TWI468371B - Novel triarylmethane compound - Google Patents

Description

Novel triarylmethane compounds

This invention relates to a novel triarylmethane compound.

The triarylmethane dyes are characterized by very vivid and high color rendering properties and are used as various materials for purple, blue or green colored materials, water-based inks, oil-based inks, inkjet inks, and color filter inks. And so on a wide range of uses. In general, the properties required for colored materials vary depending on the application. However, in any application, color tone is required to be vivid, and coloration is high, and the coloring matter is firmer against light and heat. A triarylmethane dye is known as a cationic dye having a cationic group such as a quaternary nitrogen in a structure; and an anionic dye such as a sulfhydryl group is introduced into the cationic dye structure to form an anionic anionic dye, whichever is Both of them have excellent color rendering properties, and on the other hand, they have disadvantages such as poor light resistance, heat resistance, moist heat resistance, and water resistance.

Therefore, the present invention is expected to have the sharpness and color developability of the triarylmethane dye, and has a high fast dye, but no dye having such properties has been found. Patent Document 1 describes a chloride of a cationic triarylmethane compound and a chloride ion or an arylsulfonate ion, but the results of studies by the inventors of the present invention are: the light resistance of the triarylmethane compound described in the patent document. Heat resistance and water resistance are insufficient. Further, Patent Document 2 describes a triarylmethane-based cationic dye having a fluorinated alkylsulfonyl-based counter ion, but there is no specific compound, and there is no light resistance, heat resistance, moist heat resistance, and water resistance. The record of firmness. Further, a chloride of a cationic triphenylmethane compound and a chloride ion or an oxalic acid ion is commercially available, but the results of studies by the inventors of the present invention are: light resistance, heat resistance, and resistance of the known triphenylmethane compounds. Wet heat and water resistance are not sufficient.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2008-304766

[Patent Document 2] Japanese Patent Laid-Open No. 8-253705

An object of the present invention is to provide a novel triarylmethane compound having excellent sharpness and color developability of a triarylmethane-based dye as described above, and excellent in light fastness, heat resistance, moist heat resistance, water resistance, and the like. An oily or aqueous dye composition of the compound.

The inventors of the present invention conducted intensive studies to solve the above problems, and found that the cationic triarylmethane and the chloride of a specific anion maintain the vividness and color rendering of the triarylmethane dye, and the former phase The present invention has been accomplished by drastically improving light resistance, heat resistance, moist heat resistance, and water resistance.

That is, the present invention relates to:

(1) A triarylmethane compound represented by the formula (1):

[Chemical 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 bis(trifluoromethanesulfonyl)imide anion or Tris(trifluoromethanesulfonate) methide anion);

(2) A triarylmethane compound of (1), which is represented by the formula (2):

[Chemical 2]

(In the 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 and a carbon number of 1 to 6; An alkyl group, a halogen atom; the meaning of X ^{- is} the same as the above formula (1));

(3) A triarylmethane compound according to (2), wherein X ^- is a tris(trifluoromethanesulfonate) methide anion;

(4) A triarylmethane compound of (1), which is represented by the formula (3):

[Chemical 3]

(In the 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 and a carbon number of 1 to 6; An 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 amine group, and X ^{- has} the same meaning as in the above formula (1));

(5) A triarylmethane compound according to (4), wherein X ^- is a tris(trifluoromethanesulfonate) methide anion;

(6) An oil-based dye composition containing 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.

The triarylmethane compound of the present invention is excellent in sharpness and color developability as described above, and when the oil-based or aqueous dye composition is formed and the dye-colored body is processed, it exhibits more excellent fastness characteristics than the prior art. That is, the triarylmethane compound of the present invention can be used for dye colorants, and can be applied to a wide range of applications such as inks for color filters or inks for inkjet.

The triarylmethane compound of the present invention is represented by the above 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.

Examples of the aromatic residue in Ar ₁ , Ar ₂ and Ar ₃ in the formula (1) include aromatic hydrocarbon residues such as a phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a fluorenyl group and a benzofluorenyl group. Pyridyl, pyridyl An aromatic heterocyclic residue such as a pyridyl group, a pyrimidinyl group, a quinolyl group, an isoquinolyl group, a pyrrolyl group, a pseudoindolyl group, an imidazolyl group, a carbazolyl group, a thienyl group or a furyl group, etc., particularly preferably a phenyl group, Or naphthyl.

