁵² may be bonded to each other to form -NH-, -S-, or -SO ₂ -. However, in the alkyl group, the adjacent methylene group is not replaced with an oxygen atom at the same time, and the terminal methylene group is not replaced with an oxygen atom or -CO-.

The ring T ¹ represents an aromatic heterocyclic ring having 3 to 10 carbon atoms, and the aromatic heterocyclic ring may have a saturated hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent. The substituent which the aromatic hydrocarbon group may have may be -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f .

M ^r+ represents a hydrogen ion, an r-valent metal ion or a substituted or unsubstituted ammonium ion.

k represents the sum of the number of -SO ₃ ^{- and} the number of -SO ₂ -N ^- -SO ₂ -R ^f of the compound represented by the formula (AI).

r represents an integer of 1 or more.

R ^f represents a fluoroalkyl group having 1 to 12 carbon atoms.

However, the compound represented by the formula (AI) has at least one -SO ₂ -N ^- -SO ₂ -R ^f . ]

The aromatic heterocyclic ring represented by the ring T ¹ may be a single ring or a fused ring. The aromatic heterocyclic ring represented by the ring T ¹ has a carbon number of 3 to 10, preferably 3 to 8. Further, the aromatic heterocyclic ring is preferably a 5- to 10-membered ring, and more preferably a 5- to 9-membered ring. Examples of the monocyclic aromatic heterocyclic ring include a 5-membered ring containing a nitrogen atom such as a pyrrole ring, an oxazole ring, a pyrazole ring, an imidazole ring, and a thiazole ring; and a nitrogen-free ring such as a furan ring or a thiophene ring; a ring of a 6-membered ring containing a nitrogen atom such as a pyridine ring, a pyrimidine ring, a pyridazine ring or a pyrazine ring, etc., and examples of the aromatic heterocyclic ring of the condensed ring include an anthracene ring, a benzimidazole ring, and a benzo ring. a fused ring containing a nitrogen atom such as a thiazole ring or a quinoline ring; a fused ring containing no nitrogen atom such as a benzofuran ring; and the like.

Examples of the substituent which the aromatic heterocyclic ring of the ring T ¹ may have include a halogen atom, a cyano group, and a saturated hydrocarbon group having 1 to 20 carbon atoms (preferably an alkyl group having 1 to 20 carbon atoms) which may have a substituent. The substituted or unsubstituted amino group or the carbon number 6 to 20 aromatic hydrocarbon group which may have a substituent, etc., preferably a saturated hydrocarbon group having 1 to 20 carbon atoms (preferably an alkyl group having 1 to 20 carbon atoms) A substituted or unsubstituted amino group or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

Among them, the aromatic heterocyclic ring of the ring T ¹ is preferably an aromatic heterocyclic ring containing a nitrogen atom, and more preferably a 5-membered aromatic heterocyclic ring containing a nitrogen atom.

Further, the ring T ^{1 is} more preferably a ring represented by the formula (A-t1).

In the formula (A-t1), the ring T ² represents an aromatic heterocyclic ring having 3 to 10 carbon atoms.

R ⁴⁵ and R ⁴⁶ each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a carbon number which may have a substituent of 7~ In the case of the aralkyl group of 30, the carbon number of the saturated hydrocarbon group is 2 to 20, and the methylene group contained in the saturated hydrocarbon group may be replaced with an oxygen atom or -CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, the adjacent methylene group is not replaced with an oxygen atom at the same time, and the terminal methylene group is not replaced with an oxygen atom or -CO-. R ⁴⁵ and R ⁴⁶ may bond together with the nitrogen atom to which they are bound to form a ring.

R ⁵⁵ represents a saturated hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

K1 represents 0 or 1.

* indicates the bonding end with a carbocation. ]

The aromatic heterocyclic ring of the ring T ² may be the same ring as the aromatic hetero ring exemplified in the ring T1.

Further, the ring T ^{1 is} particularly preferably a ring represented by the formula (A-t1-1).

In the formula (A-t1-1), R ⁵⁶ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

X2 represents an oxygen atom, -N(R ⁵⁷ )- or a sulfur atom.

R ⁵⁷ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

R ⁴⁵ and R ^{46 are} synonymous with the above.

* indicates the bonding end with a carbocation. ]

Further, the ring T ^{1 is} also preferably a ring represented by the formula (A-t2).

In the formula (A-t2), the ring T ³ represents an aromatic heterocyclic ring having 3 to 10 carbon atoms and having a nitrogen atom.

R ⁵⁸ represents a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f .

R ⁵⁹ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent.

K2 represents 0 or 1.

* indicates the bonding end with a carbocation. ]

The ring T ^{1 is} also more preferably a ring represented by the formula (A-t2-1).

In the formula (A-t2-1), R ⁶⁰ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

R ⁶¹ represents a hydrogen atom, -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f .

R ⁵⁹ is synonymous with the above.

* indicates the bonding end with a carbocation. ]

The saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ⁴¹ to R ⁴⁶ , R ⁵⁵ , R ⁵⁶ and R ⁵⁸ to R ⁶⁰ may be any of a linear chain, a branched chain and a cyclic group. Examples of the linear or branched chain saturated hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, a dodecyl group, and a decyl group. A linear alkyl group such as a hexaalkyl group or an eicosyl group; a branched chain alkyl group such as an isopropyl group, an isobutyl group, an isopentyl group, a neopentyl group or a 2-ethylhexyl group; and the like. The number of carbon atoms of the saturated hydrocarbon group is preferably from 1 to 10, more preferably from 1 to 8, still more preferably from 1 to 6.

The cyclic saturated hydrocarbon group represented by R ⁴¹ to R ⁴⁶ , R ⁵⁵ , R ⁵⁶ and R ⁵⁸ to R ⁶⁰ may be a single ring or a polycyclic ring. Examples of the cyclic saturated hydrocarbon group include an alicyclic saturated hydrocarbon group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group or an adamantyl group. The number of carbon atoms of the cyclic saturated hydrocarbon group is preferably from 3 to 10, and more preferably from 6 to 10.

Specific examples of the saturated hydrocarbon group represented by R ⁴¹ to R ⁴⁶ , R ⁵⁵ , R ⁵⁶ and R ⁵⁸ to R ⁶⁰ include a group represented by the following formula. In the following formula, * denotes a bonding end.

The saturated hydrocarbon group represented by R ⁴¹ to R ⁴⁶ , R ⁵⁵ , R ⁵⁶ and R ⁵⁸ to R ⁶⁰ may be substituted with a substituted or unsubstituted amino group or a halogen atom. The substituted amine group may, for example, be an alkylamine group such as a dimethylamino group or a diethylamino group. Further, examples of the halogen atom include fluorine, chlorine, bromine, and iodine. Further, in the case where the halogen atom is a fluorine atom, the saturated hydrocarbon group substituted by a halogen atom (fluorine atom) represented by R ⁴¹ to R ⁴⁶ , R ⁵⁵ , R ⁵⁶ and R ⁵⁸ to R ⁶⁰ is preferably a trifluoromethyl group or a fifth group. Perfluoroalkyl group such as fluoroethyl or heptafluoropropyl.

Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms which have a substituent include a group represented by the following formula. In the following formula, * represents a nitrogen atom or the like Bonding end.

The alkyl group having 1 to 8 carbon atoms represented by R ⁴⁷ to R ⁵⁴ is a group having 1 to 8 carbon atoms in a linear or branched chain saturated hydrocarbon group exemplified as the saturated hydrocarbon group represented by R ⁴¹ . group.

In addition, as the alkyl group having 1 to 10 carbon atoms represented by R ⁵⁷ , a group having 1 to 10 carbon atoms in a linear or branched chain saturated hydrocarbon group exemplified as the saturated hydrocarbon group represented by R ⁴¹ is exemplified. .

When the carbon number of the saturated hydrocarbon group represented by R ⁴¹ to R ⁴⁶ is 2 to 20, the methylene group contained in the saturated hydrocarbon group may be replaced with an oxygen atom or -CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, the adjacent methylene group is not simultaneously substituted with an oxygen atom, and the terminal methylene group is not replaced with an oxygen atom or -CO-. In this case, as the saturated hydrocarbon group, a linear or branched saturated hydrocarbon group (that is, a linear or branched alkyl group) is preferable, and a linear saturated hydrocarbon group (that is, a linear alkyl group) is more preferable. The preferred carbon number of the methylene group which may be replaced by an oxygen atom or a saturated hydrocarbon group of -CO- is from 2 to 10, more preferably from 2 to 8. When the methylene group is replaced by an oxygen atom or -CO-, the carbon number between the terminal and the oxygen atom or -CO-, or between the oxygen atom or -CO- and the oxygen atom or -CO- is 1 or more, preferably It is 1 to 5, more preferably 2 to 3, still more preferably 2. In the group in which the methylene group of the saturated hydrocarbon group is replaced with an oxygen atom or -CO-, for example, an alkoxyalkyl group; or an (alkoxyalkoxy)alkyl group, (alkoxy alkoxy alkoxy group) Alkyl, (alkoxyalkoxyalkoxyalkoxy)alkyl, (alkoxyalkoxyalkoxyalkoxyalkoxy)alkyl, (alkoxy alkoxyalkane) The number of repetitions of the alkoxy unit is, for example, 1 to 6, preferably 1 to 4, and more preferably 1 to 2, such as a polyalkoxyalkyl group such as an oxyalkoxy alkoxyalkoxy)alkyl group. In a more preferable specific example, a group represented by the following formula is mentioned. In the following formula, * represents a bonding end with a nitrogen atom.

Further, the number of carbon atoms of the aromatic hydrocarbon group which may have a substituent represented by R ⁴¹ to R ⁴⁶ , R ⁵⁵ , R ⁵⁶ and R ⁵⁸ to R ⁶⁰ is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 ~12. Examples of the aromatic hydrocarbon group include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a biphenyl group, and a terphenyl group, and a phenyl group, a naphthyl group, a tolyl group, and a xylene group are preferable. The base is particularly preferably a phenyl group. Further, the aromatic hydrocarbon group may have one or two or more substituents. Examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom or a bromine atom; a halogenated alkyl group having 1 to 6 carbon atoms such as a chloromethyl group or a trifluoromethyl group; and a carbon such as a methoxy group or an ethoxy group. Alkoxy groups of 1 to 6; hydroxyl groups; amine sulfonyl groups; alkylsulfonyl groups having 1 to 6 carbon atoms such as methylsulfonyl; methoxycarbonyl and ethoxycarbonyl having 1 to 6 carbon atoms; Alkoxycarbonyl; -SO ₃ ^- ; -SO ₂ -N ^- -SO ₂ -R ^{f ,} etc., may be -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f . However, -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f is preferably directly bonded to an aromatic hydrocarbon ring of an aromatic hydrocarbon group, that is, a hydrogen atom bonded to an aromatic hydrocarbon ring.

Specific examples of the aromatic hydrocarbon group which may have a substituent include a group represented by the following formula. In the following formula, * represents a bonding end with a nitrogen atom.

Examples of the aralkyl group which may have a substituent represented by R ⁴¹ to R ⁴⁶ and R ⁵⁹ include a carbon group such as a methylene group, an ethylene group or a propylene group bonded to a group described as the above aromatic hydrocarbon group. A group of an alkylene group having 1 to 10 (preferably 1 to 5 carbon atoms). The number of carbon atoms of the aralkyl group is preferably 7 to 30, more preferably 7 to 20, still more preferably 7 to 17 carbon atoms.

a ring formed by a ring in which R ⁴¹ and R ⁴² are bonded together with a nitrogen atom to which they are bonded, a ring formed by R ⁴³ and R ⁴⁴ bonded together with a nitrogen atom to which they are bonded, and a nitrogen bonded to and bonded to R ⁴⁵ and R ⁴⁶ Examples of the ring formed by the atom include a nitrogen-containing non-aromatic 4-7-membered ring such as a pyrrolidine ring, a morpholine ring, a piperidine ring or a piperazine ring. Preferred examples thereof include a pyrrolidine ring and a piperidine ring. A 4 to 7 membered ring having only one nitrogen atom as a hetero atom.

R ⁵⁸ is preferably a saturated hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

In particular, R ⁴¹ to R ⁴⁴ , R ⁵⁵ , R ⁵⁶ and R ⁵⁸ to R ^{60 are} preferably a saturated hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having a substituent, and each independently, more preferably a carbon number of 1 a saturated hydrocarbon group of ~8 or an aromatic hydrocarbon group represented by the following formula. R ⁵⁵ , R ⁵⁶ and R ⁵⁸ to R ^{60 are} more preferably an aromatic hydrocarbon group represented by the following formula. In the following formula, * represents a bonding end with a nitrogen atom.

R ⁴⁵ to R ⁴⁶ are each preferably a saturated hydrocarbon group having 1 to 20 carbon atoms, a methylene group constituting an alkyl group having 2 to 20 carbon atoms, a group substituted with an oxygen atom or -CO-, or a substituent. The aromatic hydrocarbon group, or R ^{45 ,} binds to R ⁴⁶ and forms a ring together with the nitrogen atom to which they are bonded. More preferably, R ⁴⁵ to R ⁴⁶ are each independently a saturated hydrocarbon group having 1 to 8 carbon atoms, an alkoxyalkyl group, or an aromatic hydrocarbon group represented by the following formula, or R ⁴⁵ and R ^{46 are} bonded to each other to form only one The 4 to 7-membered ring having a nitrogen atom as a hetero atom is more preferably a saturated hydrocarbon group having 1 to 8 carbon atoms, an alkoxyalkyl group or an aromatic hydrocarbon group represented by the following formula. In the following formula, * represents a bonding end with a nitrogen atom.

