JP2012036301A - Triarylmethane-based dye - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a triarylmethane-based dye which is not only electrochemically and thermally stable but also excellent in durability to light, has good solubility in both organic solvents and resins, and further has high NMP (N-methylpyrrolidone) resistance.SOLUTION: The triarylmethane-based dye is expressed by general formula (I); (wherein, R, R, R, R, Rand Rare each independently a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent; any of Rand R, Rand R, and Rand Rmay be bonded to form a part of a ring structure or a heterocyclic ring structure; X denotes a bivalent hydrocarbon group; Y denotes an alkyl group in which at least a part of a hydrogen atom may be substituted with a fluorine atom; and Rdenotes an alkyl group).

Description

  The present invention relates to a novel triarylmethane dye, and more particularly to a triarylmethane dye excellent in light durability and solubility.

  Many dyes are known today and are largely distinguished as natural and synthetic dyes. Such synthetic dyes include, for example, aniline blue, fuchsin or methyl orange, but most synthetic dyes are aromatic or heterocyclic and are ionic (eg, all water-soluble dyes) or nonionic Or a disperse dye (for example, a disperse dye). In the case of ionic dyes, a distinction is made between anionic (anionic) dyes and cationic (cationic) dyes.

  The cationic dye is composed of an organic cation having a positive charge delocalized over a conjugated bond and usually an inorganic anion. These are usually dyes in which an optionally substituted amino group participates in resonance. Therefore, the selection of the cationic dye often depends on the number and type of anions which are counter ions. Examples of counter anions include chloride ions, bromide ions, iodide ions, perchlorate ions, tetrafluoroborate ions, Examples include hexafluorophosphate ions, alkyl or aryl sulfate ions, tosylate ions, acetic acid or oxalate ions.

  The cationic dyes rhodamine, safranin or Victoria blue usually have chloride ions or tosylic acid as counter ions. However, these compounds are not very electrochemically stable. For this reason, a technique for introducing a novel counter anion that makes these dyes more chemically stable has been studied.

  For example, as means for improving the durability of cationic dyes such as triarylmethane, the use of cyanoborate ions, fluoroalkylphosphate ions, fluoroalkylborate ions, imido ion as counter anions is disclosed. (For example, see Patent Document 1) Improvement of solubility and improvement of durability are problems.

  In addition, it has been proposed to introduce a metal alkoxide such as alkoxysilane in order to fix a dye or pigment in a coating film and obtain sufficient heat resistance (see, for example, Patent Documents 2 and 3). For example, in Patent Document 3, a pigment is included in a polymer network structure made of a metal-oxygen bond using a sol-gel method, or a polymer made of a metal-oxygen bond. It is said that the pigment is not eluted by an organic solvent or the like (see Patent Document 3, paragraph 0028).

Further, a colorant for a color filter containing a binder polymer, a crosslinkable monomer, a photopolymerization initiator, a dye as a colorant, and a silane compound having a photocrosslinkable functional group and a reactive group that forms a siloxane bond by a dehydration polymerization reaction. A composition has been proposed (see Patent Document 4). This color filter colorant composition uses a dye as a colorant and is said to have excellent transparency and colorability and high durability (see Patent Document 4, paragraph 0004).
Further, a color having a triarylmethane dye monomer or a polymer obtained by polymerizing the dye monomer, an aromatic sulfonic acid having a photoreactive group as a counter anion, and a resin as a binder A photosensitive coloring composition suitable for a filter has been proposed (see Patent Document 5). According to this photosensitive coloring composition, it is said that a photosensitive coloring composition for a color filter having excellent light resistance, heat resistance and transparency can be obtained (see Patent Document 5, Paragraph 0008).

JP 2007-503477 A U.S. Pat. No. 4,948,843 JP-A-6-308314 JP 2000-47020 A Japanese Patent No. 4266627

  Although the cationic dye described in Patent Document 1 has a certain degree of electrochemical and thermal stability, the fluoroalkyl phosphate ion and the fluoroalkyl borate ion have insufficient light resistance, and light resistance. When trying to improve the properties, there is a problem that the solubility in various solvents decreases. Furthermore, when the cyanoborate ion and imidoate ion are used in combination with a polymerizable monomer, for example, there is a problem that the coexistence with a radical initiator causes a deactivation factor.

