WO2013108591A1 - Triarylmethane-based coloring matter for color filter and color filter using said coloring matter - Google Patents

Abstract

[Problem] To provide a triarylmethane-based coloring matter having excellent heat resistance and good solubility in propylene glycol monomethyl ether acetate (PGMEA) or another ester-based organic solvent, and a color filter that uses the coloring matter. [Solution] A color filter configured using a triarylmethane-based coloring matter for a color filter as represented by general formula (1).

Description

Triarylmethane dye for color filter and color filter using the dye

The present invention relates to a color filter dye and a color filter using the dye, and more particularly to a triarylmethane dye having high heat resistance and excellent solubility in an organic solvent, and a color filter using the dye.

Color filters may be used in liquid crystal and electroluminescent (EL) display devices. The color filter has a structure in which a colored layer is laminated on a substrate, and the colored layer is required to have heat resistance and light resistance. A triarylmethane dye is known as a material used for the colored layer. For example, in Patent Documents 1 and 2, aromatic sulfonic acid is used as a counter anion to improve the heat resistance and light resistance of the dye. .

In particular, in Patent Document 1, durability is improved by introducing a photopolymerizable functional group into the aromatic ring of the aromatic sulfonic acid and forming a chemical bond between the photopolymerizable resin and the crosslinkable monomer contained therein. However, triarylmethane dyes with aromatic sulfonic acid as a counter anion have poor solubility in ester solvents such as propylene glycol monomethyl ether acetate (PGMEA), acrylic acid resins and crosslinkable monomers, and have a uniform ink composition It is difficult to obtain a product, and even if it can be made into a solution, the pigment is deposited in the coating film, and there is a problem that the high permeability characteristic of the pigment is impaired. It has not yet been put into practical use because it does not sufficiently satisfy the specifications as an agent. Further, Patent Document 2 describes a composition containing a colorant having a triarylmethane dye having a specific structure and an aromatic sulfonate ion as a counter anion. However, the adhesion to a substrate and light resistance are described. It was not enough.

On the other hand, as means for improving the durability of cationic dyes such as triarylmethane, use of imido acid ions as a counter anion is disclosed in Patent Document 3, and it is described that a uniform coating film is provided. .

JP 2003-246935 A JP 2008-304766 A Japanese Published Patent Publication No. 2007-503477

However, conventional triarylmethane-based dyes can ensure heat resistance to some extent, but have insufficient solubility in various solvents.
The present invention has been made in order to solve the above-mentioned problems, and is a triarylmethane dye for color filters having excellent heat resistance and good solubility in an ester organic solvent such as PGMEA, and the use of the dye. The purpose is to provide a color filter.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have improved the solubility in organic solvents while maintaining heat resistance by using a sulfonylimide acid ion as a counter anion in the triarylmethane dye. The present invention has been completed. That is, the gist of the present invention is as follows.

1. A triarylmethane dye for a color filter represented by the following general formula (1).

(Wherein R ₁ to R ₄ may be the same or different and each has a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, or a substituent. An optionally substituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, R ₁ and R ₂ , R ₃ and R ₄ may be bonded to each other via a single bond to form a ring, R ₅ to R ₇ may be the same or different, and may be a halogen atom, A linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 20 carbon atoms which may have a substituent, and a substituent. Straight chain having 2 to 6 carbon atoms which may be Or a branched alkenyl group, a linear or branched alkoxy group having 1 to 20 carbon atoms which may have a substituent, and a carbon atom having 3 to 20 carbon atoms which may have a substituent. Represents a cycloalkoxy group, and these substituents may be bonded to each other via a single bond to form a ring, r ₅ and r ₆ represent an integer of 0 to 4, and r ₇ represents an integer of 0 to 5 Represents an integer, A and B may be the same or different and may have a substituent, a linear or branched alkyl group having 1 to 20 carbon atoms or a substituent. A cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group.

2. The triarylmethane dye represented by the general formula (1) is represented by the following general formula (2): The triarylmethane dye described in 1.

(Wherein R ₁ to R ₄ may be the same or different and each has a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, or a substituent. An optionally substituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, R ₁ and R ₂ , R ₃ and R ₄ may be bonded to each other via a single bond to form a ring, and R ₆ to R ₈ may be the same or different, and may be a halogen atom, A linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 20 carbon atoms which may have a substituent, and a substituent. Straight chain having 2 to 6 carbon atoms which may be Or a branched alkenyl group, a linear or branched alkoxy group having 1 to 20 carbon atoms which may have a substituent, and a carbon atom having 3 to 20 carbon atoms which may have a substituent. Represents a cycloalkoxy group, and these substituents may be bonded to each other via a single bond to form a ring, r ₆ represents an integer of 0 to 4, and r ₇ represents an integer of 0 to 5. , R ₈ represents an integer of 0 to 2. A and B may be the same or different and each may have a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent. An optionally substituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aroma Represents a group.)