In addition, examples of the alkyl group having 1 to 8 carbon atoms represented by R ⁴⁷ to R ⁵⁴ include a carbon number of 1 to 8 in a linear or branched chain saturated hydrocarbon group exemplified as the saturated hydrocarbon group represented by R ⁴¹ . Group. Further, the methylene group constituting the alkyl group having 2 to 8 carbon atoms represented by R ⁴⁷ to R ⁵⁴ is replaced with an oxygen atom or a group of -CO- (however, in the alkyl group, the adjacent methylene group is not At the same time, it is replaced with an oxygen atom, and the methylene group at the end is not replaced with an oxygen atom or -CO-), and an alkyl group having a carbon number of 2 to 20 represented by the above R ⁴¹ to R ⁴⁶ may be mentioned. The methyl group is replaced with a group having 8 or less carbon atoms selected from the group consisting of an oxygen atom or -CO-. The alkyl group having 1 to 8 carbon atoms represented by R ⁴⁷ to R ⁵⁴ is more preferably a group represented by the following formula. In the following formula, * represents a bonding end with a carbon atom.

R ⁴⁷ to R ^{54 are} preferably independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms, and more preferably each independently a hydrogen atom, a methyl group or a fluorine atom, or from the viewpoint of easiness of synthesis. Chlorine atom.

Further, as R ⁵⁷ , a hydrogen atom or an alkyl group having 1 to 5 carbon atoms is preferable.

As R ⁶¹ , a hydrogen atom is preferred.

Examples of the r-valent metal ion represented by Mr ⁺ include alkali metal ions such as lithium ions, sodium ions, and potassium ions; alkaline earth metal ions such as barium ions, magnesium ions, calcium ions, barium ions, and barium ions; and titanium ions; , zirconium ions, chromium ions, manganese ions, iron ions, cobalt ions, nickel ions, copper ions and other transition metal ions; zinc ions, cadmium ions, aluminum ions, indium ions, tin ions, lead ions, barium ions and other typical metal ions Wait. r is 1 or more, preferably 2 or more, preferably 5 or less, more preferably 4 or less, still more preferably 3 or less. Further, examples of the substituted or unsubstituted ammonium ion represented by Mr ⁺ include a quaternary ammonium ion such as a tetraalkylammonium ion.

As M ^{r +,} from the viewpoint of the voltage holding ratio, r is preferably divalent metal ions, alkaline earth metal ion and more preferably, typical metal ion, more preferably a magnesium ion, barium ion, zinc ion. As M ^r+ , a hydrogen ion or an alkali metal ion is preferable from the viewpoint of absorbance, and hydrogen ion is more preferable.

In the formula (AI), the number of Mr ⁺ becomes the sum of the number of -SO ₃ ^{- and} the number of -SO ₂ -N ^- -SO ₂ -R ^{f which} are represented by the compound represented by the formula (AI) (k) ) One less number. Therefore, the compound (AI) is a compound having a valence of 0, that is, electrically neutral. When -SO ₃ ^{- is} contained, the number of -SO ₃ ^- is preferably 6 or less, more preferably 3 or less, and may be 1 or more. Further, the number of -SO ₃ ^- is also preferably 0.

Examples of the fluoroalkyl group having 1 to 12 carbon atoms represented by R ^f include a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group (perfluoromethyl group), a monofluoroethyl group, and a difluoroethyl group. Trifluoroethyl, tetrafluoroethyl, pentafluoroethyl (perfluoroethyl), monofluoropropyl, difluoropropyl, trifluoropropyl, tetrafluoropropyl, pentafluoropropyl, hexafluoropropyl , heptafluoropropyl (perfluoropropyl), monofluorobutyl, difluorobutyl, trifluorobutyl, tetrafluorobutyl, pentafluorobutyl, hexafluorobutyl, heptafluorobutyl, octafluorobutane Base, nonafluorobutyl (perfluorobutyl) and the like. Among them, an alkyl group (fluoroalkyl group) in which all or a part of the hydrogen atom represented by R ^f is substituted with a fluorine atom is preferably a perfluoroalkyl group. Further, the number of carbon atoms of the alkyl group (fluoroalkyl group) in which all or a part of the hydrogen atoms represented by R ^f is substituted by a fluorine atom is preferably from 1 to 10, more preferably from 1 to 5, still more preferably from 1 to 3.

The compound (AI) has at least one -SO ₂ -N ^- -SO ₂ -R ^f . The number of -SO ₂ -N ^- -SO ₂ -R ^f is 1 or more, preferably 1 to 7, more preferably 1 to 4, still more preferably 1 or 2, and particularly preferably 2.

Further, the compound (AI) preferably also has -SO ₂ -N ^- -SO ₂ -R ^f and does not have -SO ₃ ^- , and preferably has -SO ₂ -N ^- -SO ₂ -R ^f and -SO ₃ ^- . In the case of -SO ₂ -N ^- -SO ₂ -R ^f and -SO ₃ ^- , at least one -SO ₂ -N ^- -SO ₂ -R ^f , -SO ₂ -N is contained in the compound (AI) ^- -SO ₂ -R ^f, and -SO ₃ ^- the total number of preferably 2 to 7, more preferably 2 to 4, more preferably 2.

The -SO ₂ -N ^- -SO ₂ -R ^f or -SO ₃ ^- is preferably contained as any one of the above R ⁴⁷ to R ⁵⁴ or a carbon number which may have a substituent represented by R ⁴¹ to R ⁴⁴ 6 to 20 aromatic hydrocarbon groups, a C 7 to 30 aralkyl group which may have a substituent represented by R ⁴¹ to R ⁴⁴ , and a carbon number 6 to be substituted with a hydrogen atom of an aromatic hetero ring represented by T ¹ the aromatic hydrocarbon according to any one of the binding 20, and more preferably, R ⁴¹ ~ by the aromatic hydrocarbon group having 6 to 20 carbon atoms may have a substituent group represented by R ^44, R ⁴¹ ~ R ⁴⁴ may have a substituent represented by the group carbon aralkyl group having 7 to 30 in combination, more preferably, R ⁴¹ ~ by the aromatic hydrocarbon group having 6 to 20 carbon atoms may have a substituent group R ⁴⁴ represented by R ⁴¹ ~ R ⁴⁴ may have represented The para-bonding of the aromatic hydrocarbon ring (benzene ring) in the aralkyl group having 7 to 30 carbon atoms of the substituent from the position of bonding with the nitrogen atom.

However, in the case where -SO ₂ -N ^- -SO ₂ -R ^f or -SO ₃ ^- is bonded to the aromatic hydrocarbon group or the aralkyl group, -SO ₂ -N ^- -SO ₂ -R ^f or -SO ₃ ^- preferably directly bonded to an aromatic hydrocarbon ring of an aromatic hydrocarbon group or an aralkyl group. That is, -SO ₂ -N ^- -SO ₂ -R ^f or -SO ₃ ^- is preferably substituted with a hydrogen atom bonded to an aromatic hydrocarbon ring.

-SO ₂ -N ^- -SO ₂ -R ^f and -SO ₃ ^- may be bonded to the same aromatic hydrocarbon ring, but are preferably bonded to different aromatic hydrocarbon rings.

Further, the compound (A-I) preferably does not have an ethylenically unsaturated bond.

As the compound (AI), it is also preferred to have a compound having -SO ₂ -N ^- -SO ₂ -R ^f and having no -SO ₃ ^- and having -SO ₂ -N ^- -SO ₂ -R ^f and -SO ₃ ^- The compound is used in combination. In this case, a compound having -SO ₂ -N ^- -SO ₂ -R ^f and having no -SO ₃ ^{- and} a compound having -SO ₂ -N ^- -SO ₂ -R ^f and -SO ₃ ^- The ratio (compound having -SO ₂ -N ^- -SO ₂ -R ^f and having no -SO ₃ ^- /compound having -SO ₂ -N ^- -SO ₂ -R ^f and -SO ₃ ^- ) is preferably 0.01 or more It is more preferably 0.05 or more, further preferably 0.1 or more, and may be 50 or less, more preferably 10 or less, further preferably 5 or less, and particularly preferably 1 or less.

The compound (A-I) is preferably a compound represented by the following formula (A-I1).

[In the formula (A-I1), R ⁸¹ to R ⁹⁰ each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f .

K1 represents the sum of the number of -SO ₃ ^{- and} the number of -SO ₂ -N ^- -SO ₂ -R ^f of the compound represented by the formula (A-I1).

R ⁴¹ , R ⁴³ , R ⁴⁷ to R ⁵⁴ , T ¹ , M ^r+ , r, R ^{f are} synonymous with the above.

However, the compound represented by the formula (A-I1) has at least one -SO ₂ -N ^- -SO ₂ -R ^f . ]

Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ⁸¹ to R ⁹⁰ include the same groups as those exemplified as the saturated hydrocarbon group represented by R ⁴¹ . R ⁸¹ to R ^{90 are} preferably a hydrogen atom, a saturated hydrocarbon group having 1 to 8 carbon atoms, -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f , more preferably a hydrogen atom, -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^{f is} further preferably a hydrogen atom or -SO ₂ -N ^- -SO ₂ -R ^f .

Further, -SO ₂ -N ^- -SO ₂ -R ^f or -SO ₃ ^- is preferably (e) contained as either of R ⁴⁷ to R ⁵⁴ or (f) as R ⁸¹ to R ⁹⁰ One or more, or (g) is bonded to an aromatic hydrocarbon group having 6 to 20 carbon atoms substituted with a hydrogen atom of an aromatic hetero ring represented by T ¹ , or a combination of these (e) to (g), more preferably Further, it is preferably present as (f) as a combination of (f), (g) or these (f) to (g). Further, among R ⁸¹ to R ⁹⁰ , one or more selected from the group consisting of R ⁸⁶ and R ⁸⁹ are preferable.

The number of -SO ₂ -N ^- -SO ₂ -R ^f contained in the compound (A-I1) is preferably from 1 to 7, more preferably from 1 to 4, still more preferably 1 or 2. Further, in the case where the compound (A-I1) has -SO ₂ -N ^- -SO ₂ -R ^f and -SO ₃ ^- , at least one -SO ₂ -N ^- -SO ₂ is contained in the compound (A-I1) The total number (k1) of -R ^f , -SO ₂ -N ^- -SO ₂ -R ^f and -SO ₃ ^- is preferably 2 to 7, more preferably 2 to 4, still more preferably 2.

As the compound (A-I1), a compound having -SO ₂ -N ^- -SO ₂ -R ^f and having no -SO ₃ ^- and having -SO ₂ -N ^- -SO ₂ -R ^f and -SO are also preferable. ₃ ^- compounds are used together. In this case, a compound having -SO ₂ -N ^- -SO ₂ -R ^f and having no -SO ₃ ^{- and} a compound having -SO ₂ -N ^- -SO ₂ -R ^f and -SO ₃ ^- The ratio (compound having -SO ₂ -N ^- -SO ₂ -R ^f and having no -SO ₃ ^- /compound having -SO ₂ -N ^- -SO ₂ -R ^f and -SO ₃ ^- ) is preferably 0.01 or more It is more preferably 0.05 or more, further preferably 0.1 or more, and may be 50 or less, more preferably 10 or less, further preferably 5 or less, and particularly preferably 1 or less.

The compound (A-I), as shown in the following Tables 1 to 12, may, for example, be a compound (A-I-1) to a compound (A-I-632) represented by the formula (A-I-I). In the table, * indicates the bonding end.

However, the compound represented by the formula (AII) has 2 -SO ₂ -N ^- -SO ₂ -CF ₃ or has 1 -SO ₂ -N ^- -SO ₂ -CF ₃ and 1 -SO ₃ ^- , The -SO ₂ -N ^- -SO ₂ -CF ₃ or -SO ₃ ^- is contained as either R ^h or in combination with an aromatic hydrocarbon ring (benzene ring) of an aromatic hydrocarbon group represented by Ph1 to Ph12. Preferably, it is bonded to the aromatic hydrocarbon ring (benzene ring) of the aromatic hydrocarbon group represented by Ph1 to Ph12 in R ⁴¹ to R ⁴⁴ from the bonding end.

In Tables 1 to 12, Me represents a methyl group, Et represents an ethyl group, iPr represents an isopropyl group, Bt represents an n-butyl group, EOE represents an ethoxyethyl group, and 14Bt represents a butane-1,4-diyl group, Ph1~. Ph12 means a group represented by the following formula. Where * represents the bond end.

In addition, as the compound (A-I), as shown in the following Table 13, the compound (A-I-634) to the compound (A-I-657) represented by the formula (A-I-II) may be mentioned. In the table, * indicates the bonding end.

However, the compound represented by the formula (AI-II) has an average of -SO ₂ -N ^- -SO ₂ -CF ₃ and -SO ₂ -NH-SO ₂ -CF ₃ , the -SO ₂ -N ^- -SO ₂ -CF ₃ and -SO ₂ -NH-SO ₂ -CF ₃ are contained as either of R ^h or an aromatic hydrocarbon ring represented by any one of Ph1, Ph13, and Ph14 (benzene ring) ) combined.

In Table 13, Me represents a methyl group, Et represents an ethyl group, iPr represents an isopropyl group, Bt represents an n-butyl group, EOE represents an ethoxyethyl group, Hex represents an n-hexyl group, and Ph1, Ph13, and Ph14 are represented by the following formula. The group represented.

Where * represents the bond end.

The compound (A-I) can also be used by mixing a compound represented by the following formula (A-III) (hereinafter also referred to as a compound (A-III)).

