WO2010123071A1

WO2010123071A1 - Novel triarylmethane compound

Info

Publication number: WO2010123071A1
Application number: PCT/JP2010/057160
Authority: WO
Inventors: 高明倉田; 裕石井; 宜樹赤谷; 諒寺西; あさ子近藤; 秀洋新井
Original assignee: 日本化薬株式会社
Priority date: 2009-04-24
Filing date: 2010-04-22
Publication date: 2010-10-28
Also published as: CN102300938A; JPWO2010123071A1; TWI468371B; KR20120014111A; JP5442004B2; TW201100358A

Abstract

Disclosed is a dye composition which has high clarity and color developability, while exhibiting excellent fastnesses such as heat resistance, wet heat resistance and water resistance. Specifically disclosed are a triarylmethane compound represented by formula (1) and an oil-based or aqueous dye composition that contains the triarylmethane compound. (In formula (1), Ar1, Ar2 and Ar3 each independently represents an aromatic residue having a carbon atom that is bonded to the central carbon atom; and X- represents a bis(trifluoromethanesulfonyl)imide anion or a tris(trifluoromethanesulfonyl)methide anion.)

Description

Novel triarylmethane compounds

The present invention relates to novel triarylmethane compounds.

Triarylmethane dyes are characterized by their extremely sharp color and high color developability, and they are used as a wide range of applications such as various paints, water-based inks, oil-based inks, ink-jet inks, and color filter inks as violet, blue or green color materials. Used in In general, the properties required for coloring materials are different depending on the application, but the hue is sharp, high color forming ability is required, and in many applications, it is required that the coloring matter is fast to light, heat, etc. . As a triarylmethane dye, a cationic dye having a cationic group such as quaternary nitrogen in the structure and an anionic dye having an anionic group such as a sulfone group introduced into the cationic dye structure are known. Although all of them have excellent color forming properties, they have the disadvantage that they have poor fastness such as light resistance, heat resistance, moist heat resistance, water resistance and the like.

Therefore, there is a demand for a dye having the sharpness and color-forming properties of a triarylmethane dye and a highly robust dye, but no dye having these properties has been found. Patent Document 1 describes a salt compound of a cationic triarylmethane compound and a chloride ion or an arylsulfonate ion, but as a result of studies by the present inventors, a triarylmethane disclosed in this patent document The compound was insufficient in light resistance, heat resistance and water resistance. Patent Document 2 also describes a triarylmethane cationic dye having a fluorinated alkylsulfonyl counter ion, but there is no specific example of a compound, and light resistance, heat resistance, moist heat resistance, water resistance, etc. There is no mention of robustness. In addition, although salt compounds of a cationic triphenylmethane compound and a chloride ion or an oxalate ion are commercially available, as a result of studies by the present inventors, these known triphenylmethane compounds have light resistance, heat resistance, and moisture resistance. The heat resistance and water resistance were insufficient.

JP 2008-304766 JP-A-8-253705

As described above, the present invention is a novel triarylmethane compound which has the sharpness and color forming properties of triarylmethane dyes and is excellent in fastness such as light resistance, heat resistance, moist heat resistance, water resistance, etc. It is an object of the present invention to provide an oily or aqueous dye composition used.

The present inventors conducted intensive studies to solve the problems as described above, and as a result, a salt compound of cationic triarylmethane and a specific anion maintains the sharpness and colorability of triarylmethane dyes. And, it has been found that the light resistance, heat resistance, moisture heat resistance and water resistance are dramatically improved as compared with the prior art, and the present invention has been completed.

That is, the present invention
(1) triarylmethane compounds represented by the general formula (1),

(In the formula (1), Ar ₁ , Ar ₂ and Ar ₃ each independently represent an aromatic residue bonded to a central carbon atom by a carbon atom, and X ⁻ represents a bistrifluoromethanesulfonyl imide anion or tristrifluoromethanesulfonyl Represents methide anion)
(2) The triarylmethane compound according to (1), which is represented by the general formula (2):

(In formula (2), R _1a to R _6a each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group or a benzyl group, and R _7a to R _20a each independently represent a hydrogen atom or carbon And represents an alkyl group of 1 to 6 or a halogen atom, and X ^- is as defined in the above formula (1)),
(3) The triarylmethane compound according to (2), wherein X ⁻ is a tristrifluoromethanesulfonyl methide anion,
(4) The triarylmethane compound according to (1), which is represented by the general formula (3):

(In Formula (3), R _1b to R _4b each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group or a benzyl group, and R _5b to R _16b each independently represent a hydrogen atom or carbon represents a number 1-6 alkyl group or a halogen atom, R _17b represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a halogen atom or an amino group, X ^- is as defined in the above formula (1)). ,
(5) The triarylmethane compound according to (4), wherein X ^- is a tristrifluoromethanesulfonyl methide anion,
(6) An oil dye composition comprising the triarylmethane compound according to any one of (1) to (5) and an oil-soluble organic solvent,
(7) An aqueous dye composition comprising the triarylmethane compound according to any one of (1) to (5) and an aqueous medium,
About.

The triarylmethane compound of the present invention is excellent in sharpness and color development as described above, and when it is formed into an oil or aqueous dye composition and processed into a dye colored body, exhibits superior fastness to conventional products. It is. That is, the triarylmethane compound of the present invention can be used as a dye-colored material, and can be applied to a wide range of applications such as color filter inks and inkjet inks.

The triarylmethane compound of the present invention is represented by the above formula (1).