3. The triarylmethane dye represented by the general formula (1) is represented by the following general formula (3): The triarylmethane dye described in 1.

(Wherein R ₁ to R ₄ may be the same or different and each has a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, or a substituent. An optionally substituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, R ₁ and R ₂ , R ₃ and R ₄ may be bonded to each other via a single bond to form a ring, and R ₅ , R ₇ and R ₉ may be the same or different, A halogen atom, an optionally substituted linear or branched alkyl group having 1 to 20 carbon atoms, an optionally substituted cycloalkyl group having 3 to 20 carbon atoms, a substituent Straight chain of 2 to 6 carbon atoms which may have a group A linear or branched alkoxy group having 1 to 20 carbon atoms which may have a chain or branched alkenyl group or a substituent, or a carbon atom having 3 to 20 carbon atoms which may have a substituent And these substituents may be bonded to each other through a single bond to form a ring, r ₅ represents an integer of 0 to 4, and r ₇ represents an integer of 0 to 5. R ₉ represents an integer of 0 to 2. A and B may be the same or different, and may have a substituent, a linear or branched alkyl group having 1 to 20 carbon atoms, Optionally substituted cycloalkyl group having 3 to 20 carbon atoms, substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group, substituted or unsubstituted condensed polycycle Represents an aromatic group.)

4. The triarylmethane dye represented by the general formula (1) is represented by the following general formula (4): The triarylmethane dye described in 1.

(Wherein R ₁ to R ₄ may be the same or different and each has a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, or a substituent. An optionally substituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, R ₁ and R ₂ , R ₃ and R ₄ may be bonded to each other via a single bond to form a ring, and R ₅ , R ₆ and R ₁₀ may be the same or different, A halogen atom, an optionally substituted linear or branched alkyl group having 1 to 20 carbon atoms, an optionally substituted cycloalkyl group having 3 to 20 carbon atoms, a substituent Optionally having 2 to 6 carbon atoms A linear or branched alkenyl group, an optionally substituted linear or branched alkoxy group having 1 to 20 carbon atoms, an optionally substituted carbon atom having 3 to And these substituents may be bonded to each other via a single bond to form a ring, r ₅ and r ₆ represent an integer of 0 to 4, and r ₁₀ represents 0 to Represents an integer of 3. A and B may be the same or different, and may have a linear or branched alkyl group having 1 to 20 carbon atoms, which may have a substituent, or a substituent. A cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group.

5. In the triarylmethane dye represented by the general formula (1), r ₅ is 0, The triarylmethane dye described in 1.

6). In the triarylmethane dye represented by the general formula (1), r ₆ is 0, The triarylmethane dye described in 1.

7). In the triarylmethane dye represented by the general formula (1), r ₇ is 0. The triarylmethane dye described in 1.

8). In the triarylmethane dye represented by the general formula (1), r ₅ and r ₆ are 0, The triarylmethane dye described in 1.

9. In the triarylmethane dye represented by the general formula (1), r ₅ and r ₇ are 0, The triarylmethane dye described in 1.

10. In the triarylmethane dye represented by the general formula (1), r ₆ and r ₇ are 0, The triarylmethane dye described in 1.

11. In the triarylmethane dye represented by the general formula (1), r ₅ to r ₇ are 0, The triarylmethane dye described in 1.

12. In the general formula (1), A and B are a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, or a substituted or unsubstituted aromatic hydrocarbon. 1. characterized by being a group The triarylmethane dye described in 1.

13. In the general formula (1), A and B are each a linear or branched alkyl group having 1 to 20 carbon atoms having a fluorine atom as a substituent, or a fluorine atom or a fluorine atom as a substituent. It is an aromatic hydrocarbon group having a straight-chain or branched alkyl group having 1 to 10 carbon atoms. The triarylmethane dye described in 1.

14. In the general formula (1), A and B are trifluoromethyl groups. The triarylmethane dye described in 1.

15. The dye represented by the general formula (1) is a triarylmethane dye having a solubility in propylene glycol monomethyl ether acetate at 25 ° C. and normal pressure of 1% by weight or more. The triarylmethane dye described in 1.

16. 3. In the triarylmethane dye represented by the general formula (4), r ₅ is 0. The triarylmethane dye described in 1.

17. 3. In the triarylmethane dye represented by the general formula (4), r ₆ is 0. The triarylmethane dye described in 1.

