KR20120014111A - Novel triarylmethane compound - Google Patents

Abstract

화학식(1) 중에서, Ar₁, Ar₂ 및 Ar₃은 각각 독립적으로 탄소원자에서 중심 탄소원자에 결합되어 있는 방향족 잔기를 나타내고, X^-는 비스트리플루오로메탄설포닐 이미드 음이온 또는 트리스트리플루오로메탄설포닐메티드 음이온을 나타냄. <Problem> The dye composition which has the characteristics of high clarity and color development, and is excellent in fastness, such as heat resistance, heat and humidity resistance, and water resistance, is provided.
<Solution> Triarylmethane compound represented by following General formula (1), and oil-soluble or aqueous dye composition containing this compound:

In Formula (1), Ar ₁ , Ar ₂ And Ar ₃ each independently represents an aromatic moiety bound to a central carbon atom at a carbon atom, and X ⁻ represents a bistrifluoromethanesulfonyl imide anion or a tristrifluoromethanesulfonylmethide anion.

Description

Novel triarylmethane compound

The present invention relates to novel triarylmethane compounds.

Triarylmethane-based dyes are characterized by very clear and high color development, and are used in a wide range of applications such as violet, blue, or green colorants, various paints, aqueous inks, oil inks, inkjet inks, and color filter inks. In general, the characteristics required for the colorant are different depending on the application, but the color is clear, the color development is high, and the coloring matter is required for any application in that the fastness to light, heat and the like. As the triarylmethane-based dyes, cationic dyes having a cationic group such as quaternary nitrogen in the structure and anionic dyes which have been made anionic by introducing anionic groups such as sulfone groups into the cationic dye structure are known. There is a drawback of inferior fastness such as light resistance, heat resistance, heat and humidity resistance, and water resistance.

For this reason, although the dye which has the clarity and color development of a triarylmethane dye, and high fastness is desired, the dye which has these performances is not known. Patent Document 1 describes a cationic triarylmethane compound and salt compounds of chlorine ions and arylsulfonic acid ions. As a result of the inventors' investigation, the triarylmethane compounds described in this patent document have light resistance, heat resistance and water resistance. Insufficient. Moreover, although there exist description about triaryl methane type cationic dye which has a fluorinated alkylsulfonyl counterion in patent document 2, there is no illustration of a specific compound, and also description regarding fastness, such as light resistance, heat resistance, heat and humidity resistance, and water resistance, Not. Although cationic triphenylmethane compounds and salt compounds of chlorine ions and oxalic acid ions are commercially available, these known triphenylmethane compounds have insufficient light resistance, heat resistance, moist heat resistance, and water resistance.

Prior art literature

Patent Literature

Patent Document 1: Japanese Patent Laid-Open No. 2008-304766

Patent Document 2: Japanese Patent Laid-Open No. 8-253705

Summary of the Invention

Problems to be Solved by the Invention

The present invention, as described above, is a novel triarylmethane compound having clearness and color development of triarylmethane-based dyes and excellent fastness such as light resistance, heat resistance, moist heat resistance, and water resistance, and an oily or aqueous dye using the compound. It is an object to provide a composition.

Means to solve the problem

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to solve the subject mentioned above, the present inventors found that cationic triaryl methane and the salt compound of a specific anion maintain the vividness and color development of a triaryl methane dye, and are remarkable compared with the past. As a result, it was found that the light resistance, heat resistance, heat and humidity resistance, and water resistance were improved, and the present invention was completed.

That is, the present invention relates to:

(1) Triarylmethane compounds represented by the following general formula (1):

In formula (1), Ar ₁ , Ar ₂ And Ar ₃ each independently represents an aromatic moiety bonded to a central carbon atom at a carbon atom, and X ⁻ represents a bistrifluoromethanesulfonyl imide anion or a tristrifluoromethanesulfonylmethide anion;

(2) The triarylmethane compound as described in (1) characterized by the following 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, an alkyl group having 1 to 6 carbon atoms, A halogen atom, X ⁻ has the same meaning as in formula (1);

(3) The triarylmethane compound according to (2), wherein X ⁻ is tristrifluoromethanesulfonylmethed anion;

(4) The triarylmethane compound as described in (1) characterized by the following 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, an alkyl group having 1 to 6 carbon atoms, 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, and X ⁻ has the same meaning as in formula (1);

(5) The triarylmethane compound according to (4), wherein X ⁻ is tristrifluoromethanesulfonylmethed anion;

(6) an oil 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 containing the triarylmethane compound according to any one of (1) to (5) and an aqueous solvent.