  By the way, in a color filter used for a liquid crystal display, an alignment film is an essential component, and a polyimide film is often used as the alignment film. As the polyimide film, N-methylpyrrolidone (hereinafter abbreviated as “NMP”) is usually used as a solvent in the production process. When the polyimide film is used in contact with the color filter, the color filter is used. However, it is required to have resistance to NMP. Such a problem does not occur when a conventional pigment dispersion resist is used as a color filter. However, in a system using a dye, it is a very big problem that the dye has a property of eluting into NMP. Even when it is in contact with NMP, it is required that the dye is immobilized in the film.

The cationic dye disclosed in Patent Document 1 cannot suppress elution of the dye into the solvent even if the resist is sufficiently cured, and cannot be used as a coloring composition for a color filter.
Moreover, the cationic dye which introduce | transduced metal alkoxides, such as alkoxysilane to the counter ion disclosed by the above-mentioned patent documents 2-5 has the dye fixed in the film | membrane, and a dye does not flow out easily into an organic solvent. However, it has become clear from the examination of the present inventors that the resistance to NMP is insufficient and further improvement is necessary.

  That is, the present invention has been made to solve the above-described problems, and is not only electrochemically and thermally stable, but also excellent in durability against light and good dissolution in organic solvents and resins. It is an object to provide a triarylmethane dye having high compatibility with NMP and having high resistance to NMP.

As a result of diligent studies to solve the above problems, the present inventors have made the counter anion in the triarylmethane dye a sulfonylimide acid ion having a specific alkoxysilane group introduced therein, while maintaining heat resistance. The inventors have found that both solubility in organic solvents and resins and light resistance can be achieved, and that resistance to NMP can be improved, and the present invention has been completed.
That is, the present invention
(1) a triarylmethane dye represented by the following general formula (I):

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may each independently have a hydrogen atom, an alkyl group which may have a substituent, or a substituent. Any one of aryl groups, and any of R ¹ and R ² , R ³ and R ⁴ , and R ⁵ and R ⁶ may be bonded to form part of a ring structure or heterocyclic structure; X in the formula represents a divalent hydrocarbon group, Y represents an alkyl group in which at least a part of the hydrogen atoms may be substituted with fluorine atoms, and R ⁷ represents an alkyl group.)
(2) The triarylmethane dye according to (1), wherein X in the general formula (I) is an arylene group,
(3) The triarylmethane dye according to (1), wherein X in the general formula (I) is an arylalkylene group,
(4) The triarylmethane dye according to any one of (1) to (3), wherein Y in the general formula (I) is a perfluoroalkyl group,
(5) In the above general formula (I), R ⁵ is a hydrogen atom, and R ¹ , R ² , R ³ , R ⁴ , and R ⁶ are each independently an alkyl group having 1 to 20 carbon atoms (1 ) To (4), a triarylmethane dye,
(6) The triarylmethane dye according to (5) above, wherein R ¹ , R ² , R ³ , R ⁴ and R ⁶ are all the same, and (7) R ⁷ is alkyl having 1 to 4 carbon atoms. The triarylmethane dye according to any one of (1) to (6) above,
Is to provide.

  According to the present invention, triarylmethane is not only electrochemically and thermally stable, but also has excellent durability against light, good solubility in organic solvents and resins, and high resistance to NMP. Based dyes can be provided.

Embodiments of the present invention will be described in detail below, but the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the present invention.
The triarylmethane dye of this embodiment is represented by the following general formula (I).

In the above formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may each independently have a hydrogen atom, an alkyl group which may have a substituent, or a substituent. Any one of aryl groups, and any of R ¹ and R ² , R ³ and R ⁴ , and R ⁵ and R ⁶ may be bonded to form part of a ring structure or heterocyclic structure; . In the formula, X represents a divalent hydrocarbon group, Y represents an alkyl group in which at least part of the hydrogen atoms may be substituted with fluorine atoms, and R ⁷ represents an alkyl group.