18. 3. In the triarylmethane dye represented by the general formula (4), r ₁₀ is 0. The triarylmethane dye described in 1.

19. 3. In the triarylmethane dye represented by the general formula (4), r ₅ and r ₆ are 0. The triarylmethane dye described in 1.

20. 3. In the triarylmethane dye represented by the general formula (4), r ₅ and r ₁₀ are 0. The triarylmethane dye described in 1.

21. 3. The triarylmethane dye represented by the general formula (4) is characterized in that r ₆ and r ₁₀ are 0. The triarylmethane dye described in 1.

22. 3. In the triarylmethane dye represented by the general formula (4), r ₅ , r ₆ , and r ₁₀ are 0. The triarylmethane dye described in 1.

23. 1 above. Thru 22. A color filter using the triarylmethane dye according to any one of the above.

The triarylmethane dye of the present invention has high heat resistance and is excellent in solubility in an organic solvent such as PGMEA, and thus is useful as a dye used for a color filter.

Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited thereto.

“An optionally substituted linear or branched alkyl group having 1 to 20 carbon atoms” represented by R ₁ to R ₄ in the general formulas (1) to (4) or “ “C1-C20 linear or branched alkyl group” or “C3-C20 cycloalkyl” in “C3-C20 cycloalkyl group optionally having substituent (s)” As the group, specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tridecyl group, pentadecyl group, hexadecyl group , Octadecyl group, nonadecyl group and other linear alkyl groups; isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isooctyl group and other branched alkyl groups ; It can be exemplified cyclopropyl group, a cyclopentyl group, a cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, a cycloalkyl group such as cyclodecyl. Further, these substituents may be bonded to each other via a single bond to form a ring.

“An optionally substituted linear or branched alkyl group having 1 to 20 carbon atoms” represented by R ₁ to R ₄ in the general formulas (1) to (4) or “ The “substituent” in the “cycloalkyl group having 3 to 20 carbon atoms which may have a substituent” includes a halogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a carbon atom A cycloalkyl group having 3 to 20 carbon atoms, a linear or branched alkoxy group having 1 to 20 carbon atoms, a cycloalkoxy group having 3 to 20 carbon atoms, or a carbon atom having 1 to 20 carbon atoms substituted with a halogen atom Examples thereof include a linear or branched alkyl group and a linear or branched alkoxy group having 1 to 20 carbon atoms substituted with a halogen atom. Specifically, halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; direct methyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, etc. Chain alkyl group; branched alkyl group such as isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isooctyl group; cycloalkyl group such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group; Group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group and the like linear alkoxy group; isopropoxy group, isobutoxy group, sec-butoxy Group, tert-butoxy group, isooctyloxy Branched alkoxy groups such as a group; cycloalkoxy groups such as a cyclopropoxy group, a cyclopentyloxy group, a cyclohexyloxy group, and a cyclopropylmethyloxy group; a trifluoromethyl group, a pentafluoroethyl group, a nonafluorobutyl group, and a trifluoromethoxy group Etc.

The “substituted or unsubstituted aromatic hydrocarbon group”, “substituted or unsubstituted aromatic heterocyclic group” or “substituted or substituted” represented by R ₁ to R ₄ in the general formulas (1) to (4) As the “aromatic hydrocarbon group”, “aromatic heterocyclic group” or “fused polycyclic aromatic group” in the “unsubstituted fused polycyclic aromatic group”, specifically, phenyl group, naphthyl group, biphenyl group Aromatic hydrocarbon groups having 6 to 20 carbon atoms such as azulenyl group, anthracenyl group, terphenyl group, pyrenyl group; 5 such as furan ring, thiophene ring, pyrrole ring, imidazole ring, thiazole ring, oxadiazole ring 6-membered monocyclic ring such as pyridine ring and pyrazine ring, polycyclic ring such as terthiophene ring, phenanthrene ring, quinoline ring, isoquinoline ring, quinoxaline ring, benzofuran ring, Bazoru ring, having 2 to aromatic heterocyclic group or a carbon atom of 20 C 2 -C having a skeleton structure of a condensed ring, such as such as dibenzothiophene ring can be given 20 condensed polycyclic aromatic group.

R ₁ and R ₂ , R ₃ and R ₄ in the general formulas (1) to (4) may be bonded to each other to form a ring. Specific examples of the ring formed include piperidine, Examples include morpholine, pyrrolidine, piperazine, hexamethyleneimine and the like. Specific examples of the group represented by R ₁ R ₂ N— or R ₃ R ₄ N— thus formed include pyrrolidino group, piperazino group, morpholino group, N-ethylpiperazine group, Dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, N-ethyl-N-isobutylamino group, N-ethyl-benzylamino group, diamylamino group, dihexylamino group, dioctylamino group, N-ethyl-N -Tetrafurfurylamino group, dibenzylamino group and the like can be mentioned. Among these, a 5-membered ring or a 6-membered ring is particularly preferable.