The phenyl group or the naphthyl group in Ar ₁ , Ar ₂ and Ar ₃ of the formula (1) may have a substituent, and the substituent is not particularly limited, and examples thereof include an aliphatic hydrocarbon residue, an aromatic residue, and a cyano group. , isocyano group, thiocyanate group, isothiocyanate group, nitro group, mercapto group, halogen atom, hydroxyl group, substituted or unsubstituted amine group, alkoxy group, alkoxyalkyl group, may have a substituent An aromatic oxy group, a carboxyl group, an amine carbaryl group, an aldehyde group, an alkoxycarbonyl group, an aromatic oxycarbonyl group or the like.

Of formula X (1) in the ^- methylation represents bis (trifluoromethanesulfonyl XI) imide anion or a tris (trifluoromethanesulfonyl XI) methide anion, which preferably is tris (trifluoromethanesulfonyl XI) was Anion.

The triarylmethane compound of the present invention is preferably a compound of the above formula (2) in terms of excellent fastness such as heat resistance, moist heat resistance and water resistance. In the 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 and an alkyl group having 1 to 6 carbon atoms. , halogen atom. Further, X ^- in the formula (2) represents a bis(trifluoromethanesulfonyl)imide anion or a tris(trifluoromethanesulfonate) methide anion, and particularly preferably a tris(trifluoromethanesulfonate) methide Anion.

In the examples of R _1a to R _6a in 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 and a hexyl group. An alkyl group such as cyclohexyl, 1-ethylpropyl, 1-methylpropyl or 1,2-dimethylpropyl. The alkyl group may have a substituent, and the substituent is not particularly limited. Examples of the alkyl group having 1 to 6 carbon atoms having a substituent include a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, and a 2-sulfonyl group. Ethyl ethyl, carboxyethyl, cyanoethyl, methoxyethyl, ethoxyethyl, butoxyethyl, trifluoromethyl, pentafluoroethyl, phenylmethyl 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, a butyl group, and a third group. a butyl group, a pentyl group or the like (carbon number: 1 to 5) alkyl group, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, a sulfonic acid group, a methoxy group, an ethoxy group, a propoxy group or a butoxy group. , a third alkoxy group, a hexyloxy group or the like (carbon number 1 to 6) alkoxy group; a hydroxyethyl group, a hydroxypropyl group or the like hydroxyl group (carbon number 1 to 5) alkyl group; a methoxyethyl group, an ethoxy group Ethyl, ethoxypropyl, butoxyethyl, etc. (carbon number 1 to 5) alkoxy group (carbon number 1 to 5) alkyl group; 2-hydroxyethoxy group and other hydroxyl group (carbon number 1 to 5) Alkoxy; 2-methoxyethoxy, 2-ethoxyethoxy, etc. (carbon number 1-5) alkoxy (carbon number 1-5) alkoxy; 2-sulfoethyl, Carboxyethyl, cyanoethyl and the like.

Among R _1a to R _6a in 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 are preferred.

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

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 and a hexyl group. An alkyl group such as cyclohexyl. The alkyl group may have a substituent, and the substituent is not particularly limited. Examples of the alkyl group having 1 to 6 carbon atoms having a substituent include a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, and a 2-sulfonyl group. Ethyl ethyl, carboxyethyl, cyanoethyl, methoxyethyl, ethoxyethyl, butoxyethyl, trifluoromethyl, pentafluoroethyl and the like.

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

Further, the triarylmethane compound of the present invention is preferably a compound of the above formula (3) in terms of excellent fastness such as heat resistance, moist heat resistance and water resistance. In the 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 and an alkyl group having 1 to 6 carbon atoms. Or a halogen atom, and R _17b represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a halogen atom or an amine group. Further, X ^- in the formula (3) represents a bis(trifluoromethanesulfonyl)imide anion or a tris(trifluoromethanesulfonate) methide anion, and particularly preferably a tris(trifluoromethanesulfonate) methide Anion.

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 and a hexyl group. An alkyl group such as cyclohexyl, 1-ethylpropyl, 1-methylpropyl or 1,2-dimethylpropyl. The alkyl group may have a substituent, and the substituent is not particularly limited. Examples of the alkyl group having 1 to 6 carbon atoms having a substituent include a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, and a 2-sulfonyl group. Ethyl ethyl, carboxyethyl, cyanoethyl, methoxyethyl, ethoxyethyl, butoxyethyl, trifluoromethyl, pentafluoroethyl, phenylmethyl and the like.