In Formula (1), Ar ₁ , Ar ₂ and Ar ₃ each independently represent an aromatic residue bonded to a central carbon atom at a carbon atom.

The aromatic residue in Ar ₁ , Ar ₂ and Ar ₃ of the formula (1) is, for example, an aromatic hydrocarbon residue such as phenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group and benzopyrenyl group; And aromatic heterocyclic residues such as pyridyl group, pyrazyl group, pyrimidyl group, quinolyl group, isoquinolyl group, pyrrolyl group, indoleyl group, imidazolyl group, carbazolyl group, thienyl group, furyl group, etc. A naphthyl group is preferred.

In Ar ₁ , Ar ₂ and Ar ₃ of the formula (1), a phenyl group or a naphthyl group may have a substituent, and the substituent is not particularly limited, but an aliphatic hydrocarbon residue, an aromatic Group, cyano group, isocyano group, thiocyanato group, isothiocyanato group, nitro group, acyl group, halogen atom, hydroxyl group, substituted or unsubstituted amino group, alkoxyl group, alkoxyalkyl group, and substituent group Aromatic oxy group, carboxyl group, carbamoyl group, aldehyde group, alkoxycarbonyl group, aromatic oxycarbonyl group and the like can be mentioned.

In the formula (1), X 2 ^- represents a bistrifluoromethanesulfonylimide anion or a tristrifluoromethanesulfonyl methide anion, and among these, a tristrifluoromethanesulfonyl methide anion is preferable.

As the triarylmethane compound of the present invention, the compound of the above formula (2) is preferable in that it is excellent in fastness such as heat resistance, moist heat resistance and water resistance. In formula (2), R _1a to R _6a each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group or a benzyl group, and R _7a to R _20a each independently represent a hydrogen atom or a carbon number It represents an alkyl group of 1 to 6 and a halogen atom. Further, in the formula (2), X ^- represents a bistrifluoromethanesulfonylimide anion or a tristrifluoromethanesulfonyl methide anion, and a tristrifluoromethanesulfonyl methide anion is particularly preferable.

In R _1a to R _6a of the formula (2), examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a pentyl group, a cyclopentyl group, a hexyl group and a cyclohexyl group And alkyl groups such as 1-ethylpropyl group, 1-methylpropyl group and 1,2-dimethylpropyl group. These alkyl groups may have a substituent, and the substituent is not particularly limited, and as the alkyl group having 1 to 6 carbon atoms having a substituent, for example, hydroxyethyl group, hydroxypropyl group, Examples thereof include hydroxybutyl group, 2-sulfoethyl group, carboxyethyl group, cyanoethyl group, methoxyethyl group, ethoxyethyl group, butoxyethyl group, trifluoromethyl group, pentafluoroethyl group, phenylmethyl group and the like.

In R _1a to R _6a of the formula (2), the phenyl group or the benzyl group may have a substituent, and examples of the substituent include a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group (C1-C5) alkyl group such as t-butyl group, pentyl group, etc., fluorine atom, halogen atom such as chlorine atom, bromine atom, iodine atom, etc., sulfonic acid group, methoxy group, ethoxy group, propoxy group, butoxy group (C1-C6) alkoxy group such as t-butoxy group and hexyloxy group; hydroxy (C1-C5) alkyl group such as hydroxyethyl group and hydroxypropyl group; methoxyethyl group, ethoxyethyl group, ethoxy (C1-C5) alkoxy (C1-C5) alkyl group such as propyl group and butoxyethyl group; hydroxyl group such as 2-hydroxyethoxy group (C1-C5) alkoxy group; (C1-C5) alkoxy (C1-C5) alkoxy group such as 2-methoxyethoxy group, 2-ethoxyethoxy group etc .; 2-sulfoethyl group, carboxyethyl group, A cyanoethyl group etc. are mentioned.

In R _1a to R _6a of the formula (2), a hydrogen atom, an unsubstituted alkyl group having 1 to 6 carbon atoms, an unsubstituted phenyl group or an unsubstituted benzyl group is preferable.

Examples of R _7a to R _{20a in} the formula (2) include a hydrogen atom, a halogen atom, or a C 1 to C 6 unsubstituted alkyl group.

In R _7a to R _20a of the formula (2), examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a pentyl group, a cyclopentyl group, a hexyl group and a cyclohexyl group And alkyl groups such as. These alkyl groups may have a substituent, and the substituent is not particularly limited, and examples of the alkyl group having 1 to 6 carbon atoms having a substituent include hydroxyethyl, hydroxypropyl and hydroxy. Examples thereof include a butyl group, 2-sulfoethyl group, carboxyethyl group, cyanoethyl group, methoxyethyl group, ethoxyethyl group, butoxyethyl group, trifluoromethyl group and pentafluoroethyl group.

Examples of the halogen atom in R _7a to R _20a of the formula (2) include fluorine, chlorine, bromine and iodine.

Moreover, as a triarylmethane compound of this invention, the compound of said Formula (3) is also preferable at the point which is excellent in fastnesses, such as heat resistance, wet heat resistance, and water resistance. In formula (3), R _1b to R _4b each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group or a benzyl group, and R _5b to R _16b each independently represent a hydrogen atom or a carbon number R _1-7 represents an alkyl group or a halogen atom, and R _{17 b} represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a halogen atom or an amino group. In the formula (3), X ^- represents a bistrifluoromethanesulfonylimide anion or a tristrifluoromethanesulfonyl methide anion, and a tristrifluoromethanesulfonyl methide anion is particularly preferred.