Examples of the alkyl group in R ^{1 to} R ⁶ include a saturated alkyl group, an unsaturated alkyl group, and a cycloalkyl group, and these include an aryl group, an alkyloxy group, an aryloxy group, an acyloxy group, a halogen atom, and an acylamino group. May have a substituent such as a group, an alkyloxycarbonyl group, an aminocarbonyl group, a hydroxy group, and a cyano group.
More specifically, the alkyl group may be a linear, branched or cyclic alkyl group, such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-amyl group, an n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosanyl group, i-propyl group, sec-butyl group, i-butyl group, t-butyl group, 1-methylbutyl group, 1-ethylpropyl group 2-methylbutyl group, i-amyl group, neopentyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, t-amyl group, 1,3-dimethylbutyl group 3,3-dimethylbutyl group, 2-ethylbutyl group, 2-ethyl-2-methylpropyl group, linear or branched heptyl group, 1-methylheptyl group, 2-ethylhexyl group, 1,5-dimethylhexyl group, t-octyl group, branched nonyl group, branched decyl group, branched undecyl group, branched dodecyl group, branched tridecyl group, branched tetradecyl group, branched pentadecyl group, branched hexadecyl group, branched heptadecyl group, Branched octadecyl group, linear or branched nonadecyl group, linear or branched eicosanyl group, cyclopropyl group, cyclopropylmethyl group, cyclobutyl group, cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, cycloheptyl Group, cyclooctyl group, cyclohexyl Rupropyl group, cyclododecyl group, norbornyl group, bornyl group, cis-miltanyl group, isopinocanphenyl group, noradamantyl group, adamantyl group, adamantylmethyl group, 1- (1-adamantyl) ethyl group, 3,5-dimethyl Preferred examples include an adamantyl group, a quinuclidinyl group, a cyclopentylethyl group, and a bicyclooctyl group.

Examples of the aryl group in R ^{1 to} R ⁶ include a phenyl group, a naphthyl group, a biphenylenyl group, an acenaphthenyl group, a fluorenyl group, an anthracenyl group, an anthraquinonyl group, a pyrenyl group, and a heterocyclic group. , Alkyloxy group, aryloxy group, halogen atom, nitro group, cyano group, hydroxy group, substituted carbamoyl group, substituted sulfamoyl group, substituted amino group, substituted oxycarbonyl group, substituted oxysulfonyl group, alkylthio group, arylsulfonyl group, And may have a substituent such as a phenyl group.

More specifically, for example, the substituted phenyl group includes an o-, m- or p-methylphenyl group, an o-, m- or p-ethylphenyl group, an o-, m- or p-propylphenyl group. , O-, m- or p-isopropylphenyl group, o-, m- or p-tert-butylphenyl group, o-, m- or p-aminophenyl group, o-, m- or p- (N, N-dimethylamino) phenyl group, o-, m- or p-nitrophenyl group, o-, m- or p-hydroxyphenyl group, o-, m- or p-methoxyphenyl group, o-, m- or p-ethoxyphenyl group, o-, m- or p- (trifluoromethyl) phenyl group, o-, m- or p- (trifluoromethoxy) phenyl group, o-, m- Or p- (trifluoromethylsulfanyl) phenyl group, o-, m- or p-fluorophenyl group, o-, m- or p-chlorophenyl group, o-, m- or p-bromophenyl group, o- M- or p-iodophenyl group, 3,4- or 3,5-dimethoxyphenyl group, 5-fluoro-2-methylphenyl group, 3,4,5-trimethoxyphenyl group, or 2,4,5- A trimethylphenyl group etc. are mentioned.
Further, for example, as an aryl group having an alkyl group as a substituent, a benzyl group, 4-methoxyphenylethyl group, 3-methoxyphenylethyl group, 2-methoxybenzyl group, 3-methoxybenzyl group, 4-methoxybenzyl group, 2-ethoxybenzyl group, 2-methylbenzyl group, 3-methylbenzyl group, 4-tert-butylbenzyl group, 2- (trifluoromethyl) benzyl group, 3- (trifluoromethyl) benzyl group, 4-fluorobenzyl Group, 3-iodobenzyl group, 4- (trifluoromethoxy) benzyl group, 3- (trifluoromethoxy) benzyl group and 4- (trifluoromethylsulfanyl) benzyl group.