In R _1b to R _4b of the 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, an isopropyl group, and a butyl group. a (C1~C5) alkyl group such as a tributyl group or a pentyl group, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, a sulfonic acid group, a methoxy group, an ethoxy group, a propoxy group or a butoxy group. a (C1~C6) alkoxy group such as a benzyl group, a third butyloxy group or a hexyloxy group; a hydroxy group (C1-C5) alkyl group such as a hydroxyethyl group or a hydroxypropyl group; a methoxyethyl group and an ethoxyethyl group; (C1~C5) alkoxy (C1~C5) alkyl group such as ethoxypropyl group, butoxyethyl group; hydroxyl (C1~C5) alkoxy group such as 2-hydroxyethoxy group; 2-methoxyB (C1~C5) alkoxy (C1~C5) alkoxy group such as an oxy group or a 2-ethoxyethoxy group; 2-sulfoethyl group, carboxyethyl group, cyanoethyl group or the like.

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

In R _5b to R _17b 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 and a hexyl group. An alkyl group such as cyclohexyl. The alkyl group may have a substituent, and the substituent is not particularly limited. Examples of the alkyl group having 1 to 6 carbon atoms having a substituent include a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, and a 2-sulfonyl group. Ethyl ethyl, carboxyethyl, cyanoethyl, methoxyethyl, ethoxyethyl, butoxyethyl, trifluoromethyl, pentafluoroethyl and the like.

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

The amine group in R _17b of the formula (3) may have a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a phenyl group or a benzyl group, and these may further have a substituent, and the substituent may further have a substituent. The alkyl group having 1 to 6 carbon atoms having a substituent may, for example, be a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a 2-sulfoethyl group, a carboxyethyl group or a cyanoethyl group. , methoxyethyl, ethoxyethyl, butoxyethyl, trifluoromethyl, pentafluoroethyl 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 a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group or a pentyl group. a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, a sulfonic acid group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a third butoxy group, a hexyloxy group or the like (C1 to C6) Alkoxy; hydroxyethyl, hydroxypropyl and the like hydroxy (C1~C5) alkyl; methoxyethyl, ethoxyethyl, ethoxypropyl, butoxyethyl, etc. (C1~C5) Alkoxy (C1~C5) alkyl; hydroxyl (C1~C5) alkoxy group such as 2-hydroxyethoxy; 2-methoxyethoxy, 2-ethoxyethoxy, etc. (C1~C5) Alkoxy (C1~C5) alkoxy; 2-sulfoethyl, carboxyethyl, cyanoethyl and the like.

R _5b to R _{16b of the} formula (3) are preferably a hydrogen atom, a chlorine atom or an unsubstituted alkyl group having 1 to 6 carbon atoms, and R _{17b is} preferably a hydrogen atom or an amine group.

The triarylmethane compound of the present invention can be obtained, for example, by the well-known synthesis method described in "Theory for the manufacture of dye chemistry" (pages 781 to 787) issued by Hiroshi Tetsuya Co., Ltd., or by the following means. Synthesis: Commercially available products in which X ^- is a chlorine anion are purchased, and a corresponding salt or acid is added for salt exchange.

In the case of synthesizing the triarylmethane compound of the present invention by salt exchange, it can be obtained by dissolving a compound in which X ^- is a chlorine anion is dissolved in a reaction solvent (for example, water, or methanol, ethanol, or isopropyl alcohol) Alcohol, acetone, N,N-dimethylformamide (hereinafter abbreviated as DMF), water-soluble polar solvent such as N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP), these solvents may be used alone or mixed When it is used, the corresponding salt or acid is added in an amount of about 0.5 to 3 equivalents, and stirred at a specific temperature (for example, 0 to 100 ° C) to be easily synthesized, and the precipitated crystals are removed by filtration.

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

In Tables 1 and 2, with respect to the substituent R, Me represents a methyl group, Et represents an ethyl group, Ph represents a phenyl group, Bz represents a benzyl group, CF ₃ represents a trifluoromethyl group, and n-Bu represents an n-butyl group, sec- Bu represents a second butyl group, i-Pr represents an isopropyl group, and CyHex represents a cyclohexyl group. Further, on the X ^- in the case when the lines α represents the tris (trifluoromethanesulfonyl XI) methide anion, in X ^- represents bis (trifluoromethanesulfonyl XI) imide anion based on the case where β.