In R _1b to R _4b of the formula (3), examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a pentyl group, a cyclopentyl group, a hexyl group and a cyclohexyl group And alkyl groups such as 1-ethylpropyl group, 1-methylpropyl group and 1,2-dimethylpropyl group. These alkyl groups may have a substituent, and the substituent is not particularly limited, and as the alkyl group having 1 to 6 carbon atoms having a substituent, for example, hydroxyethyl group, hydroxypropyl group, Examples thereof include hydroxybutyl group, 2-sulfoethyl group, carboxyethyl group, cyanoethyl group, methoxyethyl group, ethoxyethyl group, butoxyethyl group, trifluoromethyl group, pentafluoroethyl group, phenylmethyl group and the like.

In R _1b to R _4b of formula (3), the phenyl group or the benzyl group may have a substituent, and the substituent is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group and isopropyl Group, butyl group, t-butyl group, (C1 to C5) alkyl group such as pentyl group, fluorine atom, halogen atom such as chlorine atom, bromine atom or iodine atom, sulfonic acid group, methoxy group, ethoxy group, propoxy group (C1 to C6) alkoxy groups such as butoxy, t-butoxy and hexyloxy; hydroxy (C1 to C5) alkyl groups such as hydroxyethyl and hydroxypropyl; methoxyethyl, ethoxyethyl and ethoxypropyl Groups, (C1-C5) alkoxy (C1-C5) alkyl groups such as butoxyethyl group; and 2-hydroxyethoxy groups And alkoxy (C1 to C5) alkoxy groups such as 2-methoxyethoxy group and 2-ethoxyethoxy group (C1 to C5); 2-sulfoethyl group, carboxyethyl group, cyanoethyl group and the like. Be

As R _1b to R _{4b in} the formula (3), a hydrogen atom, an unsubstituted alkyl group having 1 to 6 carbon atoms, an unsubstituted phenyl group, or an unsubstituted benzyl group is preferable.

In R _5b to R _17b of formula (3), examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a pentyl group, a cyclopentyl group, a hexyl group and a cyclohexyl group And alkyl groups such as. These alkyl groups may have a substituent, and the substituent is not particularly limited, and examples of the alkyl group having 1 to 6 carbon atoms having a substituent include hydroxyethyl and hydroxypropyl. And hydroxybutyl group, 2-sulfoethyl group, carboxyethyl group, cyanoethyl group, methoxyethyl group, ethoxyethyl group, butoxyethyl group, trifluoromethyl group, pentafluoroethyl group and the like.

Examples of the halogen atom in R _5b to R _17b of the formula (3) include fluorine, chlorine, bromine and iodine.

The amino group in R _17b of Formula (3) may have a substituent, and the substituent includes, for example, an alkyl group having 1 to 6 carbon atoms, a phenyl group or a benzyl group, and these are further substituted It may have a group, and the substituent is not particularly limited, and as the alkyl group having 1 to 6 carbon atoms having a substituent, for example, hydroxyethyl, hydroxypropyl, hydroxybutyl, 2-sulfoethyl Groups, carboxyethyl group, cyanoethyl group, methoxyethyl group, ethoxyethyl group, butoxyethyl group, trifluoromethyl group, pentafluoroethyl group and the like. In the case of a phenyl group or a benzyl group, examples of the substituent include a (C1 to C5) alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group and pentyl group, fluorine atom, chlorine A halogen atom such as an atom, a bromine atom and an iodine atom, a sulfonic acid group, a sulfonic acid group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a t-butoxy group and a hexyloxy group, and a (C1-C6) alkoxy group; Hydroxy (C1-C5) alkyl group such as hydroxypropyl group; (C1-C5) alkoxy (C1-C5) alkyl group such as methoxyethyl group, ethoxyethyl group, ethoxypropyl group, butoxyethyl group; 2-hydroxyethoxy group And the like hydroxy (C1-C5) alkoxy group such as Alkoxy group (C1 ~ C5) alkoxy (C1 ~ C5) alkoxy group such as, 2-sulfoethyl, carboxyethyl group, cyanoethyl group and the like.

As R _5b to R _{16b in} the formula (3), a hydrogen atom, a chlorine atom, or an unsubstituted alkyl group having 1 to 6 carbon atoms is preferable, and R _17b is preferably a hydrogen atom or an amino group.

Triarylmethane compound of the present invention may, for example, obtained by a known synthesis method described in Yutaka Hosoda al, issued by Gihodo Co. "Theoretical production Dye Chemistry" (781-787 pages), X ^- is chlorine anion It can also be synthesized by purchasing a commercially available product, adding the corresponding salt or acid, and performing salt exchange.

When the triarylmethane compound of the present invention is synthesized by salt exchange, a compound in which X ⁻ is a chloride anion is a reaction solvent (eg, water, methanol, ethanol, isopropanol, acetone, N, N-dimethylformamide) And water-soluble polar solvents such as N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP), which may be used alone or in combination, and the corresponding salts or The acid can be added by about 0.5 to 3 equivalents, stirred at a predetermined temperature (for example, 0 to 100 ° C.), easily synthesized, and obtained by filtering the precipitated crystals.

Specific examples of the triarylmethane compounds represented by the formula (2) are shown in Table 1 below, and specific examples of the triarylmethane compounds represented by the formula (3) are shown in Table 2 below, but the present invention It is not limited.