In the “substituted aromatic hydrocarbon group”, “substituted aromatic heterocyclic group” or “substituted condensed polycyclic aromatic group” represented by R ₁ to R ₄ in the general formulas (1) to (4), Examples of the “substituent” include a halogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and a linear or branched group having 1 to 20 carbon atoms. An alkoxy group having 3 to 20 carbon atoms, a linear or branched alkyl group having 1 to 20 carbon atoms substituted with a halogen atom, or 1 to 20 carbon atoms substituted with a halogen atom And a straight-chain or branched alkoxy group. Specifically, halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; direct groups such as methyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group. Chain alkyl group; branched alkyl group such as isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isooctyl group, 2-ethylhexyl group; cyclopropyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, etc. Cycloalkyl group; linear alkoxy group such as methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group; isopropoxy group, isobutoxy group Group, sec-butoxy group, tert-butoxy group Group, branched alkoxy group such as isooctyloxy group; cycloalkoxy group such as cyclopropoxy group, cyclopentyloxy group, cyclohexyloxy group, cyclopropylmethyloxy group; fluoromethyl group, difluoromethyl group, trifluoromethyl group, penta Halogen atoms (fluorine atoms) such as fluoroethyl group, 2,2,2-trifluoroethyl group, 2-fluoroethyl group, 3,3,3-trifluoropropyl group, 3-fluoropropyl group, nonafluorobutyl group And an alkoxy group substituted with a halogen atom (fluorine atom) such as a trifluoromethoxy group.

R ₁ to R ₄ in the general formulas (1) to (4) have a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, or a substituent. It is preferably an optionally substituted cycloalkyl group having 3 to 20 carbon atoms, more preferably a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent. More preferably a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent, and a methyl group or an ethyl group which may have a substituent. Is particularly preferred. Further, as described above, R ₁ to R ₄ may be the same or different, but are preferably the same from the viewpoint of the dye structure.

A “halogen atom” represented by R ₅ to R ₁₀ in the general formulas (1) to (4), “a linear or branched group having 1 to 20 carbon atoms which may have a substituent. Alkyl group "," optionally substituted cycloalkyl group having 3 to 20 carbon atoms "," optionally substituted straight chain or branched chain having 2 to 6 carbon atoms ""Alkenylgroup","optionally substituted linear or branched alkoxy group having 1 to 20 carbon atoms", "optionally substituted cyclohexane having 3 to 20 carbon atoms" “Halogen atom” in “alkoxy group”, “straight or branched alkyl group having 1 to 20 carbon atoms”, “cycloalkyl group having 3 to 20 carbon atoms”, “directly having 2 to 6 carbon atoms” Chain or branched alkenyl group "," Examples of the “straight or branched alkoxy group having 1 to 20 elemental atoms” and “cycloalkoxy group having 3 to 20 carbon atoms” include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Halogen atom: direct methyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tridecyl group, pentadecyl group, hexadecyl group, octadecyl group, nonadecyl group, etc. Chain alkyl group; branched alkyl group such as isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isooctyl group; cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, etc. A cycloalkyl group of: vinyl group, allyl group, butenyl group, Alkenyl groups such as senyl groups; linear alkoxy groups such as methoxy groups, ethoxy groups, propoxy groups, butoxy groups, pentyloxy groups, hexyloxy groups, heptyloxy groups, octyloxy groups, nonyloxy groups, decyloxy groups; isopropyloxy Group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, branched alkoxy group such as isooctyloxy group; cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy group, cyclooctyloxy group, cyclononyloxy group, A cycloalkoxy group such as a cyclodecyloxy group can be mentioned. In addition, these substituents may be bonded to each other through a single bond to form a ring.