In the formula (A-III), R ^21a to R ^24a each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a substituent which may have a substituent. The aralkyl group having 7 to 30 carbon atoms, the aromatic hydrocarbon group and the aralkyl group may have a substituent of -SO ₃ ^- , and the saturated hydrocarbon group having 1 to 20 carbon atoms is contained in the saturated hydrocarbon group The hydrogen atom may be substituted by a substituted or unsubstituted amino group or a halogen atom. When the saturated hydrocarbon group having 1 to 20 carbon atoms is an alkyl group having 2 to 20 carbon atoms, the methylene group contained in the alkyl group may be Replace with an oxygen atom or -CO-. However, in the alkyl group having 2 to 20 carbon atoms, the adjacent methylene group is not replaced with an oxygen atom at the same time, and the terminal methylene group is not replaced with an oxygen atom or -CO-. R ^21a and R ^22a may bond and form a ring together with the nitrogen atom to which they are bonded, and R ^23a and R ^24a may bond and form a ring together with the nitrogen atom to which they are bonded.

R ^27a to R ^34a each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, -SO ₃ ^- or an alkyl group having 1 to 8 carbon atoms, and the methylene group constituting the alkyl group may be replaced with an oxygen atom or - CO-. R ^28a and R ^32a may be bonded to each other to form -NH-, -S-, or -SO ₂ -.

The ring T ¹⁰ represents an aromatic heterocyclic ring having 3 to 10 carbon atoms, and the aromatic heterocyclic ring may have a saturated hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent. The substituent which the aromatic hydrocarbon group may have may be -SO ₃ ^- .

M ^r+ and r are synonymous with the above.

K2 represents the number of -SO ₃ ^- which the compound represented by the formula (A-III) has.

However, the compound represented by the formula (A-III) has at least one -SO ₃ ^- . ]

Each of the saturated hydrocarbon group, the aromatic hydrocarbon group, and the aralkyl group represented by R ^21a to R ^24a may be the same as the saturated hydrocarbon group, the aromatic hydrocarbon group or the aralkyl group represented by R ⁴¹ to R ⁴⁴ .

In addition, examples of the alkyl group represented by R ^27a to R ^34a include the same groups as the alkyl group represented by R ⁴⁷ to R ⁵⁴ .

Further, the compound (A-III) preferably has one or more -SO ₃ ^- , and specifically, -SO ₃ ^- more preferably (a') is contained as either R ^27a to R ^34a or (b') Binding to an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent represented by the above R ^21a to R ^24a , or (c') and a carbon number 7 to 30 which may have a substituent represented by R ^21a to R ^24a The aralkyl group is bonded, or (d') is bonded to any one of 6 to 20 carbon atoms substituted with a hydrogen atom of an aromatic hetero ring represented by T ³ , or these (a') ~ (d) The combination of ') is more preferably (b'), (c'), (d') or a combination of these (b') to (d'). The number of -SO ₃ ^- is preferably 0 to 6, more preferably 1 to 6, still more preferably 1 to 3.

-SO ₃ ^- may be bonded to the same aromatic hydrocarbon ring, but is preferably bonded to a different aromatic hydrocarbon ring.

When the compound (AI) and the compound (A-III) are mixed, the content of the compound (A-III) is preferably 1 mol or more, more preferably 20 mol or more, more preferably 20 mol or more based on 100 mol of the compound (AI). 40 mol or more, preferably 90 mol or less, more preferably 80 mol or less, further preferably 70 mol or less.

The compound (AI) can be produced, for example, by sulfonating a compound represented by the formula (A-IV) (hereinafter sometimes referred to as a compound (A-IV)) to give a compound (A-III), and the following formula (A- The compound represented by II) is produced by reaction. The compound (AI) can be reacted with a halide (preferably chloride), an acetate, a phosphate, a sulfate, a citrate, a cyanide or the like containing a r-valent metal ion Mr ⁺ as needed. The compound (A-IV) is preferably a hydrochloride, a phosphate, a perchlorate, a BF ₄ salt, a PF ₆ salt or the like.

In the formula (A-IV), R ^1a to R ^4a each independently represent a saturated hydrocarbon group having 1 to 20 carbon atoms and an alkyl group having 2 to 20 carbon atoms which may be substituted with an amino group or a halogen atom which may be substituted or unsubstituted. a group in which a methylene group constituting the alkyl group is replaced with an oxygen atom or -CO-, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and an aralkyl group having 7 to 30 carbon atoms which may have a substituent Or a hydrogen atom. R ^1a and R ^2a may bond and form a ring together with the nitrogen atom to which they are bonded, and R ^3a and R ^4a may bond and form a ring together with the nitrogen atom to which they are bonded.

R ^7a to R ^14a each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group or an alkyl group having 1 to 8 carbon atoms, and the methylene group constituting the alkyl group may be replaced with an oxygen atom or -CO-. R ^8a and R ^12a may be bonded to each other to form -NH-, -S-, or -SO ₂ -.

The ring T ¹¹ represents an aromatic heterocyclic ring having 3 to 10 carbon atoms, and the aromatic heterocyclic ring may have a saturated hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

M ¹ represents Cl ^- , a phosphate ion, a perchlorate ion, BF ₄ ^- , PF ₆ ^- . ]

[In the formula (A-III), R ^21a to R ^24a , R ^27a to R ^34a , ring T ¹⁰ , M ^r+ , r, k2 are synonymous with the above.

However, the compound represented by the formula (A-III) has at least one -SO ₃ ^- . ]

[In the formula (A-II), R ^f is synonymous with the above. ]

[In the formula (AI), R ⁴¹ to R ⁴⁴ , R ⁴⁷ to R ⁵⁴ , and the rings T ¹ , k, M ^r+ and r are synonymous with the above. ]

As a method of sulfonation, various well-known methods are mentioned, for example, the method of Journal of Organic Chemistry, (1994), Vol. 59, #11, pp. 3232-3236.

The compound (A-I) of the present invention can be applied to a fiber product, and the fiber material can be colored, for example, by kneading, dipping, or adhering to a fiber material.

The coloring composition of the present invention contains a coloring agent (A), and the coloring agent (A) contains the compound (A-I). The coloring composition of the present invention preferably further contains a solvent (E), and more preferably further contains a resin (B), a polymerizable compound (C), and a polymerization initiator (D). A polymerization initiation aid (D1) and a leveling agent (F) may be further included.

Hereinafter, the colored composition containing the resin (B), the polymerizable compound (C), and the polymerization initiator (D) may be referred to as a colored curable resin composition.

In the present specification, the compounds exemplified as the respective components can be used singly or in combination of plural kinds unless otherwise specified.

Solvent (E)

The solvent (E) is not particularly limited, and a solvent which is generally used in the field can be used. For example, an ester solvent (a solvent containing -COO- or a -O- in a molecule), an ether solvent (a solvent containing -O- in the molecule, a solvent containing no -COO-), an ether ester solvent (in the molecule) a solvent containing -COO- and -O-), a ketone solvent (a solvent containing -CO- in the molecule, a solvent not containing -COO-), alcohol soluble The agent (solvent containing OH, no -O-, -CO- and -COO- in the molecule), an aromatic hydrocarbon solvent, a guanamine solvent, dimethyl hydrazine or the like.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, and isoamyl acetate. Butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, cyclohexane Alcohol acetate, γ-butyrolactone and the like.

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, and diethylene glycol single. Ethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methyl Oxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, Diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenethyl ether and methyl anisole.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and methyl 3-methoxypropionate. Ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate Ester, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2-B Ethyl oxy-2-methylpropanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol B Ethyl acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, digan Alcohol monobutyl ether acetate and dipropylene glycol methyl ether acetate.

Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, and 4-methyl-2-pentyl Ketone, cyclopentanone, cyclohexanone and isophorone.

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and 1,3,5-trimethylbenzene.

Examples of the guanamine solvent include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

These solvents may be used singly or in combination of two or more.

Among them, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, Dipropylene glycol methyl ether acetate, 3-methoxy-1-butanol, 3-methoxybutyl acetate, ethyl 3-ethoxypropionate, ethyl lactate, N-methylpyrrolidone , 4-hydroxy-4-methyl-2-pentanone, N,N-dimethylformamide, etc., more preferably ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate Ester, dipropylene glycol methyl ether acetate, 3-methoxy-1-butanol, 3-methoxybutyl acetate, ethyl 3-ethoxypropionate, ethyl lactate, N-A Pyrrolidone.

When the solvent (E) is contained, the content of the solvent (E) is preferably 70 to 95% by mass based on the total amount of the coloring composition. It is preferably 75 to 92% by mass. In other words, the total amount of the solid content of the coloring composition is preferably 5 to 30% by mass, and more preferably 8 to 25% by mass. When the content of the solvent (E) is in the above range, the flatness at the time of application is good, and the color density is not insufficient when the color filter is formed. Therefore, the display characteristics tend to be good.

The "total amount of solid content" in the present specification means the total amount of components from which the solvent (E) is removed from the coloring composition. The total amount of the solid components and the content of each component with respect to the solid components can be measured, for example, by a known analytical means such as liquid chromatography or gas chromatography.

Colorant (A)

The coloring agent (A) may independently use a dye having the compound (AI) of the present invention as an active ingredient, but may further contain other dyes (A1), pigments (P), for color adjustment, that is, for adjusting the spectral characteristics. Or a mixture of them.

Examples of the dye (A1) include dyes such as oil-soluble dyes, acid dyes, basic dyes, direct dyes, mordant dyes, amine salts of acid dyes, and sulfonamide derivatives of acid dyes, and examples thereof include color index (The A well-known dye described in the dyed note (color dyeing company) of a compound classified as a dye in the Society of Dyers and Colourists. Further, examples of the chemical structure include azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, naphthoquinone dyes, quinone imine dyes, methine dyes, azomethine dyes, and squares. Acid dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, and nitro dyes. Among these, an organic solvent-soluble dye is preferably used.

Specific examples of the dye (A1) include CI Solvent Yellow 4 (hereinafter, the description of CI Solvent Yellow is omitted, and only the serial number is described), 14, 15, 23, 24, 25, 38, 62, 63, 68, 79. , 81, 82, 83, 89, 94, 98, 99, 162; CI solvent red 24, 45, 49, 90, 91, 118, 119, 122, 124, 125, 127, 130, 132, 145, 160, 218; CI solvent orange 2, 7, 11, 15, 26, 41, 54, 56, 99; CI solvent blue 4, 5, 37, 67, 70, 90; CI solvent green 1, 4, 5, 7, 34 , 35, etc. CI solvent dye, CI acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 91, 92, 97, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 151, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 211, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251, 274, 289; CI acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426; CI Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64 , 74, 75, 94, 95, 107, 108, 169, 173; CI Acid Violet 6B, 7, 9, 17, 19, 30, 102, 120; CI Acid Blue 1, 7, 9, 15, 18, 22 , 29, 42, 59, 60, 62, 70, 72, 74, 82, 83, 86, 87, 90, 92, 93, 100, 102, 103, 104, 113, 117, 120, 126, 130, 131 , 142, 147, 151, 154, 158, 161, 166, 167, 168, 170, 171, 184, 187, 192, 199, 210, 229, 234, 236, 242, 243, 256, 259, 267, 285 , 296, 315, 335; CI acid green 1, 3, 5, 9, 16, 50, 58, 63, 65, 80, 104, 105, 106, 109, etc. CI acid dye, CI direct yellow 2, 33, 34 , 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141; CI Direct red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220 221, 222, 232, 233, 234, 241, 243, 246, 250; CI Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75 , 94, 95, 107, 108, 149, 162, 169, 173; CI direct yellow 2, 4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 132, 136, 138, 141; CI Direct Orange 26 , 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; CI direct purple 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104; CI direct blue 1, 2, 6, 8, 15, 22, 25, 41, 57, 71, 76 , 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120 , 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192 , 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242 ,243,244,245,246,247,248,249,250,251,252,256,257,259,260,268,274,275,293; CI Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 and other CI direct dyes, CI disperse yellow 51, 54, 76 and other CI disperse dyes, CI alkaline red 1, 10; CI alkaline blue 1, 3, 5 , 7, 9, 19, 24, 25, 26, 28, 29, 40, 41, 54, 58, 59, 64, 65, 66, 67, 68; CI alkaline green 1 and other CI basic dyes, CI active yellow 2, 76, 116; CI active orange 16; CI active red 36 and other CI reactive dyes, CI mordant yellow 5, 8, 10, 16, 20, 26, 30 , 31, 33, 42, 43, 45, 56, 61, 62, 65; CI mordant red 1, 2, 4, 9, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 30, 32, 33, 36, 37, 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95; CI mord Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48; CI mordant purple 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58; CI mordant blue 1, 2, 3, 7, 9 , 12, 13, 15, 16, 19, 20, 21, 22, 26, 30, 31, 39, 40, 41, 43, 44, 49, 53, 61, 74, 77, 83, 84; CI mord green CI mordant dyes such as 1, 3, 4, 5, 10, 15, 26, 29, 33, 34, 35, 41, 43, and 53, and CI vat dyes such as CI reduction green 1. Among them, a violet dye is preferred.

The pigment (P) is not particularly limited, and a known pigment can be used. For example, a pigment classified as a pigment in the excellent index (published by The Society of Dyers and Colourists) can be cited.

Examples of the pigment include CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, and 125. Yellow pigments such as 128, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214; CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, Orange pigments such as 55, 59, 61, 64, 65, 71, 73; CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215 , 216, 224, 242, 254, 255, 264, 265 and other red pigments; CI pigment blue 15, 15:3, 15:4, 15:6, 60 and other cyan pigments; CI pigment purple 1, 19, 23, 29 , purple pigments such as 32, 36, 38; CI pigment green 7, 36, 58 and other green pigments; CI pigment brown 23, 25 and other brown pigments; CI pigment black 1, 7 and other black pigments.

The pigment (P) is preferably a phthalocyanine pigment and a dioxazine pigment, and more preferably at least one selected from the group consisting of C.I. Pigment Blue 15:6 and Pigment Violet 23. By including the above-described pigment, the optimization of the transmission spectrum is easy, and the light resistance and chemical resistance of the color filter become good.