The triarylmethane compound of the present invention is used as an oil-based dye composition or an aqueous dye composition, and is used in various coloring compositions such as paints, aqueous inks, oil-based inks, inks for inkjets, and inks for color filters. The oily dye composition and the aqueous dye composition can be used for coloring materials such as plain paper, coat paper, plastic film, plastic substrate, and the like. Further, examples of the method of imparting the dye composition of the present invention to a material to be colored include various printing methods such as offset printing, letterpress printing, flexographic printing, and inkjet printing, or spin coating. Coating method such as machine or roll coater.

The oily or aqueous dye composition of the present invention contains the triarylmethane compound of the present invention and an oil-soluble organic solvent in the case of an oily dye composition, and the triarylmethane compound and aqueous medium of the present invention in the case of an aqueous dye. . The oily or aqueous dye composition of the present invention preferably contains 0.2 to 40% by weight, more preferably 0.5 to 20% by weight, based on the triarylmethane compound of the present invention. Further, in the oily or aqueous dye composition of the present invention, in order to adjust the color tone or the like, a colored material other than the above formula (1) may be added as needed. Examples of the coloring material 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. It is added in a state of being dissolved in a solvent or in a state of being dispersed.

As the aqueous dye composition of the present invention, the triarylmethane compound of the above formula (1) can be prepared by dispersing it in an aqueous medium. As an aqueous medium, water or a water-soluble organic solvent is mentioned. Examples of the water-soluble organic solvent include alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, pentanol, and benzyl alcohol; ethylene glycol and diethylene glycol; , triethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerol, trimethylolpropane, 1,3-pentanediol, 1,5-pentanediol and other polyols; ethylene glycol a diol derivative such as methyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, dipropylene glycol monomethyl ether or the like Ethanolamine, diethanolamine, triethanolamine, An amine such as a phenyl group; 2-pyrrolidone, NMP, 1,3-dimethyl-imidazolidinone or the like.

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 of oil-soluble organic solvents. Examples of the oil-soluble organic solvent that can be used include alcohols such as ethanol, pentanol, octanol, cyclohexanol, benzyl alcohol, and tetrafluoropropanol; ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, and a glycol derivative such as ethylene glycol monobutyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol diacetate, propylene glycol diacetate; methyl Ketones such as ethyl ketone and cyclohexanone; ethers such as butyl phenyl ether, benzyl ether and hexyl ether; ethyl acetate, butyl acetate, ethyl benzoate, butyl benzoate, ethyl laurate, lauric acid An ester such as butyl ester; a polar organic solvent such as acetonitrile, DFM, dimethyl hydrazine, cyclobutyl hydrazine, NMP or 2-pyrrolidone. These solvents may be used singly or in combination of two or more.

Examples of the dispersing agent which can be used in the oily dye composition include sodium dodecylbenzenesulfonate, sodium laurate, formaldehyde condensate of naphthalenesulfonic acid, formaldehyde condensate of alkylnaphthalenesulfonic acid, and sulfonic acid sulfonic acid. a known anionic surfactant such as a formaldehyde condensate, an ammonium salt of a polyoxyethylene alkyl ether sulfate, an ammonium polyoxyethylene alkyl phenyl ether sulfate, a polyoxyalkyl ether phosphate salt, etc.; An aliphatic alcohol ester of an α,β-ethylenically unsaturated carboxylic acid, etc., styrene, a styrene derivative, an acrylic acid, an acrylic acid derivative, a methacrylic acid, a methacrylic acid derivative, a maleic acid, a cis At least 2 selected from the group consisting of a butenedioic acid derivative, a maleic anhydride, a maleic anhydride derivative, an itaconic acid, an itaconic acid derivative, a fumaric acid, a fumaric acid derivative, and the like A block copolymer of the above monomers, a random copolymer, or a polymer dispersant such as a salt thereof, is preferably used in an amount of 10 to 100% by weight based on the dispersed pigment compound. More than one species. Optionally, when the pigment is dispersed and/or after the pigment is dispersed, the polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, epoxy is added together with the dispersing agent. A well-known nonionic surfactant such as a copolymer of ethane and propylene oxide, or a known antifoaming agent of an oxime type or an acetylene type.