Effects of the Invention

As described above, the triarylmethane compound of the present invention exhibits excellent clarity and color development, and forms an oily or aqueous dye composition and is processed into a dye dye chromophore. 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 ink for color filters and inkjet inks.

Carrying out the invention  Form for

The triarylmethane compound of this invention is represented by the said General formula (1).

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

Of Formula (1), Ar ₁ , Ar ₂ and As an aromatic residue in Ar <_3> , For example, aromatic hydrocarbon residues, such as a phenyl group, a naphthyl group, anthryl group, a phenanthryl group, a pyrenyl group, a benzopyrenyl group; Aromatic heterocyclic residues such as pyridyl, pyrazyl, pyrimidyl, quinolyl, isoquinolyl, pyrrolyl, indorenyl, imidazolyl, carbazolyl, thienyl and furyl In particular, a phenyl group or a naphthyl group is preferable.

Of Formula (1), Ar ₁ , Ar ₂ and The phenyl group or naphthyl group in Ar _{3 may} have a substituent, and the substituent is not particularly limited, but is not limited to aliphatic hydrocarbon residue, aromatic residue, 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, aromatic oxy group which may have a substituent, carboxyl group, carbamoyl group, aldehyde group, alkoxycarbonyl group, aromatic oxycarbonyl group, etc. Can be mentioned.

X <^-> in General formula (1) represents a bistrifluoromethanesulfonyl imide anion or a tristrifluoromethanesulfonylmethion anion, Especially, a tristrifluoromethanesulfonylmethion anion is preferable.

As the triaryl methane compound of the present invention, the compound of formula (2) is preferable in view of excellent 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, an alkyl group having 1 to 6 carbon atoms, Represents a halogen atom. In the formula (2), X ⁻ represents a bistrifluoromethanesulfonyl imide anion or a tristrifluoromethanesulfonylmethion anion, and tristrifluoromethanesulfonylmethion 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 methyl group, ethyl group, propyl group, butyl group, isobutyl group, pentyl group, cyclopentyl group, hexyl group and 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 there is no restriction | limiting in particular as said substituent, As a C1-C6 alkyl group which has a substituent, For example, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, 2-sulfo Ethyl group, carboxyethyl group, cyanoethyl group, methoxyethyl group, ethoxyethyl group, butoxyethyl group, trifluoromethyl group, pentafluoroethyl group, phenylmethyl group, etc. are mentioned.

A phenyl group in R _1a ~ R _6a of the formula _(2), or benzyl group may have a substituent, as the substituent, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t- butyl group, a pentyl group Halogen atoms, such as (C1-C5) alkyl groups, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, a sulfonic acid group, a methoxy group, an ethoxy group, a propoxy group, butoxy group, t-butoxy group, hexyloxy group, etc. (C1-C6) alkoxy groups, such as these; Hydroxy (C1-C5) alkyl groups, such as a hydroxyethyl group and a hydroxypropyl group; (C1-C5) alkoxy (C1-C5) alkyl groups, such as a methoxyethyl group, an ethoxyethyl group, an ethoxypropyl group, butoxyethyl group; Hydroxy (C1-C5) alkoxy groups, such as 2-hydroxyethoxy group; (C1-C5) alkoxy (C1-C5) alkoxy groups, such as 2-methoxyethoxy group and 2-ethoxyethoxy group; 2-sulfoethyl group, carboxyethyl group, 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.

As R <_7a> -R <_20a> of general formula (2), a hydrogen atom, a halogen atom, or a C1-C6 unsubstituted alkyl group is mentioned.

In R _7a to R _20a of the formula (2), examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, butyl group, isobutyl group, pentyl group, cyclopentyl group, hexyl group and cyclohexyl group Alkyl groups, such as these, are mentioned. These alkyl groups may have a substituent and there is no restriction | limiting in particular as said substituent, As a C1-C6 alkyl group which has a substituent, For example, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, 2-sulfo Ethyl group, carboxyethyl group, cyanoethyl group, methoxyethyl group, ethoxyethyl group, butoxyethyl group, trifluoromethyl group, pentafluoroethyl group, etc. are mentioned.