In Tables 1 and 2, for the substituent R, Me is methyl, Et is ethyl, Ph is phenyl, Bz is benzyl, CF ₃ is trifluoromethyl, n-Bu is normal Sec-Bu represents a secondary butyl group, i-Pr represents an isopropyl group, and CyHex represents a cyclohexyl group. In addition, when X ^- is α, it represents a tristrifluoromethanesulfonyl methide anion, and when it is a β, it represents a bistrifluoromethanesulfonyl imide anion.

The triarylmethane compound of the present invention is used as an oil-based dye composition, or a coloring composition such as various paints, water-based inks, oil-based inks, inks for inkjets, inks for color filters as an aqueous dye composition. Oily dye compositions and aqueous dye compositions are used, for example, for colored materials such as plain paper, coated paper, plastic films, plastic substrates and the like. Moreover, as a method of applying the dye composition of the present invention to a material to be colored, various printing methods such as offset printing, letterpress printing, flexographic printing, ink jet printing, or coating methods using a spin coater, roll coater or the like can be mentioned.

The oily or aqueous dye compositions according to the invention comprise the triarylmethane compounds according to the invention and, in the case of oily dye compositions, an oil-soluble organic solvent, and in the case of aqueous dyes, an aqueous medium. In the oily or aqueous dye composition of the present invention, the triarylmethane compound of the present invention is preferably contained in an amount of 0.2 to 40% by weight, more preferably 0.5 to 20% by weight. Further, in the oil-based or aqueous dye composition of the present invention, a coloring material other than the above-mentioned formula (1) may be added as needed for the purpose of adjusting the hue and the like. Examples of coloring materials that can be added include water-soluble dyes such as acid dyes, reactive dyes, direct dyes, cationic dyes and basic dyes, oil-soluble dyes such as disperse dyes and solvent dyes, organic pigments, carbon black and the like. And added in a state of being dissolved or dispersed in a solvent.

The aqueous dye composition of the present invention can be prepared by dispersing the triarylmethane compound of the formula (1) in an aqueous medium. Aqueous media include water or water soluble organic solvents. Examples of the water-soluble organic solvent include alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol and benzyl alcohol; ethylene ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene Polyhydric alcohols such as glycol, polypropylene glycol, glycerin, trimethylolpropane, 1,3-pentanediol and 1,5-pentanediol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, Triethylene glycol monoethyl ether, triethylene glycol monobutyl Ether, glycol derivatives such as dipropylene glycol monomethyl ether; ethanolamine, diethanolamine, triethanolamine, amines such as morpholine; 2-pyrrolidone, NMP, 1,3-dimethyl - imidazolidinone.

The oil-based dye composition of the present invention can be prepared by dissolving or dispersing the triarylmethane compound of the above formula (1) in at least one or more oil-soluble organic solvents. As the oil-soluble organic solvent to be used, for example, alcohols such as ethanol, pentanol, octanol, cyclohexanol, benzyl alcohol and tetrafluoropropanol; ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol mono Glycol derivatives such as ethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol diacetate, propylene glycol diacetate; ketones such as methyl ethyl ketone and cyclohexanone; butyl phenyl ether, benzyl Ethers such as ether and hexyl ether; acetic acid Chill, butyl acetate, ethyl benzoate, butyl benzoate, ethyl laurate, esters such as butyl laurate; acetonitrile, DMF, dimethyl sulfoxide, sulfolane, NMP, polar organic solvents such as 2-pyrrolidone. These solvents may be used alone or in combination of two or more.

Dispersants used in the oil-based dye composition include sodium dodecylbenzene sulfonate, sodium lauryl acid, formalin condensate of naphthalene sulfonic acid, formalin condensate of alkyl naphthalene sulfonic acid, formalin condensate of creosote oil sulfonic acid, poly Well-known anionic surfactants such as ammonium salt of oxyethylene alkyl ether sulfate, ammonium salt of polyoxyethylene alkyl phenyl ether sulfate, polyoxyalkyl ether phosphate ester salt, etc., vinyl naphthalene derivative, fat of α, β-ethylenically unsaturated carboxylic acid Alcohol ester etc., styrene, styrene derivative, acrylic acid, acrylic acid derivative, methacrylic acid, methacrylic acid derivative, maleic acid, maleic acid derivative, maleic anhydride, maleic anhydride Block copolymers comprising at least two or more monomers selected from leic acid derivatives, itaconic acid, itaconic acid derivatives, fumaric acid, fumaric acid derivatives, etc., or random copolymers, or salts thereof Molecular dispersants and the like can be mentioned, and it is preferable to use at 10 to 100% by weight with respect to the dye compound for dispersing one or more of these. In addition to these dispersants, known nonionic surfactants and silicones such as polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, copolymer of ethylene oxide and propylene oxide, etc. If necessary, known antifoaming agents based on acetylene may be added during and / or after pigment dispersion.

Examples of the method of dispersing the pigment into fine particles include a method using a sand mill (beads mill), a roll mill, a ball mill, a paint shaker, an ultrasonic disperser, a microfluidizer, etc., among which sand mills (bead mills) are preferred. In the grinding of the pigment in the sand mill (bead mill), it is preferable to use a small diameter bead, to increase the packing ratio of the beads, etc., and to treat under conditions that increase the grinding efficiency. It is preferable to remove elementary particles by separation or the like. The dye composition of the present invention may contain, as other additives, surface conditioners, preservatives, fungicides, pH adjusters and the like. Surface conditioners include polysiloxane or polydimethylsiloxane surfactants; preservatives and fungicides include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, zinc pyridinethione-1-oxide And an amine salt of 1,2-benzisothiazolin-3-one, 1-benzisothiazolin-3-one and the like, and as a pH adjuster, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, Examples thereof include tertiary amines such as triethanolamine, diethanolamine, dimethylethanolamine, diethylethanolamine and the like, and these can be added as necessary.