Further, in the general formula (I), any ^one of R ¹ and R ² , R ³ and R ⁴ , and R ⁵ and R ⁶ is bonded to form a part of a ring structure or a heterocyclic structure. Examples of the ring include piperidine, morpholine, pyrrolidine, piperazine, hexamethyleneimine and the like. Examples of the substituent represented by R ₁ R ₂ N—, R ₃ R ₄ N—, and R ₅ R ₆ N— include, for example, a pyrrolidino group, a piperazino group, a morpholino group, an N-ethylpiperazino 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, etc. are mentioned. Among these, a 5-membered ring and a 6-membered ring are preferable.

Among these, R ⁵ is a hydrogen atom, and R ¹ , R ² , R ³ , R ⁴ and R ⁶ are preferably each independently an alkyl group from the viewpoint of ease of dye production. Preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and particularly preferably an ethyl group and a methyl group.
Further, as described above, R ¹ , R ² , R ³ , R ⁴ and R ⁶ may be different or the same, but are preferably the same from the viewpoint of the dye structure.

On the other hand, in the sulfonyl imido ion introduced with an alkoxysilane group as a counter anion, as described above, X is a divalent hydrocarbon group, and Y has at least a part of hydrogen atoms substituted with fluorine atoms. R ⁷ is an alkyl group.
The divalent hydrocarbon group represented by X is not particularly limited, and for example, a linear or branched alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms, or an aryl having 7 to 20 carbon atoms. Examples include an alkylene group. Specific examples of the alkylene group include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, and various butylene groups. Examples of the arylene group include a phenylene group and a naphthylene group. Examples of the arylalkylene group include an arylmethylene group, an arylethylene group, and an arylpropylene group. Of these, an arylalkylene group having 7 to 10 carbon atoms is preferable from the viewpoint of availability of raw materials and production, and an arylmethylene group, an arylethylene group, and an arylpropylene group are particularly preferable.
The arylalkylene group includes an ortho form, a meta form and a para form, but is preferably a para form from the viewpoint of no steric hindrance.

Next, examples of the alkyl group constituting Y include the same alkyl groups as those described above for R ^{1 to} R ^6, and a part of the hydrogen atoms may be substituted with fluorine atoms. In particular, a fluorinated alkyl group having 1 to 3 carbon atoms and in which some or all of the hydrogen atoms are substituted with fluorine atoms is preferred. Among them, a perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms is an imide. This is particularly preferred from the viewpoint of increasing the acidity of the acid and improving the stability of the dye.
Specifically, for example, trifluoromethyl group, difluoromethyl group, fluoromethyl group, pentafluoroethyl group, 2,2,2-trifluoroethyl group, 2-fluoroethyl group, 3,3,3-trifluoro A propyl group, a 3-fluoropropyl group, etc. can be mentioned.
R ⁷ is an alkyl group, preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group. A plurality of R ⁷ may be the same or different, but are preferably the same from the viewpoint of ease of production.

  Examples of the triarylmethane dye represented by the general formula (I) include compounds represented by the following exemplified compounds (1) to (3). Here, Me means a methyl group.

As the exemplified compounds (1) to (3), a compound in which R ⁵ in the general formula (I) is a hydrogen atom and R ¹ , R ² , R ³ , R ⁴ and R ⁶ are alkyl groups is preferable. Furthermore, Exemplified Compound (1) in which R ¹ , R ² , R ³ , R ⁴ and R ⁶ are all the same is particularly preferred.

The triarylmethane dye represented by the general formula (I) can be synthesized by a known method. As a synthesis method, for example, the method described in “Review Review Synthetic Dyes” (Horiguchi Hiroshi, Sankyo Publishing, 1968) is useful.
Counter anion, a dye represented by the following formula, for example counter anion Cl ^- to the dye represented by the corresponding sulfonyl imide acid was added, can be synthesized by a salt exchange.