Examples of the method of dispersing the pigment in the fine particles include a sand mill (bead mill), a roll mill, a ball mill, a paint shaker, an ultrasonic disperser, and a high-pressure microfluidizer. Among these, a sand mill (bead mill) is preferred. Further, in the case of pulverizing the pigment in the sand mill (bead mill), it is preferred to carry out the treatment under conditions in which the pulverization efficiency is improved by using beads having a small particle size, increasing the filling ratio of the beads, and the like. After the pulverization treatment, the elementary particles are removed by filtration, centrifugation or the like. The dye composition of the present invention may contain a surface conditioner, a preservative, a mold inhibitor, a pH adjuster, and the like as other additives. Examples of the surface conditioning agent include polyoxyalkylene-based or polydimethyloxane-based surfactants; and examples of the antiseptic and anti-mold agents include sodium dehydroacetate, sodium benzoate, and pyrithione-1-oxide. , pyrithione-1-zinc oxide, 1,2-benzisothiazolin-3-one, 1-benzisothiazolin-3-one amine salt, etc.; as a pH adjuster, exemplified by oxidation An alkali metal hydroxide such as sodium, potassium hydroxide or lithium hydroxide; a tertiary amine such as triethanolamine, diethanolamine, dimethylethanolamine or diethylethanolamine, and may be added as needed.

Further, in the oil-based or aqueous dye composition of the present invention, in order to improve the fixability of the pigment to the colored body, it is preferred to contain a polyamine-based compound which is compatible with the medium in the composition within a necessary range. A urethane type, a polyester type, an epoxy type or a polyacrylic type resin. Further, in order to improve the fixability, a monomer having an ethylenically unsaturated group, an oligomer or a polymerization initiator may be contained in an essential range. The oily or aqueous dye composition of the present invention can be prepared by dissolving or dispersing and mixing the above components in a solvent.

Example

Hereinafter, the present invention will be specifically described by way of examples, but the invention is not limited to the examples. In addition, in the examples, "parts" means "parts by weight" unless otherwise specified. The decomposition temperatures of the various compounds obtained in the examples were determined by TG/DTA. Further, the evaluation of the moist heat resistance, the water resistance, and the like was carried out by measuring the chromaticity (L value, a value, and b value) of the dye colored body by the following colorimetric measuring device. The measurement device name is as follows.

1. TG/DTA (indicating simultaneous measurement of thermal weight): trade name TG/DAT 220 manufactured by Seiko Instruments

2. Chroma measurement device: UV-3150 manufactured by Shimadzu Corporation

Example 1 (Synthesis of Compound No. 1a in Table 1)

2 parts of Basic Blue 7 (manufactured by Tokyo Chemical Industry Co., Ltd., decomposition temperature: 217 ° C) of the following formula (100) was dissolved in 150 parts of water, and while stirring, 30 parts of acetonitrile was added to dissolve tris(trifluoromethanesulfonate).醯) A solution of 2.1 parts of the mash of the methide. After stirring for 3 hours, the precipitated crystals were taken out by filtration, washed with water and dried to obtain 1.5 parts of a blue crystal (triarylmethane compound of the present invention). Decomposition temperature: 256 ° C.

Example 2 (Synthesis of Compound No. 2a in Table 1)

Two parts of Basic Blue 7 of the following formula (100) were dissolved in 150 parts of water, and while stirring, 1.2 parts of potassium salt of bis(trifluoromethanesulfonate)imide was dissolved in 10 parts of water. Solution. After stirring for 3 hours, the precipitated crystals were taken out by filtration, washed with water, and dried to obtain a blue crystal (triarylmethane compound of the present invention) of 0.7 part. Decomposition temperature: 240 ° C.

Example 3 Preparation of oily dye composition and dye coloring body

To the 10 parts of tetrafluoropropanol, 0.5 part of the compound No. 1a and the compound No. 2a obtained in the above examples were 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 body.

In addition, Comparative Example 1 in the following Tables 5 and 9 shows the test results of the preparation of the dye-colored body by using the basic blue 7 of the following formula (100).

[Chemical 4]

Moisture and heat resistance test 1

The dye colored body obtained by the above method was allowed to stand in a constant temperature and humidity machine at 85 ° C and 85% RH for 40 hours. The color difference L value, the a value, and the b value of the dye coloring body before and after the test were measured by a spectrophotometer using a C light source as a standard light and a viewing angle of 2 degrees, and the color difference was obtained by the following formula. Further, the smaller the color difference, the more excellent the change in hue is.

Color difference = [(L value before test - L value after test) ² + (a value before test - value a after test) ² + (b value before test - b value after test) ² ] ^1/2

The measured values and color differences of the color measurement in the damp heat resistance test are shown in Tables 3 to 6 below.

The color measurement results of Compound No. 1a are shown in Table 3 below.

The color measurement results of Compound No. 2a are shown in Table 4 below.

The colorimetric results of Comparative Example 1 are shown in Table 5 below.