For the pigment, if necessary, rosin treatment, surface treatment using a pigment derivative into which an acidic group or a basic group is introduced, graft treatment on a pigment surface using a polymer compound, or the like, and sulfuric acid micronization may be used. Micronization treatment, etc., or used to remove impurities The organic solvent, water, and the like are washed, and the ionic impurities are removed by an ion exchange method or the like. The pigment preferably has a uniform particle size.

The pigment is dispersed by a pigment dispersant, and a pigment dispersion liquid in which the pigment is uniformly dispersed in a solution can be obtained. The pigments may be separately subjected to dispersion treatment, or may be subjected to dispersion treatment by mixing a plurality of types.

The pigment dispersing agent may, for example, be a surfactant, and may be a cationic, anionic, nonionic or amphoteric surfactant. Specifically, a pigment dispersing agent such as a polyester-based, polyamine-based or acrylic-based one can be mentioned. These pigment dispersants may be used singly or in combination of two or more. In the case of the pigment dispersant, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), (made by Kyoeisha Chemical Co., Ltd.), (Trademark)( Manufactured by SFKA (registered trademark) (manufactured by BASF Corporation), (registered trademark) (Ajinomoto (manufactured by the company), Disperbyk (registered trademark) ( I made it, etc.).

In the case of using a pigment dispersant, the amount thereof is preferably 100 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less based on 100 parts by mass of the pigment. When the amount of the pigment dispersant used is in the above range, there is a tendency to obtain a pigment dispersion liquid in a uniformly dispersed state.

The content of the compound (AI) is preferably 5% by mass or more and 70% by mass or less, more preferably 5% by mass or more and 60% by mass or less, and still more preferably 5% by mass or more and 50% based on the total amount of the solid content. Below mass%.

In addition, the content of the compound (A-I) is preferably 1% by mass or more and 100% by mass or less, and more preferably 10% by mass or more and 100% by mass or less based on the total amount of the coloring agent (A).

In addition, when the compound (AI) is used in combination with the compound (A-III), the total content of the compound (AI) and the compound (A-III) is preferably 10% by mass based on the total amount of the solid component. The above is 70% by mass or less, and more preferably 15% by mass or more and 60% by mass or less.

When the dye (A1) is contained, the content thereof is preferably 0.5% by mass or more and 90% by mass or less, and more preferably 0.5% by mass or more and 70% by mass or less based on the total amount of the coloring agent (A). When the pigment (P) is contained, the content thereof is preferably 1% by mass or more and 99% by mass or less, and more preferably 1% by mass or more and 70% by mass or less based on the total amount of the coloring agent (A).

The content of the coloring agent (A) is preferably 5% by mass or more and 70% by mass or less, more preferably 5% by mass or more and 60% by mass or less, and still more preferably 5% by mass or more, based on the total amount of the solid content. 50% by mass or less.

Resin (B)

The resin (B) is preferably an alkali-soluble resin (B). The alkali-soluble resin (B) (hereinafter sometimes referred to as "resin (B)") is a copolymer containing a structural unit derived from a monomer (Ba) selected from at least one of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride.

Examples of such a resin (B) include the following resins [K1] to [K6].

The resin [K1] has a source selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides a structural unit of at least one of monomers (a) (hereinafter sometimes referred to as "(a)")) and a monomer derived from a cyclic ether structure having a carbon number of 2 to 4 and an ethylenically unsaturated bond (b) a copolymer of a structural unit (hereinafter sometimes referred to as "(b)"); a resin [K2] having a structural unit derived from (a) and a structural unit derived from (b), and a single copolymerizable from (a) The body (c) (however, different from (a) and (b).) (hereinafter sometimes referred to as "(c)")); the resin [K3] has a structural unit derived from (a) and a copolymer derived from the structural unit of (c); the resin [K4] has a resin (copolymer) which gives (b) a structural unit added from the structural unit derived from (a) and a structural unit derived from (c); a resin [ K5] has a resin (copolymer) such that (a) is added to the structural unit derived from (b) and the structural unit derived from (c); the resin [K6] has (a) added to (b) a structural unit, a structural unit in which a carboxylic anhydride is further added, and a resin (copolymer) derived from the structural unit of (c).

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid; maleic acid, fumaric acid, and citraconic acid; , mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6- An unsaturated dicarboxylic acid such as tetrahydrophthalic acid, dimethyltetrahydrophthalic acid or 1,4-cyclohexene dicarboxylic acid; Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[ 2.2.1] a carboxyl group-containing bicyclic unsaturated compound such as hept-2-ene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene; maleic anhydride, citraconic anhydride, itaconic anhydride , 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydroortylene Unsaturated dicarboxylic anhydrides such as formic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride; succinic acid mono[2-(methyl) Unsaturated mono[(meth)acryloxyloxy group of a divalent or higher polycarboxylic acid such as propylene methoxyethyl ester or phthalic acid mono [2-(methyl) propylene oxyethyl] ester An alkyl group ester; an unsaturated acrylate having a hydroxyl group and a carboxyl group in the same molecule, such as α-(hydroxymethyl)acrylic acid.

Among these, acrylic acid, methacrylic acid, maleic anhydride, and the like are preferable from the viewpoint of copolymerization reactivity and solubility of the obtained resin in an aqueous alkali solution.

(b) means, for example, a cyclic ether structure having a carbon number of 2 to 4 (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond. Polymeric compound.

(b) A monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloxy group is preferred.

In the present specification, "(meth)acrylic acid" means selected from the group consisting of At least one of acrylic acid and methacrylic acid. The expressions "(meth)acrylinyl" and "(meth)acrylate" have the same meaning.

(b), for example, a monomer (b1) having an epoxyethyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), having an oxetanyl group and an ethylenically unsaturated bond The monomer (b2) (hereinafter sometimes referred to as "(b2)"), the monomer (b3) having a tetrahydrofuranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)")).

(b1), for example, a monomer (b1-1) having a structure in which a linear or branched aliphatic hydrocarbon is epoxidized (hereinafter sometimes referred to as "(b1-1)")), A monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as "(b1-2)").

Examples of (b1-1) include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, and glycidyl vinyl ether. , o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-Methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidoxymethyl)styrene, 2, 4-bis(glycidoxymethyl)styrene, 2,5-bis(glycidoxymethyl)styrene, 2,6-bis(glycidoxymethyl)styrene, 2,3, 4-tris(glycidoxymethyl)styrene, 2,3,5-tris(glycidoxymethyl)styrene, 2,3,6-tris(glycidoxymethyl)styrene, 3,4,5-tris(glycidoxymethyl)styrene, 2,4,6-tris(glycidoxymethyl)styrene, and the like.

Examples of (b1-2) include vinylcyclohexene monooxide and 1,2-epoxy-4-vinylcyclohexane (for example, (registered trademark) 2000; manufactured by Daicel Co., Ltd., 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, (registered trademark) A400; manufactured by Daicel Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, M100; manufactured by Daicel Co., Ltd.), a compound represented by the formula (BI), a compound represented by the formula (BII), and the like.

In the formula (BI) and the formula (BII), R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group.

X ^a and X ^b represents a single ^{bond, * - R c -, *} - R c -O -, * - R c -S- or * -R ^c -NH-.

R ^c represents an alkylene group having 1 to 6 carbon atoms.

* indicates the bonding end with O. ]

Examples of the alkyl group having 1 to 4 carbon atoms of R ^a and R ^b include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, and a t-butyl group.

Examples of the alkyl group in which the hydrogen atom of R ^a and R ^b is substituted by a hydroxyl group include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, and a 3-hydroxypropyl group. Base, 1-hydroxy-1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, and the like.

R ^a and R ^{b are} preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Specifically, Preferable examples thereof include a hydrogen atom, a methyl group, an ethyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group, and more preferably a hydrogen atom or a methyl group.

Examples of the alkylene group of R ^c include a linear or branched alkylene group, and specific examples thereof include a methylene group, an ethylene group, a propane-1,3-diyl group, and a butane-1. a linear alkylene group such as a 4-diyl group, a pentane-1,5-diyl group or a hexane-1,6-diyl group; or a branched chain alkylene group such as a propane-1,2-diyl group.

As X ^a and X ^b , a single bond, *-R ^c -, or *-R ^c -O- is preferable, and a single bond or *-R ^c -O- is more preferable, and a single bond or a methylene group is particularly preferable. Ethylene, *-CH ₂ -O- and *-CH ₂ CH ₂ -O-, more preferably a single bond, *-CH ₂ CH2-O- (* represents a bonding end with O) .

The compound represented by the formula (BI) may, for example, be a compound represented by any one of the formulae (BI-1) to (BI-15). Among them, it is preferred that the formula (BI-1), the formula (BI-3), the formula (BI-5), the formula (BI-7), the formula (BI-9) or the formula (BI-11)~(BI- The compound represented by 15) is more preferably a compound represented by the formula (BI-1), the formula (BI-7), the formula (BI-9) or the formula (BI-15).

The compound represented by the formula (BII) may, for example, be a compound represented by any one of the formulae (BII-1) to (BII-15). Among them, it is preferred from the formula (BII-1), the formula (BII-3), the formula (BII-5), the formula (BII-7), the formula (BII-9) or the formula (BII-11) to the formula (BII- The compound represented by 15) is more preferably a compound represented by the formula (BII-1), the formula (BII-7), the formula (BII-9) or the formula (BII-15).

The compound represented by the formula (BI) and the compound represented by the formula (BII) may be used singly or in combination, and the compound represented by the formula (BI) may be used in combination with the compound represented by the formula (BII). When they are used in combination, the content ratio of the compound represented by the formula (BI) and the compound represented by the formula (BII) is preferably 5:95 to 95:5, more preferably 10:90 to 90, on a molar basis. :10, further preferably 20:80 to 80:20.

As (b2), a monomer having an oxetanyl group and a (meth) acryloxy group is more preferable. As (b2), 3-methyl-3- can be cited Methyl propylene methoxymethyl oxetane, 3-methyl-3-propenyloxymethyl oxetane, 3-ethyl-3-methyl propylene methoxymethyl oxalate Cyclobutane, 3-ethyl-3-propenyloxymethyloxetane, 3-methyl-3-methylpropenyloxyethyloxetane, 3-methyl-3 - propylene methoxyethyl oxetane, 3-ethyl-3-methylpropenyloxyethyl oxetane, 3-ethyl-3-propenyloxyethyl oxane Butane and so on.

As (b3), a monomer having a tetrahydrofuranyl group and a (meth)acryloxy group is more preferable. Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, V #150, manufactured by Osaka Organic Chemical Industry Co., Ltd., tetrahydrofurfuryl methacrylate, and the like.

(b) is preferably (b1) from the viewpoint of further improving the reliability of heat resistance and chemical resistance of the obtained color filter. Further, (b1-2) is more preferable in that the storage stability of the colored composition is excellent.

Examples of (c) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, and t-butyl (meth)acrylate. , 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, Cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo [5.2.1.0 ^2,6 ]decane-8-yl (meth)acrylate (in the technical field) As a conventional name, it is called "dicyclopentanyl (meth) acrylate." In addition, it is sometimes called "tricyclodecyl (meth) acrylate".), tricyclo(meth) acrylate [5.2.1.0 ^{2 , 6} ]nonene-8-yl ester (in the technical field, as a conventional name, it is called "dicyclopentenyl (meth) acrylate"), (di) pentyloxyethyl (meth) acrylate, (a) Isobornyl acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, (meth) acrylates such as benzyl (meth) acrylate; Hydroxy-containing (meth) acrylates such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; diethyl maleate, diethyl fumarate, itaconic acid a dicarboxylic acid diester such as diethyl ester; bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]heptane- 2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2. 1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[ 2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1 Hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxyl -5-Methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2 .1]hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5- Phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene a bicyclic unsaturated compound such as 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene; N-phenylmaleimide, N-cyclohexylmaleimine, N-benzylmaleimide, N-succinimide-3-maleimide benzoate, N-succinimide-4-maleimide butyrate, N - amber quinone imine-6-maleimide caproate, N-amber succinimide-3-maleimide propionate, N-(9-acridinyl) malayan Dicarbonylimine derivatives such as amines; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, etc. Aromatic compound; nitrile containing vinyl such as acrylonitrile or methacrylonitrile; halogenated hydrocarbon such as vinyl chloride or vinylidene chloride; decylamine containing vinyl group such as acrylamide or methacrylamide; vinyl acetate, etc. Ester; a diene such as 1,3-butadiene, isoprene or 2,3-dimethyl-1,3-butadiene.

Among these, as the (c), a vinyl group-containing aromatic compound, a dicarbonylimine derivative, or a bicyclic unsaturated compound is preferable from the viewpoint of copolymerization reactivity and heat resistance. Specifically, styrene, vinyl toluene, N-phenyl maleimide, N-cyclohexylmaleimide, N-benzyl maleimide, bicyclo [2.2.1] g-2 - Alkene, etc.

In the resin [K1], the ratio of the structural unit derived from each monomer is preferably a structural unit derived from (a) in all the structural units constituting the resin [K1]: 2 to 60 mol% of the structural unit derived from (b) 40 to 98 mol%, more preferably structural unit derived from (a): 10 to 50 mol% of structural unit derived from (b): 50 to 90 mol%.

If the ratio of the structural unit of the resin [K1] is within the above range, the storage stability of the colored composition, the developability when forming a colored pattern, The obtained color filter tends to be excellent in solvent resistance.

The resin [K1] can be referred to, for example, in the method described in the "Experimental Method for Polymer Synthesis" (Otsuno Ryokan Publishing Co., Ltd., First Edition, First Printing, March 1, 1972). The cited references are manufactured.