Specifically, the counter anion is Cl ^- to dissolve the dye represented by the reaction solvent, the corresponding sulfonyl imide acid was added and, after stirring, the precipitate can be synthesized by removing by filtration. The amount of sulfonylimide acid added is, for example, about 1 to 3 equivalents. Examples of the reaction solvent include water; alcohol solvents such as methanol, ethanol and 2-propanol; halogen solvents such as chloroform, dichloromethane and dichloroethylene; aromatic solvents such as benzene, toluene and xylene; acetone, methyl ethyl ketone and methyl. Ketone solvents such as isobutyl ketone; ether solvents such as diethyl ether, dibutyl ether, 1,4-dioxane and tetrahydrofuran; ester solvents such as ethyl acetate and butyl acetate; or a mixed solvent thereof. Is preferably 0 ° C. to 40 ° C., for example.

The triarylmethane dye of this embodiment has good solubility in an organic solvent or the like. The solubility can be confirmed by adding a dye to a specific solvent or a resin solution containing the solvent so as to have a certain concentration, and visually observing the degree of dissolution at that time.
Specific examples of the organic solvent that is the target of good solubility include ethylene glycol monoalkyl ether acetates such as ethyl acetate, isopropyl acetate, cellosolve acetate, butyl cellosolve acetate; diethylene glycol monomethyl ether acetate, carbitol acetate, butyl carbitol Diethylene glycol monoalkyl ether acetates such as acetate; propylene glycol monoalkyl ether acetates; acetate esters such as dipropylene glycol monoalkyl ether acetates; ethylene glycol dialkyl ethers; methyl carbitol, ethyl carbitol, butyl carbitol, etc. Diethylene glycol dialkyl ethers; triethylene glycol dialkyl ethers; Pyrene glycol dialkyl ethers; Dipropylene glycol dialkyl ethers; Ethers such as 1,4-dioxane and tetrahydrofuran; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; Alcohols such as methanol, ethanol and butanol; Benzene , Hydrocarbons such as toluene, xylene, octane and decane; petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha; lactic esters such as methyl lactate, ethyl lactate and butyl lactate; dimethylformamide, N-methylpyrrolidone etc. are mentioned. Among these solvents, it is desirable that the solubility in acetone, ethyl acetate, methanol, etc. is particularly excellent.

  In addition, the triarylmethane dye of the present embodiment is a material having an absorptivity for light in the wavelength range of 500 to 700 nm, but is high in other than the above wavelength range when dispersed in a resin or the like to form a coating. It is desirable to have transmittance. Specifically, for example, in the wavelength region of 430 to 450 nm, the transmittance is preferably 90% or more, and more preferably 93% or more.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples.

Example 1
(1) Synthesis of dye intermediate (intermediate 1) In a 200 mL eggplant type flask containing a magnetic stirrer, Basic Blue 7 (manufactured by Tokyo Chemical Industry Co., Ltd., 10 g), pure water (50 mL) and methanol (50 mL) Into a solution. Sodium hydroxide (manufactured by Kanto Chemical Co., Inc., 0.82 g) was added to the solution, and the mixture was stirred at room temperature for 2 hours. Stirring was stopped and the mixture was allowed to stand at room temperature overnight, and the precipitated reddish brown solid was collected by filtration and washed with pure water. Thereafter, it was dried under reduced pressure to obtain a reddish brown solid (hereinafter referred to as “intermediate 1”) (8.8 g, yield 92%).

(2) Synthesis of anion (intermediate 2) Dichloromethane (30 mL), trifluoromethanesulfonamide (manufactured by Tokyo Chemical Industry Co., Ltd., 0.92 g) into a 100 mL Schlenk type reaction tube containing a magnetic stir bar and purged with argon gas And triethylamine (Kanto Chemical Co., Ltd., 4.26 mL) were added. These were stirred and mixed, and then a 50% dichloromethane solution (manufactured by ACROS, 3.0 mL) of 2- (4-chlorosulfonylphenyl) ethyltrimethoxysilane was added dropwise. After attaching a reflux tube, the mixture was heated to reflux at 40 ° C. for 10 hours under an argon gas stream. The temperature was returned to room temperature, and the solvent and excess triethylamine were removed under reduced pressure to obtain a brown oily product (hereinafter referred to as “intermediate 2”). The crude product was used as such for the next reaction.