The results of the color difference of the compound No. 1a, the compound No. 2a and the comparative example 1 obtained from the above Tables 3 to 5 are shown in Table 6 below.

As is clear from the results of Table 6, the color difference of the dye-colored body of Comparative Example 1 before and after the test showed a very large value of 22.7. On the other hand, the color difference of the dye-colored body of the present invention was 1.4 and 1.6, which showed a very small value. Therefore, the heat and humidity resistance is extremely excellent.

Water resistance test 1

The dye coloring body obtained by the above method was allowed to stand in warm water of 70 ° C for 5 minutes. The color difference L value, the a value, and the b value of the dye coloring body before and after the test were measured by a spectrophotometer using a C light source as a standard light and a viewing angle of 2 degrees, and the color difference was obtained by the following formula. Further, the smaller the color difference, the more excellent the change in hue is. Color difference = [(pre-test L value - L value after test) ² + (a value before test - value a after test) ² + (b value before test - b value after test) ² ] ^1/2 .

The measured values and color differences of the color measurement in the water resistance test are shown in Tables 7 to 10 below.

The color measurement results of Compound No. 1a are shown in Table 7 below.

The color measurement results of Compound No. 2a are shown in Table 8 below.

The colorimetric results of Comparative Example 1 are shown in Table 9 below.

The results of the color difference of the compound No. 1a, the compound No. 2a and the comparative example 1 obtained from the above Tables 7 to 9 are shown in Table 10 below.

As is clear from the results of Table 10, the dye coloring body of Comparative Example 1 showed a very large value of 36.7 before and after the test, whereas the color difference of the dye colored body of the present invention showed a very small value of 2.0 and 7.4. Therefore, the water resistance is extremely excellent.

Example 4 (Synthesis of Compound No. 5a in Table 1)

2 parts of Basic Blue 26 (manufactured by Tokyo Chemical Industry Co., Ltd., decomposition temperature: 223 ° C) of the following formula (101) were dissolved in 20 parts of DMF, and while being stirred, 3 (trifluoromethyl) was dissolved in 20 parts of DMF. A solution of 2.5 parts of sulfonium sulfonate methoxide. After stirring for 2 hours, the solution was filtered, and water was added to the obtained filtrate. The precipitated crystals were taken out by filtration, washed with water, and dried to obtain a purple crystal (triarylmethane compound of the present invention) of 1.1 parts. Decomposition temperature: 267 ° C.

[Chemical 5]

Example 5 Preparation of oily dye composition and dye coloring body

An oily dye composition was prepared by dissolving 0.5 part of the compound No. 5a obtained in the above Example 4 in 10 parts of tetrafluoropropanol. 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 body.

In addition, Comparative Example 2 in the following Table 12 shows the evaluation results of the case where the dyed color body was prepared in the same manner using the basic blue 26 of the above formula (101).

Moisture and heat resistance test 2

The test method was the same as the heat and humidity resistance test 1. The measured values and color differences of the color measurement are shown in Tables 11 to 13 below.

The color measurement results of Compound No. 5a are shown in Table 11 below.

The colorimetric results of Comparative Example 2 are shown in Table 12 below.

The results of the color difference of the compound No. 5a and the comparative example obtained from the above Tables 11 and 12 are shown in Table 13.

As is clear from the results of Table 13, the dye color of Comparative Example 2 showed a very large value of 6.6 before and after the test. On the other hand, the color difference of the dye colored body of the present invention was 0.3, which showed a very small value, and thus resistant. Extremely hot and humid.

Water resistance test 2

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

The color measurement results of Compound No. 5a are shown in Table 14 below.

The colorimetric results of Comparative Example 2 are shown in Table 15 below.

The results of the color difference of Compound No. 5a and Comparative Example 2 obtained based on the above Tables 14 and 15 are shown in Table 16 below.

As is clear from the results of Table 16, the dye coloring body of Comparative Example 2 showed a very large value with a color difference of 25.5 before and after the test. On the other hand, the color difference of the dye colored body of the present invention showed a very small value of 9.2, and thus water resistance. Extremely excellent.

Example 6 (Synthesis of Compound No. 45a in Table 1)

2 parts of the dye of the following formula (102) was dissolved in a mixed solution of 30 parts of water and 75 parts of methanol, and while being stirred, 3 (trifluoromethanesulfonate) was dissolved in a mixed solution of 2 parts of DMF and 12 parts of methanol. A solution of 2.48 parts of the methoxide bismuth salt. After heating and stirring at 60 ° C for 3 hours, the precipitated crystals were taken out by filtration, washed with water and dried to obtain 1.3 parts of a blue crystal (triarylmethane compound of the present invention). Decomposition temperature: 262 ° C.