Specifically, a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like are charged into a reaction vessel, for example, oxygen is replaced with nitrogen to form a deoxidizing atmosphere, and heated and kept warm while stirring. method. In addition, the polymerization initiator, the solvent, and the like used herein are not particularly limited, and those generally used in the field can be used. Examples of the polymerization initiator include an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.), and an organic peroxide. (Benoxime peroxide, etc.), as a solvent, a solvent (E) which is a coloring composition of the present invention may be mentioned as long as it dissolves each monomer.

In addition, as for the obtained copolymer, the solution after the reaction may be used as it is, or a concentrated or diluted solution may be used, or a product obtained by reprecipitation or the like as a solid (powder) may be used. In particular, in the polymerization, by using the solvent contained in the coloring composition of the present invention as a solvent, the solution after the reaction can be used as it is in the preparation of the coloring composition of the present invention, so that the present invention can be used. The manufacturing process of the coloring composition is simplified.

In the resin [K2], the ratio of the structural unit derived from each monomer is preferably a structural unit derived from (a) in all structural units constituting the resin [K2]: 2 to 45 mol% Structural unit derived from (b): 2 to 95 mol% of structural unit derived from (c): 1 to 65 mol%, more preferably structural unit derived from (a): 5 to 40 mol% of structural unit derived from (b) : 5 to 80 mol% of the structural unit derived from (c): 5 to 60 mol%.

When the ratio of the structural unit of the resin [K2] is within the above range, the storage stability of the colored composition, the developability when the colored pattern is formed, and the solvent resistance, heat resistance and mechanical strength of the obtained color filter are excellent. Propensity.

The resin [K2] can be produced, for example, in the same manner as the method described in the production method of the resin [K1].

In the resin [K3], the ratio of the structural unit derived from each monomer is preferably a structural unit derived from (a) in all the structural units constituting the resin [K3]: 2 to 60 mol% of the structural unit derived from (c) 40 to 98 mol%, more preferably structural unit derived from (a): 10 to 50 mol% of structural unit derived from (c): 50 to 90 mol%.

The resin [K3] can be produced, for example, in the same manner as the method described in the production method of the resin [K1].

The resin [K4] can be produced by obtaining a copolymer of (a) and (c), adding (b) a cyclic ether having 2 to 4 carbon atoms, and (a) a carboxylic acid and/or a carboxylic anhydride. .

First, the copolymers (a) and (c) can be produced in the same manner as the method described in the production method of the resin [K1]. In this case, the ratio of the structural unit derived from each monomer is preferably the same ratio as the ratio enumerated in the resin [K3].

Next, the cyclic ether having 2 to 4 carbon atoms which is contained in (b) is reacted with a part of the carboxylic acid and/or carboxylic anhydride derived from (a) in the above copolymer.

Next, in the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced with nitrogen by air, and a catalyst for reacting (b), a carboxylic acid or a carboxylic anhydride with a cyclic ether (for example, tris(dimethylamino) A methyl group of phenol or the like and a polymerization inhibitor (for example, hydroquinone) are placed in a flask, and for example, at 60 to 130 ° C for 1 to 10 hours, the resin [K4] can be produced.

The amount of use of (b) is preferably 5 to 80 moles, more preferably 10 to 75 moles, per 100 moles of (a). When the amount of use of (b) is adjusted to this range, the storage stability of the coloring composition, the developability at the time of pattern formation, and the balance of solvent resistance, heat resistance, mechanical strength, and sensitivity of the obtained pattern become good. Propensity. Since the reactivity of the cyclic ether is high and the unreacted (b) is not easily retained, it is preferably (b1), more preferably (b1-1), as the (b) used for the resin [K4].

The amount of use of the above-mentioned reaction catalyst is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total of (a), (b) and (c). The amount of the polymerization inhibitor to be used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total of (a), (b) and (c).

Method for feeding each reagent, reaction temperature and reaction time The reaction conditions such as the ratio can be appropriately adjusted in consideration of the production equipment, the amount of heat generation by polymerization, and the like. In addition, similarly to the polymerization conditions, the feeding method and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generation by polymerization, and the like.

When the resin [K5] was produced, the copolymer of (b) and (c) was obtained in the same manner as in the above-described method for producing the resin [K1]. In the same manner as described above, the obtained copolymer may be used as it is, or a concentrated or diluted solution may be used, or a product obtained by reprecipitation or the like as a solid (powder) may be used.

The ratio of the structural unit derived from (b) and (c) is preferably a structural unit derived from (b) with respect to the total number of moles of all the structural units constituting the copolymer of the above (b) and (c): 5~ 95 mol% of the structural unit derived from (c): 5 to 95 mol%, more preferably structural unit derived from (b): 10 to 90 mol% of the structural unit derived from (c): 10 to 90 mol%.

Further, in the second step, under the same conditions as in the method for producing the resin [K4], (b) the (a) having a carboxylic acid or a carboxylic anhydride and a copolymer of (b) and (c) The cyclic ether reacts to obtain the resin [K5].

In the second stage, the amount of (a) used for the reaction with the copolymers of the above (b) and (c) is preferably 5 to 80 moles per 100 moles of (b). Since the cyclic ether has high reactivity, the unreacted (b) does not easily remain, so it is used as (b) of the resin [K5], preferably (b1), more preferably (b1-1).

The resin [K6] is a resin obtained by further reacting a carboxylic acid anhydride with a resin [K5]. The carboxylic anhydride is reacted with a hydroxyl group produced by the reaction of a cyclic ether with a carboxylic acid or a carboxylic anhydride.

The resin [K6] is a resin obtained by further reacting a carboxylic anhydride with a resin [K5], and specifically, by reacting a carboxylic anhydride with a carboxylic acid or a carboxylic acid anhydride derived from the cyclic ether of (b) and (a) The resulting hydroxyl groups are reacted to produce.

Examples of the carboxylic anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, and 3,4,5,6-tetrahydroortylene. Dicarboxylic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride, etc. . The amount of the carboxylic anhydride used is preferably 0.5 to 1 mol based on 1 mol of the amount of (a) used.

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer and (meth)acrylic acid 3,4-epoxytricyclo[5.2. .1.0 ^2.6 ]Resin such as oxime ester/(meth)acrylic acid copolymer [K1]; glycidyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer, (meth)acrylic acid glycidyl methacrylate / styrene / (meth) acrylic acid copolymer, (meth) acrylate, 3,4-epoxy-tricyclo [5.2.1.0 ^2.6] decyl acrylate / (meth) acrylic acid / N- acyl-cyclohexylmaleimide Imine copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl (meth)acrylic/vinyltoluene copolymer, 3-methyl-3-(methyl) (meth)acrylate Resin such as acryloxymethyloxetane/(meth)acrylic acid/styrene copolymer [K2]; benzyl (meth)acrylate/(meth)acrylic acid copolymer, styrene/(methyl a resin such as an acrylic copolymer, benzyl (meth)acrylate/tricyclodecyl (meth)acrylate/(meth)acrylic copolymer; [K3]; glycidyl (meth)acrylate and (methyl) a resin obtained by adding benzyl acrylate/(meth)acrylic acid copolymer to make (meth) propylene a resin obtained by adding a glycidyl ester to a tricyclodecyl (meth) acrylate/styrene/(meth)acrylic acid copolymer, a glycidyl (meth)acrylate and a tricyclodecyl (meth)acrylate a resin such as a resin obtained by adding a benzyl (meth) acrylate/(meth)acrylic acid copolymer [K4]; a (meth)acrylic acid and a tricyclodecyl (meth)acrylate/(meth)acrylic acid a resin obtained by reacting a copolymer of glycidyl ester, a resin such as a resin obtained by reacting a copolymer of (meth)acrylic acid and tricyclodecyl (meth)acrylate/styrene/glycidyl (meth)acrylate [K5 a resin obtained by reacting a resin obtained by reacting a copolymer of (meth)acrylic acid with tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate, and further reacting with tetrahydrophthalic anhydride Resin [K6] and the like.

The resin (B) is preferably one selected from the group consisting of a resin [K1], a resin [K2], and a resin [K3], and more preferably one selected from the group consisting of a resin [K2] and a resin [K3]. When it is these resins, the coloring composition is excellent in developability. From the viewpoint of the adhesion between the colored pattern and the substrate, the resin [K2] is more preferable.

The polystyrene-equivalent weight average molecular weight of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, still more preferably 5,000 to 30,000. If the molecular weight is within the above range, there is a coating The film hardness is increased, the residual film ratio is also high, the solubility of the unexposed portion in the developer is good, and the resolution of the colored pattern tends to be improved.

The degree of dispersion [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably from 1.1 to 6, more preferably from 1.2 to 4.

The acid value in terms of solid content of the resin (B) is preferably 30 to 170 mg-KOH/g, more preferably 40 to 150 mg-KOH/g, still more preferably 50 to 135 mg-KOH/g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B), and can be obtained, for example, by titration using a potassium hydroxide aqueous solution.

When the resin (B) is contained, the content of the resin (B) is preferably 7 to 70% by mass, more preferably 13 to 65% by mass, even more preferably 17 to 60% by mass, based on the total amount of the solid content. . When the content of the resin (B) is within the above range, a colored pattern can be formed, and the resolution of the colored pattern and the residual film ratio tend to be improved.

Polymeric compound (C)

The polymerizable compound (C) is a compound which can be polymerized by an active radical and/or an acid generated by the polymerization initiator (D), and examples thereof include a compound having a polymerizable ethylenically unsaturated bond, etc., and preferably (A) Base) acrylate compound.

Examples of the polymerizable compound having one ethylenically unsaturated bond include mercaptophenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 2-ethylhexyl carbitol acrylic acid. Ester, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, and the like, and (Ba), (Bb), and (Bc) described above.

Examples of the polymerizable compound having two ethylenically unsaturated bonds include 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, and neopentyl glycol di(a). Base) acrylate, triethylene glycol di(meth)acrylate, bis(acryloxyethyl)ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, and the like.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such a polymerizable compound include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol penta(meth)acrylate. , dipentaerythritol hexa(meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, pentaerythritol deca (meth) acrylate, pentaerythritol 九 (meth) acrylate , tris(2-(meth)acryloxyethyl)isocyanurate, ethylene glycol modified pentaerythritol tetra(meth)acrylate, ethylene glycol modified dipentaerythritol hexa(meth)acrylate , propylene glycol modified pentaerythritol tetra (meth) acrylate, propylene glycol modified dipentaerythritol hexa (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol hexa Acrylate or the like, among which dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable.

The weight average molecular weight of the polymerizable compound (C) is preferably 150 or more and 2,900 or less, and more preferably 250 to 1,500.

When the polymerizable compound (C) is contained, the content of the polymerizable compound (C) is preferably 7 with respect to the total amount of the solid component. The mass% or more and the mass% are 65% by mass or less, more preferably 10% by mass or more and 60% by mass or less, and still more preferably 12% by mass or more and 55% by mass or less.

In addition, when the resin (B) and the polymerizable compound (C) are contained, the content ratio of the resin (B) to the polymerizable compound (C) [resin (B): polymerizable compound (C)] is based on mass. It is preferably 20:80 to 80:20, more preferably 30:70 to 80:20.

When the content of the polymerizable compound (C) is within the above range, there is a tendency that the residual film ratio at the time of formation of the colored pattern and the chemical resistance of the color filter are improved.

Polymerization initiator (D)

The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating a living radical, an acid or the like by the action of light or heat, and a known polymerization initiator can be used.

Examples of the polymerization initiator (D) include an O-indenyl hydrazine compound, an alkyl phenyl ketone compound, a biimidazole compound, a triazine compound, and a fluorenyl phosphine oxide compound.

The above O-indenyl ruthenium compound is a compound having a partial structure represented by the formula (d1). Hereinafter, * indicates the bonding end.

The above O-indenyl hydrazine compound may, for example, be N-benzylideneoxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine or N-benzidine. Oxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-ya Amine, N-benzylideneoxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1- 9-ethyl-6-(2-methylbenzylidenyl)-9H-indazol-3-yl]ethane-1-imine, N-ethyloxy-1-[9-ethyl- 6-{2-Methyl-4-(3,3-dimethyl-2,4-dioxolanylmethoxy)benzylidenyl}-9H-indazol-3-yl]ethane -1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-3-cyclopentylpropane -1-imine, N-benzylideneoxy-1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-3-cyclopentyl Propane-1-keto-2-imine and the like. Commercial products such as Irgacure (registered trademark) OXE01, OXE02 (above, manufactured by BASF Corporation), and N-1919 (made by ADEKA Co., Ltd.) can be used. Wherein the O-indenyl hydrazine compound is preferably selected from the group consisting of N-benzylideneoxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzylformamide 1-(4-phenylsulfanylphenyl)octane-1-one-2-imine and N-benzylideneoxy-1-(4-phenylsulfanylphenyl)-3 At least one of cyclopentylpropan-1-one-2-imine, more preferably N-benzylideneoxy-1-(4-phenylsulfanylphenyl)octane-1-one- 2-imine.

The above alkyl phenyl ketone compound is, for example, a compound having a partial structure represented by the formula (d2) or a partial structure represented by the formula (d3). In these partial structures, the benzene ring may have a substituent.

As the compound having a partial structure represented by the formula (d2), for example, 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl) is exemplified. Propane-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[ (4-Methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one. Commercial products such as Irgacure 369, 907, and 379 (above, manufactured by BASF Corporation) can be used.

Examples of the compound having a partial structure represented by the formula (Dd3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-hydroxy-2-methyl-1-[4- (2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane-1- Olefin of ketone, α,α-diethoxyacetophenone, benzoin dimethyl ketal, and the like.

In terms of sensitivity, the alkyl phenyl ketone compound is preferably a compound having a partial structure represented by the formula (d2).

The biimidazole compound may, for example, be a compound represented by the formula (d4).

In the formula (d4), R ^d1 to R ^d6 represent an aryl group having 6 to 10 carbon atoms which may have a substituent. ]

Examples of the aryl group having 6 to 10 carbon atoms of R ^d1 to R ^d6 include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, and a naphthyl group, and a phenyl group is preferable.