Moreover, in the oil-based or aqueous dye composition of the present invention, for the purpose of improving the fixability of the dye to the colored material, a polyamide based, polyurethane based, polyester compatible with the medium in the composition within the necessary range. It is preferable to contain a system, epoxy resin or polyacrylic resin. Further, in order to improve the fixing property, monomers, oligomers, polymerization initiators and the like having an ethylenically unsaturated group may be contained within the necessary range. The oily or aqueous dye composition of the present invention can be prepared by dissolving, dispersing or mixing the above-mentioned components in a solvent.

EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. In the examples, "parts" means "parts by weight" unless specified. The decomposition temperatures of various compounds obtained in the examples were measured by TG / DTA. Moreover, evaluation of moisture-heat resistance, water resistance, etc. measured and evaluated the chromaticity (L value, a value, b value) of the dye colored body with the following chromaticity measurement apparatus. The measuring instrument names are as follows.
1. TG / DTA (simulated thermogravimetry simultaneous measurement):
Seiko Instruments Inc. trade name TG / DTA 220
2. Color measurement device: UV-3150 manufactured by Shimadzu Corporation

Example 1 (Synthesis of Compound No. 1a in Table 1)
Dissolve 2 parts of BasicBlue 7 (made by Tokyo Chemical Industry Co., Ltd., decomposition temperature: 217 ° C.) of the following formula (100) in 150 parts of water and, while stirring, add 30 parts of acetonitrile and cesium salt of tristrifluoromethanesulfonium methide 2.1. A solution in which parts were dissolved was added. After stirring for 3 hours, precipitated crystals were collected by filtration, washed with water and dried to obtain 1.5 parts of blue crystals (triarylmethane compound of the present invention). Decomposition temperature: 256 ° C

Example 2 (Synthesis of Compound No. 2a in Table 1)
Two parts of BasicBlue 7 of the following formula (100) were dissolved in 150 parts of water, and a solution of 1.2 parts of potassium salt of bistrifluoromethanesulfonium imide in 10 parts of water was added while stirring. After stirring for 3 hours, the precipitated crystals were collected by filtration, washed with water and dried to obtain 0.7 parts of blue crystals (the triarylmethane compound of the present invention). Decomposition temperature: 240 ° C

Example 3
Preparation of Oily Dye Composition and Dye Colored Material In 10 parts of tetrafluoropropanol, the compound No. 1 obtained in the above example was used. Compound No. 1a. Each 0.5 part of 2a was dissolved to prepare an oily dye composition. The obtained oily dye composition was spin-coated on a polycarbonate substrate and dried at 80 ° C. for 30 minutes to prepare a dye-colored material.

In addition, the comparative example 1 in the following Table 5 and Table 9 represents the test result of what prepared dye coloring matter similarly using BasicBlue7 of following formula (100).

Moisture and heat resistance test 1
The dye-colored material obtained by the above method was left to stand in a constant temperature and humidity chamber at 85 ° C. and 85% RH for 40 hours. The dye colored materials before and after the test were measured for L value, a value and b value with a C light source as a standard light with a spectrophotometer and a viewing angle of 2 degrees as standard light, and the color difference was determined from the following formula. The smaller the color difference is, the smaller the change in hue is.
Color difference = [(pre-test L value-post-test L value) ² + (pre-test a value-post-test a value) ² + (pre-test b value-post-test b value) ² ] ^1/2
Measured values of colorimetry and color differences in the moisture resistance test are shown in Tables 3 to 6 below.

Compound No. The color measurement results of 1a are shown in Table 3 below.
(Table 3)
Before the L value a value b value test 84.15 -6.23 -24.43
After the test 84.90 -6.37 -23.26
Difference before and after the test -0.75 0.14 -1.17

Compound No. The measurement results of 2a are shown in Table 4 below.
(Table 4)
L value a value b value test 82.71-6.45-27.04
After the test 83.37 -7.33 -25.84
Difference before and after the test -0.66 0.88 -1.20

The color measurement results of Comparative Example 1 are shown in Table 5 below.
(Table 5)
L value a value b value test before 79.62 -5.19 -31.95
After the test 89.70-4.29-11.66
Difference before and after the test -10.08 -0.90 -20.29

Compound No. 1 from Table 3 to Table 5 above. Compound No. 1a. The results of determination of color differences of 2a and Comparative Example 1 are shown in Table 6 below.
(Table 6)
Color difference compound No. 1a 1.4
Compound No. 2a 1.6
Comparative Example 1 22.7

As apparent from the results of Table 6, while the color difference between the dye colored body of Comparative Example 1 before and after the test shows a very large value of 22.7, the dye colored body of the present invention has a color difference of 1.4 and 1 It shows a very small value of .6, and it can be seen that the heat and humidity resistance is extremely excellent.