“An optionally substituted linear or branched alkyl group having 1 to 20 carbon atoms” represented by R ₅ to R ₁₀ in the general formulas (1) to (4), “ An optionally substituted cycloalkyl group having 3 to 20 carbon atoms ", an" optionally substituted linear or branched alkenyl group having 2 to 6 carbon atoms "," “In the linear or branched alkoxy group having 1 to 20 carbon atoms which may have a substituent” or “cycloalkoxy group having 3 to 20 carbon atoms which may have a substituent” Examples of the “substituent” include a halogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and a linear or branched group having 1 to 20 carbon atoms. Alkoxy group with 3 carbon atoms 20 cycloalkoxy groups, straight chain or branched alkyl groups having 1 to 20 carbon atoms substituted with halogen atoms, straight chain or branched chains having 1 to 20 carbon atoms substituted with halogen atoms An alkoxy group etc. can be mention | raise | lifted. Specifically, halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; direct methyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, etc. Chain alkyl group; branched alkyl group such as isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isooctyl group; cycloalkyl group such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group; Group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group and the like linear alkoxy group; isopropoxy group, isobutoxy group, sec-butoxy Group, tert-butoxy group, isooctyloxy Branched alkoxy groups such as a group; cycloalkoxy groups such as a cyclopropoxy group, a cyclopentyloxy group, a cyclohexyloxy group, and a cyclopropylmethyloxy group; a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group, 2 , 2,2-trifluoroethyl group, 2-fluoroethyl group, 3,3,3-trifluoropropyl group, 3-fluoropropyl group, alkyl substituted by halogen atom (fluorine atom) such as nonafluorobutyl group Group; an alkoxy group substituted with a halogen atom (fluorine atom) such as a trifluoromethoxy group, and the like can be exemplified.

R ₅ to R ₁₀ in the general formulas (1) to (4) have a linear or branched alkyl group having 1 to 20 carbon atoms and a substituent which may have a substituent. It is preferably a cycloalkyl group having 3 to 20 carbon atoms, or a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, and has a substituent. A linear or branched alkyl group having 1 to 20 carbon atoms which may be present, or a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent. More preferably, a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent, or a linear or branched group having 2 to 6 carbon atoms which may have a substituent. The alkenyl group is particularly preferably

In the sulfonylimide acid ion, which is a counter anion in the general formulas (1) to (4), represented by A and B is “a linear or 1 to 20 carbon atom which may have a substituent or “Straight or branched alkyl group having 1 to 20 carbon atoms” or “carbon” in “branched alkyl group” or “cycloalkyl group having 3 to 20 carbon atoms which may have a substituent” Specific examples of the cycloalkyl group having 3 to 20 atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, Linear alkyl groups such as tridecyl, pentadecyl, hexadecyl, octadecyl, and nonadecyl; isopropyl, isobutyl, sec-butyl, te It can be exemplified cyclopropyl group, a cyclopentyl group, a cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, a cycloalkyl group such as cyclodecyl; t-butyl group, a branched alkyl group such as isooctyl. Among these, a linear or branched alkyl group having 1 to 20 carbon atoms is preferable, a linear or branched alkyl group having 1 to 10 carbon atoms is more preferable, and a methyl group is particularly preferable.

In the sulfonylimide acid ion, which is a counter anion in the general formulas (1) to (4), represented by A and B is “a linear or 1 to 20 carbon atom which may have a substituent or The “substituent” in the “branched alkyl group” or “cycloalkyl group having 3 to 20 carbon atoms which may have a substituent” is a halogen atom, a straight chain having 1 to 20 carbon atoms or Substituted with a branched alkyl group, a cycloalkyl group having 3 to 20 carbon atoms, a linear or branched alkoxy group having 1 to 20 carbon atoms, a cycloalkoxy group having 3 to 20 carbon atoms, or a halogen atom A linear or branched alkyl group having 1 to 20 carbon atoms, or a linear or branched alkoxy group having 1 to 20 carbon atoms substituted with a halogen atom. Etc. can be mentioned. Specifically, halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; direct methyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, etc. Chain alkyl group; branched alkyl group such as isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isooctyl group; cycloalkyl group such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group; Group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group and the like linear alkoxy group; isopropoxy group, isobutoxy group, sec-butoxy Group, tert-butoxy group, isooctyloxy Branched alkoxy groups such as a group; cycloalkoxy groups such as a cyclopropoxy group, a cyclopentyloxy group, a cyclohexyloxy group, and a cyclopropylmethyloxy group; a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group, 2 , 2,2-trifluoroethyl group, 2-fluoroethyl group, 3,3,3-trifluoropropyl group, 3-fluoropropyl group, alkyl substituted by halogen atom (fluorine atom) such as nonafluorobutyl group Group: An alkoxy group substituted with a halogen atom (fluorine atom) such as a trifluoromethoxy group can be exemplified. Among these, a fluorine atom or a linear or branched alkyl group having 1 to 20 carbon atoms substituted with a fluorine atom is preferable, and a linear chain having 1 to 10 carbon atoms substituted with a fluorine atom or a fluorine atom. More preferred are branched or branched alkyl groups.