(3) Synthesis of Dye (Exemplary Compound (1)) Methanol (15 mL) was added and dissolved in a reaction vessel containing the intermediate 2 crude product. To this was added a solution of intermediate 1 (2.97 g) and methanol (15 mL), and the mixture was stirred at room temperature for 2 hours. After removing the solvent from the resulting dark blue solution under reduced pressure, acetone (10 mL) and toluene (20 mL) were added to obtain a solution. This solution was washed with pure water (30 mL). Exemplified compound (1) was obtained by removing the solvent under reduced pressure and drying (3.8 g, yield 71%: 2 steps). The reaction formula is as shown below. Hereinafter, exemplary compound (1) is referred to as “dye A”. The structure of Dye A was determined by ¹ H-NMR and ²⁹ Si-NMR. The attribution of chemical shift (peak) in ¹ H-NMR and ²⁹ Si-NMR is as follows.
¹ H-NMR (deuterated chloroform) δ (TMS, ppm): 8.18 (d, 1H), 7.96 (d, 2H), 7.44-7.16 (m, 8H), 6.93 ( t, 1H), 6.73 (d, 4H), 6.64 (d, 1H), 3.56 (q, 2H), 3.54 (s, 9H), 3.53 (q, 8H), 2.71 (m, 2H), 1.43 (t, 3H), 1.30 (t, 12H), 0.97 (m, 2H). ²⁹ Si-NMR (deuterated chloroform) δ (TMS, ppm): −42.956.

(Evaluation)
A colored composition is prepared by the following method, and the colored resin composition is used as a coating solution, which is applied onto a glass substrate by a spin coating method, dried at 80 ° C., and ultraviolet light is applied from the coating side with a high-pressure mercury lamp. A coating film for evaluation was prepared by exposing light to 200 mJ / m ² and curing it. Using this coating film, NMP resistance, heat resistance and light resistance were evaluated.

[1] Preparation of colored composition First, a photosensitive transparent resin composition having the following composition was prepared.
PGMEA solution of acrylic acid resin (active ingredient 42% by mass, resin (benzyl methacrylate / methacrylic acid = 62/38), acid value: 70 mg KOH / g, weight average molecular weight: 9000, PGMEA = propylene glycol monomethyl ether acetate): 12 Parts by mass / polyfunctional acrylate monomer (SR399E, Sakai Chemical): 2 parts by mass / photopolymerization initiator (2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name) Irgacure 907, manufactured by Ciba Specialty Chemicals)): 0.7 parts by mass / photosensitizer (4,4′-dimethylaminobenzophenone): 0.07 parts by mass / PGMEA: 5.2 parts by mass The components were mixed and stirred to prepare a colored resin composition having a nonvolatile component of 22% by mass.
A solution in which 2.7 parts by mass of dye A and 33 parts by mass of 2-methoxyethanol are mixed. The above-mentioned photosensitive transparent resin composition: 28 parts by mass. Megafac R-08MH (manufactured by Dainippon Ink & Chemicals, Inc.): 0 .02 parts by mass / PGMEA: 2 parts by mass

[2] NMP resistance As a sample for NMP resistance evaluation, a coating film that was sufficiently cured by exposure and curing with a high-pressure mercury lamp and then heating at 230 ° C. for 30 minutes was used.
For NMP resistance, one drop of NMP is dropped on the surface of the coating film on the glass substrate, and after standing for 10 seconds, the NMP is wiped with a wipe (Bencott Lint Free AZ-8, manufactured by Gardner). The coating film spectrum before and after the NMP dropping, that is, the ΔEab value was measured by using a microspectroscope OSP-SP200 manufactured by Olympus Co., Ltd. and evaluated by calculating a color difference. It can be said that the smaller the color difference, the less elution by NMP and the higher the resistance to NMP.