Water resistance test 1
The dye-colored product obtained by the above method was left in hot water at 70 ° C. for 5 minutes. The dye colored materials before and after the test were measured for L value, a value and b value with a C light source as a standard light with a spectrophotometer and a viewing angle of 2 degrees as standard light, and the color difference was determined from the following formula. The smaller the color difference is, the smaller the change in hue is, and thus the better. Color difference = [(pre-test L value-post-test L value) ² + (pre-test a value-post-test a value) ² + (pre-test b value-post-test b value) ² ] ^1/2
Measured values of colorimetry and color differences in the water resistance test are shown in Tables 7 to 10 below.

Compound No. The measurement results of 1a are shown in Table 7 below.
(Table 7)
Before the L value a value b value test 84.15 -6.23 -24.43
After the test 84.96 -6.12 -22.60
Difference before and after the test -0.81 -0.11 -1.83

Compound No. The colorimetric results of 2a are shown in Table 8 below.
(Table 8)
L value a value b value test 82.71-6.45-27.04
After the test 86.43 -6.08 -20.67
Difference before and after the test -3.72 -0.37 -6.37

The color measurement results of Comparative Example 1 are shown in Table 9 below.
(Table 9)
L value a value b value test before 79.62 -5.19 -31.95
After the test 99.26-0.58-1.53
Difference before and after the test -19.64 -4.61 -30.42

Compound No. 1 from Table 7 to Table 9 above. Compound No. 1a. The results of determination of color differences of 2a and Comparative Example 1 are shown in Table 10 below.
(Table 10)
Color difference compound No. 1a 2.0
Compound No. 2a 7.4
Comparative Example 1 36.7

As is clear from the results in Table 10, the color difference between the dye colored body of Comparative Example 1 before and after the test shows a very large value of 36.7, while the dye colored body of the present invention has a color difference of 2.0 and 7 It shows a very small value of .4, indicating that it is extremely excellent in water resistance.

Example 4 (Synthesis of Compound No. 5a in Table 1)
2 parts of BasicBlue 26 (manufactured by Tokyo Chemical Industry Co., Ltd., decomposition temperature: 223 ° C.) of the following formula (101) is dissolved in 20 parts of DMF, and 2.5 parts of cesium salt of tristrifluoromethanesulfonium methide is added to 20 parts of DMF while stirring. The dissolved solution was added. After stirring for 2 hours, liquid filtration was performed, and water was added to the obtained filtrate. The precipitated crystals were collected by filtration, washed with water and dried to obtain 1.1 parts of purple crystals (triarylmethane compound of the present invention). Decomposition temperature: 267 ° C

Example 5
Preparation of Oily Dye Composition and Dye Colored Material In 10 parts of tetrafluoropropanol, the compound No. 1 obtained in Example 4 was used. An oil dye composition was prepared by dissolving 0.5 parts of 5a. The obtained oily dye composition was spin-coated on a polycarbonate substrate and dried at 80 ° C. for 30 minutes to prepare a dye-colored material.

In addition, the comparative example 2 in the following Table 12 represents the evaluation result of what prepared dye coloring matter similarly using BasicBlue26 of said Formula (101).

Moisture and heat resistance test 2
The test method is the same as moist heat resistance test 1. The colorimetric measurement values and color differences are shown in Tables 11 to 13 below.

Compound No. The color measurement results of 5a are shown in Table 11 below.
(Table 11)
L value a value b value before the test 86.08-6.87-21.15
After the test 86.24-6.86-20.84
Difference before and after test -0.16 -0.01 -0.31

The colorimetric results of Comparative Example 2 are shown in Table 12 below.
(Table 12)
L value a value b value test 85.54-9.17-21.25
After the test 88.60 8.40-15.42
Difference before and after test -3.06 -0.77 -5.83

Compound No. 1 from Table 11 and Table 12 above. The results of determination of color differences of 5a and the comparative example are shown in Table 13 below.
(Table 13)
Color difference compound No. 5a 0.3
Comparative example 2 6.6

As is clear from the results in Table 13, the color difference between the dye-colored product of Comparative Example 2 before and after the test shows a very large value of 6.6, while the dye-colored product of the present invention is very good with a color difference of 0.3. It is understood that the heat and humidity resistance is extremely excellent.

Water resistance test 2
The test method is the same as water resistance test 1. Measured values of colorimetry and color differences are shown in Tables 14 to 16 below.

Compound No. The color measurement results of 5a are shown in Table 14 below.
(Table 14)
L value a value b value test 86.66-6.78-20.34
After the test 88.62 -3.64 -11.89
Difference before and after the test -1.96 -3.14 -8.45

The measurement results of Comparative Example 2 are shown in Table 15 below.
(Table 15)
L value a value b value before the test 85.57-9.17-21.25
After the test 94.55 3.92 -1.28
Before and after the test -8.98-13.09-19.97

Compound No. 1 from Table 14 and Table 15 above. The results of determining the color difference of 5a and Comparative Example 2 are shown in Table 16 below.
(Table 16)
Color difference compound No. 5a 9.2
Comparative example 2 25.5

As apparent from the results in Table 16, while the color difference between before and after the test of the dye colored body of Comparative Example 2 shows a very large value of 25.5, the dye colored body of the present invention is very high with a color difference of 9.2. Small value, it is understood that the water resistance is extremely excellent.