In the sulfonylimido ion which is a counter anion in the general formulas (1) to (4), “substituted or unsubstituted aromatic hydrocarbon group”, “substituted or unsubstituted aromatic” represented by A and B As the “aromatic hydrocarbon group”, “aromatic heterocyclic group” or “fused polycyclic aromatic group” in the “heterocyclic group” or “substituted or unsubstituted condensed polycyclic aromatic group”, specifically, Aromatic hydrocarbon groups having 6 to 20 carbon atoms such as phenyl group, naphthyl group, biphenyl group, azulenyl group, anthracenyl group, terphenyl group, pyrenyl group; furan ring, thiophene ring, pyrrole ring, imidazole ring, thiazole ring , 5-membered monocyclic rings such as oxadiazole ring and 6-membered monocyclic rings such as pyridine ring and pyrazine ring, polycyclic rings such as terthiophene ring, phenanthrene ring, quinoline ring, An aromatic heterocyclic group having 2 to 20 carbon atoms or a condensed polycyclic aromatic having 2 to 20 carbon atoms having a skeleton such as a condensed ring such as a soquinoline ring, a quinoxaline ring, a benzofuran ring, a carbazole ring, and a dibenzothiophene ring A group can be raised.

In the sulfonylimide acid ion which is a counter anion in the general formulas (1) to (4), “substituted aromatic hydrocarbon group”, “substituted aromatic heterocyclic group” or “substituted condensation” represented by A and B Examples of the “substituent” in the “polycyclic aromatic group” include a halogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and 1 to 1 carbon atoms. 20 linear or branched alkoxy groups, cycloalkoxy groups having 3 to 20 carbon atoms, linear or branched alkyl groups having 1 to 20 carbon atoms substituted with halogen atoms, substituted with halogen atoms Examples thereof include straight-chain or branched alkoxy groups having 1 to 20 carbon atoms. Specifically, halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; direct methyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, etc. Chain alkyl group; branched alkyl group such as isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isooctyl group; cycloalkyl group such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group; Group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group and the like linear alkoxy group; isopropoxy group, isobutoxy group, sec-butoxy Group, tert-butoxy group, isooctyloxy Branched alkoxy groups such as a group; cycloalkoxy groups such as a cyclopropoxy group, a cyclopentyloxy group, a cyclohexyloxy group, and a cyclopropylmethyloxy group; a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group, 2 , 2,2-trifluoroethyl group, 2-fluoroethyl group, 3,3,3-trifluoropropyl group, 3-fluoropropyl group, alkyl substituted by halogen atom (fluorine atom) such as nonafluorobutyl group Group: An alkoxy group substituted with a halogen atom (fluorine atom) such as a trifluoromethoxy group can be exemplified. Among these, a fluorine atom or a linear or branched alkyl group having 1 to 20 carbon atoms substituted with a fluorine atom is preferable, and a linear chain having 1 to 10 carbon atoms substituted with a fluorine atom or a fluorine atom. A branched or branched alkyl group is more preferable, and a fluorine atom or a trifluoromethyl group is particularly preferable.

In the sulfonylimide acid ion, which is a counter anion in the general formulas (1) to (4), A and B have sufficient heat resistance because the glass transition point does not decrease too much, and are easy to handle. In view of the above, a linear or branched alkyl group having 1 to 20 carbon atoms having a fluorine atom as a substituent, or a straight chain having 1 to 10 carbon atoms having a fluorine atom or a fluorine atom as a substituent Alternatively, an aromatic hydrocarbon group having a branched alkyl group as a substituent is preferable, and a linear or branched alkyl group having 1 to 10 carbon atoms having a fluorine atom as a substituent, or a fluorine atom or a fluorine atom An aromatic hydrocarbon group having a linear or branched alkyl group having 1 to 10 carbon atoms as a substituent. More preferably, it is a linear or branched alkyl group having 1 to 3 carbon atoms having a fluorine atom as a substituent, or a linear or branched alkyl group having 1 to 3 carbon atoms having a fluorine atom or a fluorine atom as a substituent, or An aromatic hydrocarbon group having a branched alkyl group as a substituent is more preferable, and a trifluoromethyl group or a phenyl group having a fluorine atom or trifluoromethyl group as a substituent is particularly preferable. Specific examples of the linear or branched alkyl group having 1 to 3 carbon atoms having a fluorine atom as a substituent include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group, 2, Examples include 2,2-trifluoroethyl group, 2-fluoroethyl group, 3,3,3-trifluoropropyl group, 3-fluoropropyl group and the like.

In the general formulas (1) to (4), r ₅ to r ₁₀ are preferably 0 or 2, and most preferably 0. In addition, when r ₅ to r ₁₀ are 2, R ₅ to R ₁₀ are preferably alkenyl groups.