[Chemical 6]

Example 7 (Synthesis of Compound No. 57a in Table 1)

2.5 parts of the dye of the following formula (103) was dissolved in a mixed solution of 2 parts of water and 38 parts of methanol, and while being stirred, 3 (trifluoromethanesulfonate) was dissolved in a mixed solution of 2 parts of DMF and 12 parts of methanol. A solution of 2.87 parts of a methoxide bismuth salt. After heating and stirring at 60 ° C for 3 hours, the precipitated crystals were taken out by filtration, washed with water and dried to obtain 2.8 parts of a blue crystal (triarylmethane compound of the present invention). Decomposition temperature: 269 ° C.

[Chemistry 7]

Example 8 (Synthesis of Compound No. 69a in Table 1)

3 parts of the dye of the following formula (104) was dissolved in a mixed solution of 10 parts of water and 53 parts of methanol, and while being stirred, 3 (trifluoromethanesulfonate) was dissolved in a mixed solution of 3 parts of DMF and 25 parts of methanol. A solution of 2.94 parts of a methicone salt. After heating and stirring at 60 ° C for 3 hours, the precipitated crystals were taken out by filtration, washed with water and dried to obtain 3.5 parts of a blue crystal (triarylmethane compound of the present invention). Decomposition temperature: 267 ° C.

[化8]

Example 9 (Synthesis of Compound No. 1b in Table 2)

1 part of the peacock oxalate salt of the following formula (105) (decomposition temperature: 175 ° C) was dissolved in 50 parts of water, and while stirring, a tris(trifluoromethanesulfonate)methyl group was dissolved in 5 parts of DMF. A solution of 2 parts of the salt of the compound. After stirring for 3 hours, the precipitated crystals were taken out by filtration, washed with water and dried to obtain a dark green crystal (triarylmethane compound of the present invention) of 0.5 part. Decomposition temperature: 190 ° C.

Example 10 (Synthesis of Compound No. 3b in Table 2)

5 parts of basic blue 1 (decomposition temperature: 190 ° C) of the following formula (106) was dissolved in 500 parts of water, and while stirring, tris(trifluoromethanesulfonate) methide was dissolved in 10 parts of DMF. A solution of 2 parts of salt. After stirring for 3 hours, the precipitated crystals were taken out by filtration, washed with water, and dried to obtain a blue crystal (triarylmethane compound of the present invention) of 0.7 part. Decomposition temperature: 230 ° C.

Example 11 (Synthesis of Compound No. 5b in Table 2)

5 parts of Basic Violet 3 (decomposition temperature: 205 ° C) of the following formula (107) was dissolved in 500 parts of water, and while stirring, tris(trifluoromethanesulfonate) methoxide was dissolved in 10 parts of DMF. A solution of 1 part of the salt. After stirring for 3 hours, the precipitated crystals were taken out by filtration, washed with water and dried to obtain 1.2 parts of a purple crystal (triarylmethane compound of the present invention). Decomposition temperature: 240 ° C.

Example 12 Preparation of oily dye composition and dye coloring body

To the 10 parts of tetrafluoropropanol, 0.5 parts of the compound No. 1b, the compound No. 3b and the compound No. 5b obtained in the above respective examples were 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 body.

In Comparative Example 3 described in the following Tables 17 and 18, the peacock oxalate salt of the following formula (105) was used, and in Comparative Example 4, the basic blue 1 of the following formula (106) was used, and the comparative example 5 was used. Basic violet 3 of the following formula (107), and a dye coloring body was prepared in the same manner.

[Chemistry 9]

[化10]

[11]

Water resistance test 3

The dye colored body obtained by the above method was allowed to stand in warm water of 70 ° C for 30 seconds. The color difference L value, the a value, and the b value of the dye coloring body before and after the test were measured by a spectrophotometer using a C light source as a standard light and a viewing angle of 2 degrees, and the color difference was obtained by the following formula. Further, the smaller the color difference, the more excellent the change in hue is. Color difference = [(pre-test L value - L value after test) ² + (a value before test - value a after test) ² + (b value before test - b value after test) ² ] ^1/2 .

The measured values and color differences of the color measurement in the water resistance test are shown in Tables 17 to 23 below.

The color measurement results of Compound No. 1b are shown in Table 17 below.

The color measurement results of Compound No. 3b are shown in Table 18 below.