[3] Heat resistance The glass substrate on which the coating film was prepared was placed on a hot plate so that the substrate surface was in contact, left at 80 ° C. for 3 minutes, and then exposed to 200 mJ / m ² with a high-pressure mercury lamp. Next, the glass substrate was processed under the following conditions (a) or (b). The color difference (ΔEab value) before and after the treatment was calculated in the same manner as described above. A smaller ΔEab value indicates better heat resistance.
Condition (a): left at 200 ° C. for 30 minutes.
Condition (b): left at 230 ° C. for 30 minutes.

[4] Light resistance The coating film on the glass substrate as it is (hereinafter referred to as “atmosphere sample”) and the glass substrate coated with an adhesive on the coating film on the glass substrate. The two states (hereinafter referred to as “sample under oxygen interruption”) were used as samples for the light resistance test.
A sample in the atmosphere uses a xenon lamp (Ci4000 weather meter manufactured by Atlas, inner filter: infrared absorption coating (CIRA), outer filter: soda lime, wavelength of 300 nm or less is cut), a wavelength of 420 nm, and an illuminance of 1.2 mW / m. ² , after irradiation for 5 hours (equivalent to 21 kJ / m ² ), the transmittance and ΔEab value were measured in the same manner as in the heat resistance evaluation.
For the sample under oxygen interruption, the transmittance and ΔEab value were measured in the same manner as the irradiation condition of the sample under the atmosphere except that the irradiation time was changed to 70 hours (equivalent to 300 kJ / m ² ).

Comparative Example 1
In the synthesis of the dye in Example 1, a dye was obtained in the same manner as in Example 1 except that the intermediate 2 was changed to bis (trifluoromethanesulfonyl) imidic acid. The dye is a compound described below as Formula (4), and is hereinafter referred to as “Dye B”. The results of evaluation in the same manner as in Example 1 are shown in Table 1.

  As shown in the results of Table 1, the triarylmethane dye of Example 1 using a sulfonylimide acid ion having an alkoxysilane group introduced as a counter anion has good heat resistance and light resistance, and NMP resistance. Is high. On the other hand, in a comparative example using a triarylmethane dye different from the present invention, although the heat resistance at 200 ° C. is good, the heat resistance at 230 ° C. and the light resistance under the air and the air shut-off are poor. Since it is sufficient and particularly inferior to NMP wiping, it is difficult to use it for a color filter used in a liquid crystal display.

  Since the triarylmethane dye of the present invention is excellent in NMP resistance, it is suitable for a color filter used in a liquid crystal display. In addition, it has excellent solubility in organic solvents and has good heat resistance and light resistance, so it can form various patterns, permanent patterns such as wiring patterns, and structural members such as columns, ribs, spacers, and partition walls. It can be suitably used for the manufacture of a high-definition wiring pattern.

Claims (7)

A triarylmethane dye represented by the following general formula (I).

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may each independently have a hydrogen atom, an alkyl group which may have a substituent, or a substituent. Any one of aryl groups, and any of R ¹ and R ² , R ³ and R ⁴ , and R ⁵ and R ⁶ may be bonded to form part of a ring structure or heterocyclic structure; X in the formula represents a divalent hydrocarbon group, Y represents an alkyl group in which at least a part of the hydrogen atoms may be substituted with fluorine atoms, and R ⁷ represents an alkyl group.)   The triarylmethane dye according to claim 1, wherein X in the general formula (I) is an arylene group.   The triarylmethane dye according to claim 1, wherein X in the general formula (I) is an arylalkylene group.   The triarylmethane dye according to any one of claims 1 to 3, wherein Y in the general formula (I) is a perfluoroalkyl group. R ⁵ in the general formula (I) is a hydrogen atom, and R ¹ , R ² , R ³ , R ⁴ , and R ⁶ are each independently an alkyl group having 1 to 20 carbon atoms. The triarylmethane dye according to any one of the above. The triarylmethane dye according to claim 5, wherein R ¹ , R ² , R ³ , R ⁴ , and R ⁶ are all the same. R < ⁷ > is a C1-C4 alkyl group, The triarylmethane type | system | group dye in any one of Claims 1-6.