Example 6 (Synthesis of Compound No. 45a in Table 1)
A cesium salt of tristrifluoromethanesulfonium methide is dissolved in a mixed solution of 2 parts of DMF and 12 parts of methanol while dissolving 2 parts of a dye of the following formula (102) in a mixed solution of 30 parts of water and 75 parts of methanol while stirring. A solution of 48 parts was added. After heating and stirring for 3 hours at 60 ° C., the precipitated crystals were collected by filtration, washed with water and dried to obtain 1.3 parts of blue crystals (triarylmethane compound of the present invention). Decomposition temperature: 262 ° C

Example 7 (Synthesis of Compound No. 57a in Table 1)
A cesium salt of tristrifluoromethanesulfonium methide is dissolved in a mixed solution of 2 parts of DMF and 12 parts of methanol while dissolving 2.5 parts of a dye of the following formula (103) in a mixed solution of 2 parts of water and 38 parts of methanol while stirring. A solution of 2.87 parts dissolved was added. After heating and stirring for 3 hours at 60 ° C., the precipitated crystals were collected by filtration, washed with water and dried to obtain 2.8 parts of blue crystals (triarylmethane compound of the present invention). Decomposition temperature: 269 ° C

Example 8 (Synthesis of Compound No. 69a in Table 1)
A cesium salt of tristrifluoromethanesulfonium methide is dissolved in a mixed solution of 3 parts of DMF and 25 parts of methanol while dissolving 3 parts of the dye of the following formula (104) in a mixed solution of 10 parts of water and 53 parts of methanol while stirring. A solution of 94 parts was added. After heating and stirring for 3 hours at 60 ° C., the precipitated crystals were collected by filtration, washed with water and dried to obtain 3.5 parts of blue crystals (triarylmethane compound of the present invention). Decomposition temperature: 267 ° C

Example 9 (Synthesis of Compound No. 1b in Table 2)
In 50 parts of water, 1 part of malachite green oxalate of the following formula (105) was dissolved in 50 parts of water, and 2 parts of a cesium salt of tristrifluoromethanesulfonium methide was dissolved in 5 parts of DMF. The solution was added. After stirring for 3 hours, the precipitated crystals were collected by filtration, washed with water and dried to obtain 0.5 parts of dark green crystals (the triarylmethane compound of the present invention). Decomposition temperature: 190 ° C

Example 10 (synthesis of compound No. 3b in Table 2)
In 500 parts of water was dissolved 5 parts of BasicBlue 1 (decomposition temperature: 190 ° C.) of the following formula (106), and a solution in which 2 parts of a cesium salt of tristrifluoromethanesulfonium methide was dissolved in 10 parts of DMF was added while stirring. . After stirring for 3 hours, the precipitated crystals were collected by filtration, washed with water and dried to obtain 0.7 parts of blue crystals (the triarylmethane compound of the present invention). Decomposition temperature: 230 ° C

Example 11 (synthesis of compound No. 5b in Table 2)
In 500 parts of water, 5 parts of BasicViolet 3 (decomposition temperature: 205 ° C.) of the following formula (107) was dissolved, and a solution in which 1 part of a cesium salt of tristrifluoromethanesulfonium methide was dissolved in 10 parts of DMF was added while stirring. . After stirring for 3 hours, the precipitated crystals were collected by filtration, washed with water and dried to obtain 1.2 parts of purple crystals (triarylmethane compound of the present invention). Decomposition temperature: 240 ° C

Example 12
Preparation of Oily Dye Composition and Dye Colored Material In 10 parts of tetrafluoropropanol, the compound No. 1 obtained in each of the above examples was used. Compound No. 1b. 3b, the compound No. An oil dye composition was prepared by dissolving 0.5 parts of 5b. The obtained oily dye composition was spin-coated on a polycarbonate substrate and dried at 80 ° C. for 30 minutes to prepare a dye-colored material.

Comparative Example 3 described in Tables 17 and 18 below is malachite green oxalate of the following Formula (105), Comparative Example 4 is BasicBlue 1 of the following Formula (106), and Comparative Example 5 is the following Formula (107) The dye-colored bodies were similarly prepared using Basic Violet 3 of the above).

Water resistance test 3
The dye-colored product obtained by the above method was left in warm water at 70 ° C. for 30 seconds. The dye colored materials before and after the test were measured for L value, a value and b value with a C light source as a standard light with a spectrophotometer and a viewing angle of 2 degrees as standard light, and the color difference was determined from the following formula. The smaller the color difference is, the smaller the change in hue is, and thus the better. Color difference = [(pre-test L value-post-test L value) ² + (pre-test a value-post-test a value) ² + (pre-test b value-post-test b value) ² ] ^1/2
Measured values of colorimetry and color differences in the water resistance test are shown in Tables 17 to 23 below.

Compound No. The measurement results of 1b are shown in Table 17 below.
(Table 17)
L value a value b value test before 93.25 -10.94 -6.37
After the test 93.58-8.79-5.62
Difference before and after test -0.33-2.15-0.75

Compound No. The color measurement results of 3b are shown in Table 18 below.
(Table 18)
L value a value b value before the test 92.12 -11.73 -10.53
After the test 92.44 -10.16 -9.37
Difference before and after test -0.32 -1.57 -1.16

Compound No. The color measurement results of 5b are shown in Table 19 below.
(Table 19)
L value a value b value test 77.97 19.33 -32.25
After the test 79.58 16.61 -28.95
Difference before and after test -1.61 2.72 -3.30

The color measurement results of Comparative Example 3 are shown in Table 20 below.
(Table 20)
L value a value b value test 89.77 -10.94 -4.49
After the test 100.22 -0.21 -0.41
Difference before and after the test -10.45-10.73-4.08