The triarylmethane dye represented by the general formula (1) can be synthesized according to a known method (for example, “Review Synthetic Dye” (Horiguchi Hiroshi, Sankyo Publishing, 1968)). Specifically, a commercially available triarylmethane dye is treated with a base to synthesize the corresponding triarylmethanol, and then synthesized by reacting the obtained triarylmethanol with the corresponding sulfonylimide. it can. That is, for example, a dye having a counter anion represented by HSO ₄ ⁻ is dissolved in a reaction solvent, and after adding a base and stirring, the corresponding triarylmethanol is synthesized by filtering the product. Subsequently, the triarylmethanol dye represented by the general formula (1) is obtained by dissolving the obtained triarylmethanol in a reaction solvent, adding and stirring the corresponding sulfonylimide acid, and filtering the precipitate. Can be synthesized. Examples of the reaction solvent include alcohol solvents such as water, methanol, ethanol, and 2-propanol; or a mixed solvent thereof. Examples of the base include potassium hydroxide, sodium hydroxide, and sodium carbonate. The reaction temperature is preferably 0 ° C. to 40 ° C., for example, and the addition amount of sulfonylimide acid is, for example, about 1 to 3 equivalents.

Specific examples of preferable compounds among the triarylmethane dyes represented by the general formula (1) according to the present invention are shown below, but the present invention is not limited to these compounds.

The triarylmethane dye of the present invention is excellent in solubility in an organic solvent, particularly PGMEA, and the solubility in PGMEA at 25 ° C. and normal pressure is preferably 1% by weight or more, and preferably 3% by weight or more. Is more preferable, and 5% by weight or more is particularly preferable. When considering application to a color filter, the higher the solubility, the better.

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

[Synthesis of Triarylmethanol]
To the reaction vessel, 40 g of Aizen Diamond Green GH (manufactured by Hodogaya Chemical Co., Ltd.) represented by the following structural formula (A-1) and 600 ml of water were heated and dissolved at 40 ° C., and then cooled to room temperature. To the obtained solution, 13 ml of 48% aqueous sodium hydroxide solution was added in portions, followed by stirring at room temperature for 1 hour, and the resulting viscous material was collected by filtration. The obtained viscous material was dissolved in 400 ml of ethyl acetate, the organic layer was washed with water, dried over anhydrous magnesium sulfate, concentrated and vacuum dried to obtain 31.4 g of triarylmethanol (A-2) having the following structural formula. It was.

[Synthesis of triarylmethane dyes]
To the reaction vessel, 10.5 g of the obtained triarylmethanol (A-2) and 60 ml of methanol were added and dissolved. A solution prepared by mixing 7.3 g of bis (trifluoromethanesulfonyl) imide and 20 ml of methanol was dropped into this solution, and the mixture was stirred at room temperature for 2 hours. After concentrating the reaction solution to a volume of about 50 ml and allowing to stand at 5 ° C. overnight, 14.8 g of a triarylmethane dye (A-3) having the following structural formula is collected by filtering the precipitated crystals. Got.

[Dye Evaluation]
About the obtained compound (A-3), using a thermogravimetric-differential thermal analyzer (manufactured by MAC Science Co., Ltd., TG-DTA 200S) and a spectrophotometer (manufactured by Hitachi High-Technologies Corporation, U-3000), Melting point, decomposition point and solubility in PGMEA at 25 ° C. and normal pressure were measured. The measurement results are summarized in Table 1.

[Comparative Example 1]
For comparison, the melting point, decomposition point, and solubility in PGMEA at 25 ° C. under normal pressure were measured under the same conditions as in Example 2, and the measurement results are summarized in Table 1. It was.

As shown in Table 1, the compound (A-3) of the examples of the present invention exhibits higher solubility in PGMEA than the comparative compound while maintaining heat resistance, and is useful as a color filter dye. I understand that.

The triarylmethane dye according to the present invention is excellent in heat resistance and excellent in solubility in organic solvents such as PGMEA, and is useful as a dye for color filters.

Claims (9)

1. A triarylmethane dye for a color filter represented by the following general formula (1).
   

   

   (Wherein R ₁ to R ₄ may be the same or different and each has a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, or a substituent. An optionally substituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, R ₁ and R ₂ , R ₃ and R ₄ may be bonded to each other via a single bond to form a ring, and R ₅ to R ₇ may be the same or different, and may be a halogen atom, A linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 20 carbon atoms which may have a substituent, and a substituent. Straight chain having 2 to 6 carbon atoms which may be Or a branched alkenyl group, a linear or branched alkoxy group having 1 to 20 carbon atoms which may have a substituent, and a carbon atom having 3 to 20 carbon atoms which may have a substituent. Represents a cycloalkoxy group, and these substituents may be bonded to each other via a single bond to form a ring, r ₅ and r ₆ represent an integer of 0 to 4, and r ₇ represents an integer of 0 to 5 Represents an integer, A and B may be the same or different and may have a substituent, a linear or branched alkyl group having 1 to 20 carbon atoms or a substituent. A cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group.
2. The triarylmethane dye according to claim 1, wherein the triarylmethane dye represented by the general formula (1) is represented by the following general formula (2).
   