Examples of the substituent of the aryl group which may be substituted for the above R ^d1 to R ^d6 include a halogen atom and an alkoxy group having 1 to 4 carbon atoms. The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and is preferably a chlorine atom. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, and a methoxy group is preferable.

Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, and 2,2'-bis(2,3-di). (Chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (for example, see JP-A-6-75372, JP-A-6-75373, etc.), 2, 2'- Bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-four (alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)biimidazole, 2,2' - bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (for example, refer to Japanese Patent Publication No. Sho 48-38403, JP-A-62-- Japanese Patent Publication No. 174204, etc., an imidazole compound in which a phenyl group at the 4,4', 5, 5'-position is substituted with an alkoxycarbonyl group (for example, see JP-A-7-10913, etc.). Among them, preferred are compounds represented by the following formulas and mixtures thereof.

The triazine compound may, for example, be 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine or 2,4-bis(trichloro). Methyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperidin-1,3,5-triazine , 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[ 2-(5-methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl) Vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]- 1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine Wait.

The above fluorenylphosphine oxide compound may, for example, be 2,4,6-trimethylbenzimidyldiphenylphosphine oxide.

Further, examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether. ; benzophenone, methyl o-benzhydrylbenzoate, 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenyl sulfide, 3,3',4 a benzophenone compound such as 4'-tetrakis(tert-butylperoxycarbonyl)benzophenone or 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, 2-ethyl Anthraquinone compounds such as ruthenium, camphorquinone, etc.; 10-butyl-2-chloroacridone, benzophenone, methyl phenylglyoxylate, titanocene compound, and the like.

These are preferably used in combination with a polymerization initiation aid (D1) (particularly an amine) to be described later.

Examples of the acid-generating polymerization initiator include 4-hydroxyphenyldimethylhydrazine-p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, and 4-ethenyloxy group. Phenyldimethylhydrazine-p-toluenesulfonate, 4-acetoxyphenylmethylbenzylphosphonium hexafluoroantimonate, triphenylsulfonium-p-toluenesulfonic acid Salt, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate and the like, nitrobenzyl tosylate, benzene Affinity tosylate and the like.

As the polymerization initiator (D), a polymerization initiator which generates a living radical is preferable, and specifically, it is selected from the group consisting of an alkylphenyl ketone compound, a triazine compound, a mercaptophosphine oxide compound, an O-fluorenyl ruthenium compound, and a combination. The polymerization initiator of at least one of the imidazole compounds is more preferably a polymerization initiator containing an O-indenyl ruthenium compound.

When the polymerization initiator (D) is contained, the content of the polymerization initiator (D) is preferably 0.1 parts by mass or more and 40 parts by mass based on 100 parts by mass of the total of the resin (B) and the polymerizable compound (C). Hereinafter, it is more preferably 1 part by mass or more and 30 parts by mass or less.

Polymerization initiation aid (D1)

The polymerization initiation aid (D1) is a compound or a sensitizer for promoting polymerization of a polymerizable compound in which polymerization is initiated by a polymerization initiator. When the polymerization initiation aid (D1) is contained, it is usually used in combination with the polymerization initiator (D).

Examples of the polymerization initiation aid (D1) include an amine compound, an alkoxyfluorene compound, a thioxanthone compound, and a carboxylic acid compound.

Examples of the amine compound include alkanolamines such as triethanolamine, methyldiethanolamine, and triisopropanolamine; methyl 4-dimethylaminobenzoate and ethyl 4-dimethylaminobenzoate; Aminobenzoic acid esters such as isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate; N, N-dimethyl-p-toluidine; 4,4'- Bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino) An alkylamino benzophenone or the like such as benzophenone is preferably an alkylaminobenzophenone, preferably 4,4'-bis(diethylamino)benzophenone. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can be used.

Examples of the alkoxyfluorene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl- 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, and the like.

Examples of the above thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1- Chloro-4-propoxythioxanthone and the like.

Examples of the carboxylic acid compound include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, and dimethylphenylsulfide. Alkyl acetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, Phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthyloxyacetic acid, and the like.

In the case of using the polymerization initiation aid (D1), the content thereof is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass based on 100 parts by mass of the total of the resin (B) and the polymerizable compound (C). Share. When the amount of the polymerization initiation aid (D1) is within this range, the coloring pattern can be further formed with high sensitivity, and the productivity of the color filter tends to increase.

Leveling agent (F)

Examples of the leveling agent (F) include an organic lanthanoid surfactant, a fluorine-based surfactant, and an organic ruthenium-based surfactant having a fluorine atom. These may have a polymerizable group in the side chain.

Examples of the organic oxime-based surfactant include a surfactant having a decane bond in the molecule. Specifically, it can be enumerated DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (manufactured by Toray-Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400 , TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 ( ‧ ‧ ‧ Contract company made) and so on.

The fluorine-based surfactant mentioned above may be a surfactant having a fluorocarbon chain in the molecule. Specifically, it can be enumerated (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), (registered trademark) F142D, F171, F172, F173, F177, F183, F554, R30, RS-718-K (manufactured by DIC Corporation), (registered trademark) EF301, EF303, EF351, EF352 (Mitsubishi Electronic Manufacturing Co., Ltd.), (registered trademark) S381, S382, SC101, SC105 (made by Asahi Glass Co., Ltd.) and E5844 (( ) Research institute manufacturing).

Examples of the organic fluorene-based surfactant having a fluorine atom include a surfactant having a decane bond and a fluorocarbon chain in the molecule. Specifically, it can be enumerated (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation).

When the leveling agent (F) is contained, the content thereof is preferably 0.001% by mass or more and 0.5% by mass or less, more preferably 0.002% by mass or more and 0.4% by mass or less based on the total amount of the coloring composition, and further preferably 0.005 mass% or more and 0.3 mass% or less. When the content rate of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

Other ingredients

The coloring composition may contain additives known in the art such as a filler, another polymer compound, an adhesion promoter, an antioxidant, a light stabilizer, and a chain transfer agent, as needed.

Method for producing colored composition

Further, the coloring composition containing the resin (B), the polymerizable compound (C), the polymerization initiator (D), and the solvent (E) can be, for example, a compound (AI), a resin (B), or a polymerizable compound. (C), and a polymerization initiator (D), a solvent (E), a coloring agent (A) other than the compound (AI), a leveling agent (F), a polymerization initiation aid (D1), and the like, which are used as needed. The ingredients are prepared by mixing.

In the case where the pigment (P) is contained, the pigment is preferably mixed with a part or all of the solvent (E) in advance, and dispersed in a bead mill or the like until the average granulated hydrocarbon of the pigment is about 0.2 μm or less. In this case, a part or all of the above-mentioned pigment dispersant and resin (B) may be blended as needed. By mixing the remaining components in the pigment dispersion liquid thus obtained to have a predetermined concentration, It is possible to prepare a target coloring composition.

In the present invention, the above compound (A-I) can be mixed with a solvent to prepare a colored dispersion. After the colored dispersion liquid is prepared and further mixed with the resin (B), the polymerizable compound (C), the polymerization initiator (D), or the like to form a coloring composition, the heat resistance at the time of forming the color filter can be further improved.

As the solvent, any solvent can be used as long as it can be used as the solvent (E) of the coloring composition. In order to disperse the compound (AI), a particularly preferred solvent (E1) is, for example, an ether ester solvent, and more preferably, one hydroxyl group of an alkylene glycol or a polyalkylene glycol is etherified, and the remaining hydroxyl group is used. Esterified solvents such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl Ethyl acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, and the like. These can be used alone or in combination.

The amount of the solvent (E1) is, for example, 4 to 1000 parts by mass, preferably 6 to 200 parts by mass, more preferably 9 to 100 parts by mass, per part by mass of the compound (A-I).

When preparing a colored dispersion, it is preferred to use a dispersing agent. As the dispersing agent, for example, a known pigment dispersing agent such as a cationic type, an anionic type, a nonionic type, an amphoteric type, a polyester type, a polyamine type, or an acrylic type can be used. These pigment dispersants may be used singly or in combination of two or more. The pigment dispersant is represented by a trade name, and KP (manufactured by Shin-Etsu Chemical Co., Ltd.), (made by Kyoeisha Chemical Co., Ltd.), ( Manufactured by EFKA (manufactured by BASF Corporation), (Ajinomoto Manufactured by), Disperbyk, BYK ( Company manufacturing) and so on.

The amount of the dispersant is, for example, 1 to 1000 parts by mass, preferably 3 to 100 parts by mass, more preferably 5 to 90 parts by mass, and particularly preferably 10 to 80 parts by mass, per 100 parts by mass of the compound (A-I).

Further, when the dye (A1) is contained in the coloring composition, a part or all, preferably all, of the dye (A1) may be contained in advance as needed. The amount of the dye (A1) in the coloring dispersion is, for example, 0.1 to 20 parts by mass, preferably 0.5 to 15 parts by mass, and more preferably 1 to 10 parts by mass, per 100 parts by mass of the compound (A-I).

The coloring dispersion may contain a part or all, preferably a part, of the resin (B) used in the coloring composition as needed. By including the resin (B) in advance, the dispersibility in the case of producing a colored composition can be further improved. The amount of the solid content of the resin (B) in the coloring dispersion is, for example, 1 to 300 parts by mass, preferably 10 to 100 parts by mass, more preferably 20 to 70 parts by mass, per 100 parts by mass of the compound (AI). .

In the preparation of the dispersion, it is preferred to carry out fine dispersion using a dispersing device after suitably adding the necessary components. As the dispersing device, a bead mill device can be used. The beads to be used are generally hard beads such as zirconia beads, and the particle diameter thereof is, for example, selected from the range of 0.05 mm or more and 20 mm or less, preferably 0.1 to 10 mm, and more preferably 0.1 to 0.5 mm.

Further, it is preferred to dissolve the compound (A-I) in advance in the solvent (E). The solution was prepared in part or in whole. More preferably, the solution is filtered with a filter having a pore diameter of about 0.01 to 1 μm.

Preferably, the mixed coloring composition is filtered by a filter having a pore diameter of about 0.01 to 10 μm.

Color filter manufacturing method

Examples of the method for producing a colored pattern from the colored composition of the present invention include a photolithography method, an inkjet method, a printing method, and the like. Among them, photolithography is preferred. The photolithography method is a method in which the coloring composition is applied onto a substrate, dried to form a colored composition layer, and the colored composition layer is exposed and developed through a photomask. In the photolithography method, a coloring coating film which is a cured product of the coloring composition layer can be formed by using a photomask and/or no development at the time of exposure. The colored pattern and the colored coating film thus formed can be used as a color filter.

The film thickness of the produced color filter is not particularly limited, and can be appropriately adjusted depending on the purpose, use, and the like, and is, for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 6 μm.

As the substrate, quartz glass, borosilicate glass, aluminosilicate glass, a glass plate such as soda lime glass coated with cerium oxide on the surface, polycarbonate, polymethyl methacrylate, and polyparaphenyl may be used. A resin sheet such as ethylene glycol diester or ruthenium or the like, and a product of aluminum, silver, silver/copper/palladium alloy thin film or the like is formed on the substrate. Additional color filter layers, resin layers, transistors, circuits, and the like can be formed on these substrates.

The formation of each color pixel by photolithography can be carried out under known or conventional devices and conditions. For example, it can be produced as follows.

First, the colored composition is coated on a substrate and dried by heating (pre After baking and/or drying under reduced pressure, volatile components such as a solvent are removed and dried to obtain a smooth colored composition layer.

Examples of the coating method include a spin coating method, a slit coating method, a slit, and a spin coating method.

The temperature at the time of heat drying is preferably 30 to 120 ° C, more preferably 50 to 110 ° C. Further, the heating time is preferably from 10 seconds to 60 minutes, and more preferably from 30 seconds to 30 minutes.

In the case of drying under reduced pressure, it is preferably carried out under a pressure of 50 to 150 Pa at a temperature of 20 to 25 °C.

The film thickness of the coloring composition layer is not particularly limited, and can be appropriately selected depending on the film thickness of the target color filter.

Next, the colored composition layer is exposed through a photomask for forming a colored pattern of the target. The pattern on the photomask is not particularly limited, and a pattern matching the intended use can be used.

As the light source for exposure, a light source that generates light having a wavelength of 250 to 450 nm is preferable. For example, a light having a wavelength of less than 350 nm may be cut off by a filter that cuts the wavelength range, or a light in the vicinity of 436 nm, around 408 nm, and around 365 nm may be selectively taken out by a band pass filter that takes out these wavelength ranges. Specifically, examples of the light source include a mercury lamp, a light-emitting diode, a metal halide lamp, a halogen lamp, and the like.

Since the parallel light rays can be uniformly irradiated to the entire exposed surface, and the correct alignment of the photomask and the substrate on which the colored composition layer is formed is performed, it is preferable to use an exposure apparatus such as a mask aligner and a stepper.

By connecting the exposed coloring composition layer to the developer The coating is developed to form a colored pattern on the substrate. By development, the unexposed portion of the colored composition layer is dissolved in the developer to be removed. As the developer, an aqueous solution of a basic compound such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate or tetramethylammonium hydroxide is preferable. The concentration in the aqueous solution of these basic compounds is preferably 0.01 to 10% by mass, and more preferably 0.03 to 5% by mass. Further, the developer may contain a surfactant.

The developing method may be any one of a spin coating immersion method, a dipping method, and a spray method. Further, the substrate can be inclined at an arbitrary angle during development.

It is preferred to carry out water washing after development.

Further, it is preferred to post-bait the obtained colored pattern. The post-baking temperature is preferably from 150 to 250 ° C, more preferably from 160 to 235 ° C. The post-baking time is preferably from 1 to 120 minutes, more preferably from 10 to 60 minutes.