The colorimetric results of Comparative Example 4 are shown in Table 21 below.
(Table 21)
L value a value b value test 95.83 -7.27 -5.93
After the test 100.16 -0.13 -0.48
The difference before and after the test -4.33 -7.14 -5.45

The measurement results of Comparative Example 5 are shown in Table 22 below.
(Table 22)
L value a value b value test 75.14 15.62-37.06
After the test 99.65 0.21 -1.13
Difference before and after the test -24.51 15.41-35.93

Compound No. 1 from Table 17 to Table 22 above. 1b, no. 3b, no. The results of determination of color differences of 5b and Comparative Examples 3, 4 and 5 are shown in Table 23 below.
(Table 23)
Color difference compound No. 1b 2.3
Compound No. 3b 2.0
Compound No. 5b 4.6
Comparative example 3 15.5
Comparative example 4 10.0
Comparative Example 5 46.1

As is clear from the results in Table 23, the color differences of the dye-colored product of Comparative Example 3 before and after the test show a large value of 15.5, while the compound No. 1 of the present invention in which the cation portion is the same. The dye-colored product of 1b exhibits a small value of color difference of 2.3, and it can be seen that it is extremely excellent in water resistance. Similarly, while the color difference between before and after the test of the dye colored body of Comparative Examples 4 and 5 shows a large value of 10.0 and 46.1, the compound No. 1 of the present invention. 3b and no. The color difference of the dye-colored material of 5b shows very small values of 2.0 and 4.6.

Example 13 (synthesis of compound No. 53b in Table 2)
In a mixed solution of 200 parts of water and 120 parts of methanol, 2.31 parts of a dye of the following formula (108) is dissolved, and 2.30 parts of a cesium salt of tristrifluoromethanesulfonium methide is dissolved in 4.2 parts of DMF while stirring. The added solution was added. After stirring for 3 hours, precipitated crystals were collected by filtration, washed with water and dried to obtain 3.64 parts of blue crystals (Compound No. 53b). Decomposition temperature: 231 ° C

Example 14 (synthesis of compound No. 21b in Table 2)
Dissolve 3.1 parts of the dye of the following formula (109) in a mixed solution of 150 parts of water and 72 parts of methanol, add cesium in tristrifluoromethanesulfonium methide to a mixed solution of 6.3 parts of DMF and 16 parts of methanol while stirring. A solution of 3.55 parts salt was added. After heating and stirring for 3 hours at 40 ° C., the precipitated crystals were collected by filtration, washed with water and dried to obtain 1.63 parts of blue crystals (Compound No. 21b). Decomposition temperature: 234 ° C

Example 15 (Synthesis of Compound No. 33b in Table 2)
Dissolve 1.0 part of a dye of the following formula (110) in a mixed solution of 100 parts of water and 40 parts of methanol, add cesium in tristrifluoromethanesulfonium methide to a mixed solution of 3.2 parts of DMF and 8 parts of methanol while stirring A solution of 1.31 parts of salt was added. After heating and stirring for 3 hours at 30 ° C., the precipitated crystals were collected by filtration, washed with water and dried to obtain 0.98 parts of blue crystals (Compound No. 33b). Decomposition temperature: 232 ° C

Example 16 (synthesis of compound No. 69b in Table 2)
Dissolve 1.0 part of the dye of the following formula (111) in a mixed solution of 100 parts of water and 40 parts of methanol, add cesium in tristrifluoromethanesulfonium methide to a mixed solution of 3.2 parts of DMF and 8 parts of methanol while stirring A solution of 0.65 parts salt was added. After heating and stirring for 3 hours at 40 ° C., the precipitated crystals were collected by filtration, washed with water and dried to obtain 0.73 parts of blue crystals (Compound No. 69b). Decomposition temperature: 277 ° C

As mentioned above, the triarylmethane compound represented by the said Formula (1) of this invention is excellent in heat resistance from the comparison of the decomposition temperature, and the dye colored body has the characteristic excellent in heat-and-moisture resistance and water resistance. It has been revealed that the triarylmethane dyes of the present invention have high industrial value such as broadening the range of applications such as color filter inks and ink jet inks.

Claims

The triarylmethane compound represented by General formula (1).

(In the formula (1), Ar 1 , Ar 2 and Ar 3 each independently represent an aromatic residue bonded to a central carbon atom by a carbon atom, and X − represents a bistrifluoromethanesulfonyl imide anion or tristrifluoromethanesulfonyl Represents methide anion)
The triarylmethane compound according to claim 1, which is represented by the general formula (2).

(In formula (2), R 1a to R 6a each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group or a benzyl group, and R 7a to R 20a each independently represent a hydrogen atom or carbon And represents an alkyl group of 1 to 6 or a halogen atom, and X - is as defined in the above formula (1).
The triarylmethane compound according to claim 2, wherein X - is tristrifluoromethanesulfonyl methide anion.
The triarylmethane compound according to claim 1, which is represented by the general formula (3).

(In Formula (3), R 1b to R 4b each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group or a benzyl group, and R 5b to R 16b each independently represent a hydrogen atom or carbon represents a number 1-6 alkyl group or a halogen atom, R 17b represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a halogen atom or an amino group, X - is as defined in the above formula (1)).
5. The triarylmethane compound according to claim 4, wherein X - is tristrifluoromethanesulfonyl methide anion.
An oil dye composition comprising the triarylmethane compound according to any one of claims 1 to 5 and at least one or more oil-soluble organic solvents.
An aqueous dye composition comprising the triarylmethane compound according to any one of claims 1 to 5 and an aqueous medium.