The color measurement results of Compound No. 5b are shown in Table 19 below.

The colorimetric results of Comparative Example 3 are shown in Table 20 below.

The colorimetric results of Comparative Example 4 are shown in Table 21 below.

The colorimetric results of Comparative Example 5 are shown in Table 22 below.

The results of the color difference of the compound No. 1b, No. 3b, No. 5b, and Comparative Examples 3, 4 and 5 based on the above Tables 17 to 22 are shown in Table 23 below.

As is clear from the results of Table 23, the color difference of the dye-colored body of Comparative Example 3 before and after the test showed a large value of 15.5, whereas the color difference of the dye-colored body of the compound No. 1b of the present invention having the same cationic portion was 2.3 shows a small value, so the water resistance is extremely excellent. Similarly, the dyes of Comparative Examples 4 and 5 showed a large difference in color difference between 10.0 and 46.1 before and after the test, whereas the color difference of the dyed bodies of Compound No. 3b and No. 5b of the present invention was 2.0. 4.6 shows a very small value.

Example 13 (Synthesis of Compound No. 53b in Table 2)

2.31 parts of the dye of the following formula (108) was dissolved in a mixed solution of 200 parts of water and 120 parts of methanol, and while stirring, a cesium salt of tris(trifluoromethanesulfonate) methoxide dissolved in 4.2 parts of DMF was added thereto. 2.30 parts of the solution. After stirring for 3 hours, the precipitated crystals were taken out by filtration, washed with water and dried to give 3.64 parts of blue crystals (Compound No. 53b). Decomposition temperature: 231 ° C.

[化12]

Example 14 (Synthesis of Compound No. 21b in Table 2)

3.1 parts of the dye of the following formula (109) was dissolved in a mixed solution of 150 parts of water and 72 parts of methanol, and while being stirred, a solution of 6.3 parts of DMF and 16 parts of methanol was added to dissolve tris(trifluoromethanesulfonate). a solution of 3.55 parts of the methoxide strontium salt. After heating and stirring at 40 ° C for 3 hours, the precipitated crystals were taken out by filtration, washed with water and dried to obtain 1.63 parts of blue crystals (Compound No. 21b). Decomposition temperature: 234 ° C.

[Chemistry 13]

Example 15 (Synthesis of Compound No. 33b in Table 2)

1.0 part of the dye of the following formula (110) was dissolved in a mixed solution of 100 parts of water and 40 parts of methanol, and while being stirred, was added to a mixed solution of 3.2 parts of DMF and 8 parts of methanol to dissolve tris(trifluoromethanesulfonate). A solution of 1.31 parts of the sulfonium salt of the methylate. After heating and stirring at 30 ° C for 3 hours, the precipitated crystals were taken out by filtration, washed with water, and dried to obtain a crystal of blue crystals (Compound No. 33b). Decomposition temperature: 232 ° C.

[Chemistry 14]

Example 16 (Synthesis of Compound No. 69b in Table 2)

1.0 part of the dye of the following formula (111) was dissolved in a mixed solution of 100 parts of water and 40 parts of methanol, and while being stirred, tris(trifluoromethanesulfonate) was dissolved in a mixed solution of 3.2 parts of DMF and 8 parts of methanol. A solution of 0.65 parts of the sulfonium salt of the methylate. After heating and stirring at 40 ° C for 3 hours, the precipitated crystals were taken out by filtration, washed with water and dried to obtain 0.73 parts of a blue crystal (Compound No. 69b). Decomposition temperature: 277 ° C

[化15]

As described above, it is clear that the triarylmethane compound represented by the above formula (1) is excellent in heat resistance according to the comparison of the decomposition temperature thereof, and the dye-colored body has characteristics excellent in moist heat resistance and water resistance. The triarylmethane-based dye-based color filter ink or inkjet ink has a wide industrial range and the like.

Claims (4)

A triarylmethane compound represented by the formula (2): (In the 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 and a carbon number of 1 to 6; alkyl group, a halogen atom; X ^- anion is tris (trifluoromethanesulfonyl XI) methide). A triarylmethane compound represented by the formula (3): [Chem. 18] (In the 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 and a carbon number of 1 to 6; An 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 amine group, and X ^- is a tris(trifluoromethanesulfonate) methide anion). An oily dye composition comprising the triarylmethane compound of claim 1 or 2 and at least one or more oil-soluble organic solvent. An aqueous dye composition comprising the triarylmethane compound of claim 1 or 2 and an aqueous medium.