The compound of the present invention has a high absorbance and a coloring composition using the same, and can produce a color filter excellent in solvent resistance. This color filter can be used as a color filter for a display device (for example, a liquid crystal display device, an organic EL device, an electronic paper, or the like) and a solid-state image pickup element.

Example

The invention is illustrated in more detail below by means of examples, but the invention is not limited by these examples. In the examples, the content and the % and the amount of the use amount are shown as the mass basis unless otherwise specified.

Further, the reaction was carried out under a nitrogen atmosphere unless otherwise specified. Hereinafter, the structure of the compound was confirmed by mass analysis (LC; Model 1200, manufactured by Agilent, MASS; LC/MSD type manufactured by Agilent).

Example 1

After adding 10.0 parts of potassium thiocyanate and 55.0 parts of acetonitrile to a flask equipped with a cooling tube and a stirring device, the mixture was stirred at room temperature for 30 minutes. 13.6 parts of 2-fluorobenzhydryl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise thereto over 10 minutes, and the mixture was stirred at room temperature for 2 hours. 11.6 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise, and the mixture was stirred at room temperature for 30 minutes. 30.0 parts of sodium chloroacetate was dissolved in 40.8 parts of ion-exchanged water, and after dropping this solution, 22.9 parts of 30% sodium hydroxide aqueous solution was dripped. After the completion of the dropwise addition, the mixture was stirred at room temperature for 20 hours. After 204.0 parts of ion-exchanged water was added, the mixture was stirred at room temperature for 1 hour, and the precipitated solid was collected by filtration. The obtained solid was washed with 41.0 parts of acetonitrile, and then washed with 200.0 parts of ion-exchanged water to obtain a wet cake of the compound represented by the formula (B-I-1). In a flask equipped with a cooling tube and a stirring device, 68.0 parts of ion-exchanged water, 68.0 parts of toluene, and 15.8 parts of acetic acid were placed, and the mixture was stirred at room temperature for 30 minutes. The entire amount of the obtained wet cake of the compound represented by the formula (B-I-1) was added, and the mixture was stirred at room temperature for 2 hours. 35.4 parts of a 30% aqueous sodium hydroxide solution was added, and the organic layer was obtained by liquid separation purification. The obtained organic layer was subjected to liquid separation purification using 68.0 parts of ion-exchanged water, and then subjected to liquid separation purification using a 35% hydrochloric acid aqueous solution. Magnesium sulfate was added to the obtained organic layer, and after stirring for 1 hour, the solid was separated by filtration. The solvent was distilled to obtain 18.5 parts of a compound represented by the formula (B-I-2). The yield was 69%.

After 15.3 parts of N-methylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) and 60 parts of N,N-dimethylformamide were placed in a flask equipped with a cooling tube and a stirring device, the mixed solution was ice-cooled. 5.7 parts of 60% sodium hydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added in a little while over 30 minutes, and the mixture was stirred for 1 hour while warming to room temperature. 10.4 parts of 4,4'-difluorobenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) was added little by little to the reaction liquid, and the mixture was stirred at room temperature for 24 hours. The reaction solution was added to 200 parts of ice water little by little, and then allowed to stand at room temperature for 15 hours, and water was removed by decantation to obtain a viscous solid as a residue. After 60 parts of methanol was added to the viscous solid, it was stirred at room temperature for 15 hours. The precipitated solid was separated by filtration and purified by column chromatography. The purified pale yellow solid was dried under reduced pressure at 60 ° C to obtain 9.8 parts of the compound of formula (BP-1). The yield was 53%.

After 8.2 parts of the compound represented by the formula (BI-2), 10.0 parts of the compound represented by the formula (BP-1), and 20.0 parts of toluene were charged in a flask having a cooling tube and a stirring device, then, oxychlorination was added. Phosphorus 12.2 The mixture was stirred at 95 to 100 ° C for 3 hours. Next, after cooling the reaction mixture to room temperature, it was diluted with 170.0 parts of isopropyl alcohol. Next, the diluted reaction solution was poured into 300.0 parts of saturated brine, and 100 parts of toluene was added thereto, followed by stirring for 30 minutes. Then, the stirring was stopped, and the mixture was allowed to stand for 30 minutes, and as a result, it was separated into an organic layer and an aqueous layer. After the water layer was discarded by a liquid separation operation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of Glauber's salt was added to the organic layer, stirred for 30 minutes, and filtered to obtain a dried organic layer. The solvent of the obtained organic layer was distilled off with an evaporator to obtain a cyan violet solid. Further, the cyan violet solid was dried under reduced pressure at 60 ° C to obtain 18.4 parts of a compound represented by the formula (A-IV-1). The yield was 100%.

Identification of the compound represented by the formula (A-IV-1) (mass analysis) ionization mode = ESI +: m / z = 687.3 [M - Cl] ⁺ accurate mass: 722.3

Into a flask having a cooling tube and a stirring device, 12.4 parts of a compound represented by the formula (A-IV-1) and 45.5 parts of chloroform were placed and stirred. Next, 10 parts of chlorosulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was charged, and the mixture was stirred at 25 to 30 ° C for 18 hours. After cooling to room temperature, 210 parts of N,N-dimethylformamide was added, and the reaction solution was added dropwise to 2610 parts of toluene. in. After stirring for 1 hour, the solid obtained by filtration was washed with 870 parts of toluene, and then dried under reduced pressure at 60 ° C to obtain 12.9 parts of a compound represented by formula (A-III-1). The yield was 89%.

Identification of the compound represented by the formula (A-III-1) (mass analysis) ionization mode = ESI +: m / z = 845.3 [M] ⁺ accurate mass: 846.2

In a flask having a cooling tube and a stirring device, 69.8 parts of a compound represented by the formula (A-III-1) and 418 parts of chloroform were added and stirred. 369.7 parts of phosphorus oxychloride was added dropwise, and the mixture was stirred at 60 ° C for 4 hours. After allowing to cool to room temperature, the reaction solution was poured into 5000 parts of cold water, and stirred for 30 minutes. Stirring was stopped and allowed to stand for 30 minutes, and the result was separated into an organic layer and an aqueous layer. The obtained organic layer was subjected to two-time liquid separation washing using 4000 parts of cold water. After dissolving 14.7 parts of trifluoromethanesulfonamide and 10 parts of triethylamine in 100 parts of chloroform, it was added to the organic layer, and the reaction was carried out for 12 hours at room temperature. After the reaction solution was poured into 5000 parts of ion-exchanged water, it was stirred for 30 minutes. Stirring was stopped and allowed to stand for 30 minutes, and the result was separated into an organic layer and an aqueous layer. The obtained organic layer was subjected to two-time liquid separation washing using 4000 parts of ion-exchanged water. 200 parts of magnesium sulfate was added to the organic layer, and after stirring for 1 hour, the obtained organic layer was obtained by an evaporator. The solvent was distilled off to give a cyan violet solid. Further, the cyan violet solid was dried at 60 ° C under reduced pressure to obtain 44.2 parts of a compound represented by the formula (A-III-1), the formula (A-II-1), and the formula (A-II-2). 32:41:16 mixture (molar basis). This mixture is referred to as a colorant (A-II-3).

Identification of the compound represented by the formula (A-II-1) (mass analysis) ionization mode = ESI +: m / z = 978.5 [M] ⁺ accurate mass: 977.2

Identification of the compound represented by the formula (A-II-2) (mass analysis) ionization mode = ESI +: m / z = 1109.5 [M] ⁺ accurate mass: 1108.1

Example 2

Put in (A-IV-1) in a flask with a cooling tube and a stirring device 2.0 parts of the compound and 5.7 parts of dichloromethane were added, and 1.6 parts of chlorosulfonic acid was added dropwise at 25 to 30 ° C, and the mixture was stirred at the same temperature for 3 hours. Next, a mixture of 3.3 parts of DMF and 0.3 parts of ion-exchanged water was added dropwise so as not to exceed 25 ° C to prepare a solution. This solution was poured into 32.7 parts of toluene, and the liquid was partially separated, and the residue was again washed with 16.3 parts of toluene. The remaining residue was concentrated under reduced pressure by an evaporator, and the concentrate was poured into 31.2 parts of ion-exchanged water to precipitate crystals and filtered. The crude filtrate was suspended in 13.0 parts of a 20% aqueous sodium chloride solution, filtered, and the filtered solid was washed with 13.0 parts of a 20% aqueous sodium chloride solution, and dried at 35 ° C under reduced pressure. Next, this dried product was dissolved in 6.2 parts of methanol, and the insoluble matter was filtered, and then concentrated under reduced pressure with an evaporator, and dried under reduced pressure at 35 ° C to obtain a formula (A-III-1) as a cyan solid. The compound represented is 1.9 parts. The yield was 97.9%.

Identification of the compound represented by the formula (A-III-1) (mass analysis) ionization mode = ESI +: m / z = 845.3 [M] ⁺ accurate mass: 846.2

The following reaction was carried out under a nitrogen atmosphere. Into a flask having a cooling tube and a stirring device, 2.0 parts of the compound represented by the formula (A-III-1) and 10.0 parts of acetonitrile obtained above were charged, and phosphorus oxychloride was added dropwise at 70 to 80 ° C. 1.0 servings. Stir at the same temperature for 2 hours. Subsequently, it was cooled to 5 ° C, and 1.0 part of trifluoromethanesulfonamide was added to the reaction liquid. Next, 2.3 parts of triethylamine was added dropwise at 5 to 15 ° C, and the mixture was stirred at 15 to 30 ° C for 2 hours. To the reaction liquid, 10.0 parts of methyl ethyl ketone and 10.0 parts of a 20% aqueous sodium chloride solution were injected, and the mixture was concentrated under reduced pressure using an evaporator. 15.0 parts of dichloromethane and 10.0 parts of ion-exchanged water were poured into the concentrated residue, and the organic layer and the aqueous layer were separated, and the organic layer was concentrated under reduced pressure with an evaporator, and dried under reduced pressure at 35 ° C to obtain a cyan solid. 3.1 parts of the compound represented by the formula (A-II-2) was obtained. The yield was 107.7%.

Identification of the compound represented by the formula (A-II-2) (mass analysis) ionization mode = ESI +: m / z = 1109.5 [M] ⁺ accurate mass: 1108.1

Example 3

2.0 parts of the compound represented by the formula (A-II-2), 3.4 parts of magnesium chloride hexahydrate, 40.0 parts of dimethyl hydrazine, and 16.0 parts of ion-exchanged water were placed in a flask having a cooling tube and a stirring device at 80 ° C. Stir for 2 hours. After cooling the reaction mixture to room temperature, a solution of 161.3 parts of ion-exchanged water and 53.8 parts of magnesium chloride hexahydrate was added dropwise thereto, and the mixture was stirred at 40 ° C for 30 minutes. The obtained suspension was filtered, and the filtered solid was washed twice with 20.0 parts of ion-exchanged water and 50.0 parts. The obtained solid was dried under reduced pressure at 60 ° C to obtain 1.9 parts of a compound represented by formula (A-II-4).

Example 4

The compound represented by the formula (A-II-5) was synthesized by the same reaction as in Example 3 except that the magnesium chloride hexahydrate was changed to zinc chloride.

Example 5

The compound represented by the formula (A-II-6) was synthesized by the same reaction as in Example 3 except that the magnesium chloride hexahydrate was changed to ruthenium chloride dihydrate.

[Chemical Formula 47]

Example 6

In the same manner as in Example 1, except that the compound represented by the formula (BP-1) was changed to the compound represented by the formula (BP-2), the formula (A-III-2) and the formula (A-II-7) were obtained. And a 30:52:9 mixture of the compound represented by the formula (A-II-8) (molar basis). This mixture is referred to as a colorant (A-II-9). In the formula, -SO ₃ ^- and -SO ₂ -N ^- -SO ₂ -CF ₃ mean that any one of the hydrogen atoms contained in the partial structure in the parentheses is substituted.

Identification of the compound represented by the formula (A-III-2) (mass analysis) ionization mode = ESI +: m / z = 931.5 [M] ⁺ accurate mass: 930.3

Identification of the compound represented by the formula (A-II-7) (mass analysis) ionization mode = ESI +: m / z = 1063.5 [M] ⁺ accurate mass: 1061.3

Identification of the compound represented by the formula (A-II-8) (mass analysis) ionization mode = ESI +: m / z = 1193.5 [M] ⁺ accurate mass: 1192.2

Example 7

The formula (A-II-8) was obtained in the same manner as in Example 2 except that the compound represented by the formula (BP-1) was changed to the compound represented by the formula (BP-2). The compound represented.

Identification of the compound represented by the formula (A-II-8) (mass analysis) ionization mode = ESI +: m / z = 1193.5 [M] ⁺ accurate mass: 1192.2

Example 8

The same reaction as in Example 3 was carried out except that the compound represented by the formula (A-II-2) was changed to the compound represented by the formula (A-II-8), and the synthesis was represented by the formula (A-II-10). compound of.

Example 9

The same reaction as in Example 4 was carried out except that the compound represented by the formula (A-II-2) was changed to the compound represented by the formula (A-II-8), and the synthesis was represented by the formula (A-II-11). compound of.

Example 10

The same reaction as in Example 5 was carried out except that the compound represented by the formula (A-II-2) was changed to the compound represented by the formula (A-II-8), and the synthesis was represented by the formula (A-II-12). compound of.

Comparative example 1, 2

The compound represented by the formula (AX-1) (hereinafter also referred to as the compound (AX-1)) and the compound represented by the formula (AX-2) were synthesized by the method described in JP-A-2015-38201 (hereinafter, Also known as compound (AX-2)).