   

   (Wherein R ₁ to R ₄ may be the same or different and each has a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, or a substituent. An optionally substituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, R ₁ and R ₂ , R ₃ and R ₄ may be bonded to each other via a single bond to form a ring, and R ₆ to R ₈ may be the same or different, and may be a halogen atom, A linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 20 carbon atoms which may have a substituent, and a substituent. Straight chain having 2 to 6 carbon atoms which may be Or a branched alkenyl group, a linear or branched alkoxy group having 1 to 20 carbon atoms which may have a substituent, and a carbon atom having 3 to 20 carbon atoms which may have a substituent. Represents a cycloalkoxy group, and these substituents may be bonded to each other via a single bond to form a ring, r ₆ represents an integer of 0 to 4, and r ₇ represents an integer of 0 to 5. , R ₈ represents an integer of 0 to 2. A and B may be the same or different and each may have a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent. An optionally substituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aroma Represents a group.)
3. The triarylmethane dye according to claim 1, wherein the triarylmethane dye represented by the general formula (1) is represented by the following general formula (3).
   

   

   (Wherein R ₁ to R ₄ may be the same or different and each has a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, or a substituent. An optionally substituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, R ₁ and R ₂ , R ₃ and R ₄ may be bonded to each other via a single bond to form a ring, and R ₅ , R ₇ and R ₉ may be the same or different, A halogen atom, an optionally substituted linear or branched alkyl group having 1 to 20 carbon atoms, an optionally substituted cycloalkyl group having 3 to 20 carbon atoms, a substituent Straight chain of 2 to 6 carbon atoms which may have a group A linear or branched alkoxy group having 1 to 20 carbon atoms which may have a chain or branched alkenyl group or a substituent, or a carbon atom having 3 to 20 carbon atoms which may have a substituent And these substituents may be bonded to each other through a single bond to form a ring, r ₅ represents an integer of 0 to 4, and r ₇ represents an integer of 0 to 5. R ₉ represents an integer of 0 to 2. A and B may be the same or different, and may have a substituent, a linear or branched alkyl group having 1 to 20 carbon atoms, Optionally substituted cycloalkyl group having 3 to 20 carbon atoms, substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group, substituted or unsubstituted condensed polycycle Represents an aromatic group.)
4. The triarylmethane dye according to claim 1, wherein the triarylmethane dye represented by the general formula (1) is represented by the following general formula (4).
   

   

   (Wherein R ₁ to R ₄ may be the same or different and each has a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, or a substituent. An optionally substituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, R ₁ and R ₂ , R ₃ and R ₄ may be bonded to each other via a single bond to form a ring, and R ₅ , R ₆ and R ₁₀ may be the same or different, A halogen atom, an optionally substituted linear or branched alkyl group having 1 to 20 carbon atoms, an optionally substituted cycloalkyl group having 3 to 20 carbon atoms, a substituent Optionally having 2 to 6 carbon atoms A linear or branched alkenyl group, an optionally substituted linear or branched alkoxy group having 1 to 20 carbon atoms, an optionally substituted carbon atom having 3 to And these substituents may be bonded to each other via a single bond to form a ring, r ₅ and r ₆ represent an integer of 0 to 4, and r ₁₀ represents 0 to Represents an integer of 3. A and B may be the same or different, and may have a linear or branched alkyl group having 1 to 20 carbon atoms, which may have a substituent, or a substituent. A cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group.
5. In the general formula (1), A and B are a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, or a substituted or unsubstituted aromatic hydrocarbon. The triarylmethane dye according to claim 1, which is a group.
6. In the general formula (1), A and B are each a linear or branched alkyl group having 1 to 20 carbon atoms having a fluorine atom as a substituent, or a fluorine atom or a fluorine atom as a substituent. The triarylmethane dye according to claim 1, which is an aromatic hydrocarbon group having a linear or branched alkyl group having 1 to 10 carbon atoms.
7. The triarylmethane dye according to claim 1, wherein in the general formula (1), A and B are trifluoromethyl groups.
8. The dye represented by the general formula (1) is a triarylmethane dye having a solubility in propylene glycol monomethyl ether acetate at 25 ° C. and normal pressure of 1% by weight or more. The triarylmethane dye described in 1.
9. A color filter using the triarylmethane dye according to any one of claims 1 to 8.