[Synthesis Example 1]

An appropriate amount of nitrogen was introduced into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to form a nitrogen atmosphere, and 100 parts of propylene glycol monomethyl ether acetate was placed, and the mixture was heated to 85 ° C while stirring. Next, 19 parts of methacrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-8-yl acrylate and the like were dropped into the flask using a drip pump for about 5 hours. Mixture of 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-9-yl acrylate (50:50 in molar ratio) (trade name "E-DCPA", Co., Ltd.璐 171 171 parts of a solution dissolved in 40 parts of propylene glycol monomethyl ether acetate. On the other hand, an additional drip pump was used to drip the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) 26 parts into the propylene glycol monomethyl group for about 5 hours. A solution of 120 parts of ether ether acetate. After completion of the dropwise addition of the polymerization initiator, the mixture was kept at the same temperature for about 3 hours, and then cooled to room temperature to obtain a solution of a copolymer (resin (B-1)) having a solid content of 43.5%. The obtained resin (B-1) had a weight average molecular weight of 8,000, a degree of dispersion of 1.98, and an acid value of 53 mg-KOH/g in terms of solid content.

[Synthesis Example 2]

An appropriate amount of nitrogen was introduced into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to form a nitrogen atmosphere, and 280 parts of propylene glycol monomethyl ether acetate was charged, and the mixture was heated to 80 ° C while stirring. Next, 38 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-8 and 9-yl acrylate were dropped into the flask over a period of about 5 hours using a drip pump. 289 parts of a mixture (containing 50:50 in molar ratio) (trade name "E-DCPA", manufactured by Daicel Corporation) was dissolved in 125 parts of propylene glycol monomethyl ether acetate. On the other hand, an additional drip pump was used to dissolve the polymerization initiator 2,2-azobis(2,4-dimethylvaleronitrile) 33 parts into the propylene glycol monomethyl group in about 6 hours. A solution of 235 parts of ether acetate. After completion of the dropwise addition of the polymerization initiator, the mixture was kept at the same temperature for about 4 hours, and then cooled to room temperature to obtain a copolymer (resin (B-2)) having a solid content of 35.1%. The obtained resin (B-2) had a weight average molecular weight of 9,200, a degree of dispersion of 2.08, and an acid value of 77 mg-KOH/g in terms of solid content.

The measurement of the polystyrene-equivalent weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin was carried out under the following conditions by the GPC method.

Device: HLC-8120GPC (manufactured by Tosoh Corporation)

Column: TSK-GELG2000HXL

Column temperature: 40 ° C

Solvent: THF

Flow rate: 1.0mL/min

Solid content concentration of the test liquid: 0.001 to 0.01% by mass

Injection volume: 50μL

Detector: RI

Standard material for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

The polystyrene-converted weight average molecular weight and number average obtained above The ratio of the sub-quantities (Mw/Mn) is taken as the degree of dispersion.

[Preparation of Colored Curable Resin Composition]

Examples 11 to 20 and Comparative Examples 3 to 4

Each component was mixed according to the following composition, and the colored curable resin composition was obtained.

In Table 14, each component represents the following compound.

(A-II-2): a compound represented by the formula (A-II-2)

(A-II-3): Colorant (A-II-3)

(A-II-4): a compound represented by the formula (A-II-4)

(A-II-5): a compound represented by the formula (A-II-5)

(A-II-6): a compound represented by the formula (A-II-6)

(A-II-8): a compound represented by the formula (A-II-8)

(A-II-9): Colorant (A-II-9)

(A-II-10): a compound represented by the formula (A-II-10)

(A-II-11): a compound represented by the formula (A-II-11)

(A-II-12): a compound represented by the formula (A-II-12)

(A-X-1): a compound represented by the formula (A-X-1)

(A-X-2): a compound represented by the formula (A-X-2)

(B-1): Resin (B-1) (solid content conversion)

(C-1): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)

(D-1): N-benzylideneoxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; BASF Corporation Manufacture; O-mercaptopurine compound)

(E-1): propylene glycol monomethyl ether acetate

(E-2): N-methylpyrrolidone

(E-3): ethyl lactate

(F-1): Polyether modified eucalyptus oil (solid content conversion) ( SH8400; manufactured by Toray Dow Corning Co., Ltd.)

[Production of color filter]

The colored curable resin composition was applied onto a 2 inch square glass substrate (#1737; manufactured by Corning Incorporated) by spin coating, and then prebaked at 100 ° C for 3 minutes to form a colored composition layer. After cooling, use an exposure machine (TME-150RSK; (manufactured by the company), exposed to an exposure amount (365 nm basis) of 150 mJ/cm ² in an air atmosphere. It should be noted that no photomask is used. A color filter (film thickness: 2.0 μm) was produced by baking the exposed coloring composition layer in an oven at 180 ° C for 20 minutes.

[Measurement of absorbance]

The obtained compound or colorant 0.35g was dissolved in chloroform, so that the volume becomes 250cm ^3, in which the 2cm ³ was diluted with chloroform, and the volume becomes 100cm ³ (concentration: 0.028g / L), using a spectrophotometer (quartz cell The optical path was long; 1 cm) the absorption spectrum was measured. The absorbance at the maximum absorption wavelength converted to 0.028 g/L was evaluated according to the following criteria.

A: 2.0 or more

B: 1.5 or more and less than 2.0

C: less than 1.5

[Solvent resistance evaluation]

The coating film of the coloring photosensitive resin composition was immersed in N-methylpyrrolidone for 40 minutes at room temperature, and the color difference before and after the immersion of the coating film was measured using a color measuring machine (OSP-SP-200; manufactured by OLYMPUS). Eab*), evaluated according to the following criteria. It should be noted that △Eab* The value is a value obtained by the following color difference formula according to the CIE1976 (L*, a*, b*) spatial color system (Japanese Color Society, New Color Science Handbook (Showa 60), p. 266).

△Eab*={(△L*)2+(△a*)2+(△b*)2}1/2

A: Less than 5.0

B: 5.0 or more and less than 10.0

C: 10.0 or more

[Measurement of voltage holding ratio]

The obtained compound was 0.025 g and liquid crystal (MCL-6608, 1 g of the mixture was mixed and heated in a sample bottle at 120 ° C for 50 minutes. Transfer the mixture to a centrifuge tube using the MICRO SIX ( The company manufactured by the company was centrifuged twice for 30 minutes. The supernatant portion of the mixture was sealed in a liquid crystal evaluation unit (KSRT-05/BIIIMINTS05X, manufactured by EHC Co., Ltd.), and a liquid crystal physical property evaluation device (Model 6252 Dongyang) was used. The product was measured under the following measurement conditions and evaluated according to the following criteria.

Measuring condition

‧Apply voltage pulse amplitude: 5V

* Voltage holding ratio: liquid crystal cell potential difference after 1000 ms / value of voltage applied at 0 msec

evaluation standard

A: 95% or more

B: 85% or more and less than 95%

C: less than 85%

Examples 21 to 24 and Comparative Examples 5 and 6

[Dispersion production method]

Each component shown in Table 17 was weighed, and 600 parts of 0.4 μm zirconia beads were placed, and the mixture was shaken for 1 hour using a paint conditioner (manufactured by LAU Co., Ltd.) to prepare dispersions 1 to 6.

In Table 17, each component represents the following compound.

(A-II-5): a compound represented by the formula (A-II-5)

(A-II-10): a compound represented by the formula (A-II-10)

(A-II-11): a compound represented by the formula (A-II-11)

(A-II-12): a compound represented by the formula (A-II-12)

(A-X-1): a compound represented by the formula (A-X-1)

(A-X-2): a compound represented by the formula (A-X-2)

Dispersant 1: DISPERBYK-162 (38% solids propylene glycol monomethyl ether acetate solution)

Dispersion resin 1: propylene glycol monomethyl ether acetate solution of resin (B-2) (solid content 35.1%)

(E-1): propylene glycol monomethyl ether acetate

[Method for Producing Colored Curable Resin Composition]

Each component shown in Table 18 was mixed to obtain a colored curable resin composition.

In Table 18, each component represents the following compound.

(B-1): Resin (B-1) (solid content conversion)

(C-1): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)

(D-1): N-benzylideneoxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; BASF Corporation Manufacture; O-mercaptopurine compound)

(E-1): propylene glycol monomethyl ether acetate

(F-1): Polyether modified eucalyptus oil (solid content conversion) ( SH8400; manufactured by Toray Dow Corning Co., Ltd.)

[Measurement of voltage holding ratio]

The colored curable resin composition was applied onto a 3 inch square glass substrate (#1737; manufactured by Corning Incorporated) by spin coating, and then prebaked at 100 ° C for 3 minutes to form a colored composition layer. After cooling, use an exposure machine (TME-150RSK; (manufactured by the company) was exposed to an exposure amount (365 nm basis) of 150 mJ/cm ² in an air atmosphere. It should be noted that no photomask is used. The exposed coloring composition layer was baked in an oven at 230 ° C for 20 minutes, and a coating film (film thickness: 2.0 μm) was produced. The coating film was scraped off from the glass substrate to obtain a powder. The obtained powder was 0.025 g and liquid crystal (MCL-6608, 1 g of the mixture was mixed and heated in a sample bottle at 120 ° C for 50 minutes. Transfer the mixture to a centrifuge tube using the MICRO SIX ( The company manufactured by the company was centrifuged twice for 30 minutes. The supernatant portion of the mixture was sealed in a liquid crystal evaluation unit (KSRT-05/BIIIMINTS05X, manufactured by EHC Co., Ltd.), and a liquid crystal physical property evaluation device (Model 6252 Dongyang) was used. The product was measured under the following measurement conditions and evaluated according to the following criteria.

Measuring condition

‧Apply voltage pulse amplitude: 5V

* Voltage holding ratio: liquid crystal cell potential difference after 1000 ms / value of voltage applied at 0 msec

evaluation standard

A: 95% or more

B: 85% or more and less than 95%

C: less than 85%

Industrial availability

The compound of the present invention is excellent in absorbance and voltage holding ratio, and a coloring composition using the compound can be used to produce a color filter excellent in solvent resistance.

Claims (6)

A compound represented by the formula (AI): In the formula (AI), R ⁴¹ to R ⁴⁴ each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a carbon number which may have a substituent of 7 The aralkyl group of ~30, the aromatic hydrocarbon group and the substituent which the aralkyl group may have may be -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f , and the saturated hydrocarbon group having 1 to 20 carbon atoms The hydrogen atom contained in the saturated hydrocarbon group may be substituted by a substituted or unsubstituted amine group or a halogen atom. When the carbon number of the saturated hydrocarbon group is 2 to 20, the methylene group contained in the saturated hydrocarbon group may be Replaced with an oxygen atom or -CO-, however, in the saturated hydrocarbon group of 2 to 20 carbon atoms, the adjacent methylene group will not be replaced with an oxygen atom at the same time, and the terminal methylene group will not be replaced with an oxygen atom or -CO-, R ⁴¹ and R ⁴² may bond and form a ring together with the nitrogen atom to which they are bonded, R ⁴³ and R ⁴⁴ may bond and form a ring together with the nitrogen atom to which they are bonded, and R ⁴⁷ to R ⁵⁴ each independently represent hydrogen. An atom, a halogen atom, a nitro group, a hydroxyl group, -SO ₃ ^- , -SO ₂ -N ^- -SO ₂ -R ^f , or an alkyl group having 1 to 8 carbon atoms, the methylene group constituting the alkyl group may be replaced with oxygen Promoter or -CO-, R ⁴⁸ R ⁵² may be bonded to each other to form with the -NH -, - S-, or -SO ₂ -, however, the alkyl, while not adjacent methylene group is replaced by an oxygen atom The methylene group at the terminal end is not replaced with an oxygen atom or -CO-, and the ring T ¹ represents an aromatic heterocyclic ring having 3 to 10 carbon atoms. The aromatic heterocyclic ring may have a saturated hydrocarbon group having 1 to 20 carbon atoms and is substituted. Or an unsubstituted amine group or a carbon number 6 to 20 aromatic hydrocarbon group which may have a substituent, and the aromatic hydrocarbon group may have a substituent of -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f , Mr ⁺ represents a hydrogen ion, a r-valent metal ion or a substituted or unsubstituted ammonium ion, and k represents the number of -SO ₃ ^- and -SO ₂ -N ^- -SO ₂ of the compound represented by the formula (AI). - the sum of the number of -R ^f , r represents an integer of 1 or more, and R ^f represents a fluoroalkyl group having 1 to 12 carbon atoms; however, the compound represented by the formula (AI) has at least one -SO ₂ -N ^- - SO ₂ -R ^f . The compound of claim 1, wherein M ^r+ is a metal ion of r valence. The compound of claim 1, wherein the aromatic heterocyclic ring represented by the above T ¹ is a ring represented by the following formula (A-t1): In the formula (A-t1), the ring T ² represents an aromatic heterocyclic ring having 3 to 10 carbon atoms, and each of R ⁴⁵ and R ⁴⁶ independently represents a hydrogen atom and a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. a substituted hydrocarbon group having 6 to 20 carbon atoms or a aralkyl group having 7 to 30 carbon atoms which may have a substituent, and when the carbon number of the saturated hydrocarbon group is 2 to 20, the saturated hydrocarbon group is contained The methylene group may be replaced by an oxygen atom or -CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, the adjacent methylene group will not be replaced with an oxygen atom at the same time, and the terminal methylene group will not be replaced. Is an oxygen atom or -CO-, R ⁴⁵ and R ⁴⁶ may bond together with a nitrogen atom to which they are bonded to form a ring, R ⁵⁵ represents a saturated hydrocarbon group having 1 to 20 carbon atoms, or a carbon number of 6 to 20 which may have a substituent An aromatic hydrocarbon group, k1 represents 0 or 1, and * represents a bonding end with a carbocation. A coloring composition comprising the compound of any one of claims 1 to 3. A color filter formed from the colored composition of claim 4. A display device comprising a color filter as in claim 5.