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

Moreover, as a triaryl methane compound of this invention, the compound of the said General formula (3) is also preferable at the point which is excellent in fastness, such as heat resistance, moist 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, an alkyl group having 1 to 6 carbon atoms, or A halogen atom is represented, _R17b represents a hydrogen atom, a C1-C6 alkyl group, a halogen atom, or an amino group. In the formula (3), X ⁻ represents a bistrifluoromethanesulfonyl imide anion or a tristrifluoromethanesulfonylmethion anion, in particular a tristrifluoromethanesulfonylmethion anion.

In R _1b to R _4b of the formula (3), examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, butyl group, isobutyl group, pentyl group, cyclopentyl group, hexyl group and 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 there is no restriction | limiting in particular as said substituent, As a C1-C6 alkyl group which has a substituent, For example, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, 2-sulfo Ethyl group, carboxyethyl group, cyanoethyl group, methoxyethyl group, ethoxyethyl group, butoxyethyl group, trifluoromethyl group, pentafluoroethyl group, phenylmethyl group, etc. are mentioned.

In R _1b to R _4b of the general formula (3), the phenyl group or the benzyl group may have a substituent, and there is no particular limitation as the substituent, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl (C1-C5) alkyl groups such as groups, pentyl groups, fluorine atoms, chlorine atoms, bromine atoms, halogen atoms such as iodine atoms, sulfonic acid groups, methoxy groups, ethoxy groups, propoxy groups, butoxy groups, t-butoxy groups, (C1-C6) alkoxy groups such as hexyloxy group; Hydroxy (C1-C5) alkyl groups such as hydroxyethyl group and hydroxypropyl group; (C1-C5) alkoxy (C1-C5) alkyl groups such as methoxyethyl group, ethoxyethyl group, ethoxypropyl group, butoxyethyl group; Hydroxy (C1-C5) alkoxy groups such as 2-hydroxyethoxy group; Alkoxy (C1-C5) alkoxy groups, such as 2-methoxyethoxy group and 2-ethoxyethoxy group (C1-C5); 2-sulfoethyl group, carboxyethyl group, cyanoethyl group, etc. are mentioned.

As R <_1b> -R <_4b> of general formula (3), a hydrogen atom, an unsubstituted C1-C6 alkyl group, an unsubstituted phenyl group, or an unsubstituted benzyl group is preferable.

In R _5b to R _17b of the formula (3), examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, butyl group, isobutyl group, pentyl group, cyclopentyl group, hexyl group and cyclohexyl group Alkyl groups, such as these, are mentioned. These alkyl groups may have a substituent and there is no restriction | limiting in particular as said substituent, As a C1-C6 alkyl group which has a substituent, For example, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, 2-sulfo Ethyl group, carboxyethyl group, cyanoethyl group, methoxyethyl group, ethoxyethyl group, butoxyethyl group, trifluoromethyl group, pentafluoroethyl group, etc. are mentioned.

_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 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, but these may also 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 hydroxyethyl group, hydroxypropyl group, hydroxybutyl group, 2-sulfoethyl group, carboxyethyl group, cyanoethyl group, methoxyethyl group, ethoxyethyl group, and A oxyethyl group, a trifluoromethyl group, a pentafluoroethyl group, etc. are mentioned. In the case of a phenyl group or benzyl group, as a substituent, (C1-C5) alkyl groups, such as a methyl group, an ethyl group, a propyl group, isopropyl group, a butyl group, t-butyl group, a pentyl group, a fluorine atom, a chlorine atom, bromine (C1-C6) alkoxy groups such as halogen atoms such as atoms and iodine atoms, sulfonic acid groups, methoxy groups, ethoxy groups, propoxy groups, butoxy groups, t-butoxy groups and hexyloxy groups; hydroxyethyl groups and hydroxypropyl Hydroxy (C1-C5) alkyl groups such as groups; (C1-C5) alkoxy (C1-C5) alkyl groups such as methoxyethyl group, ethoxyethyl group, ethoxypropyl group, butoxyethyl group; Hydroxy (C1-C5) alkoxy groups such as 2-hydroxyethoxy group; Alkoxy (C1-C5) alkoxy groups, such as 2-methoxyethoxy group and 2-ethoxyethoxy group (C1-C5); 2-sulfoethyl group, carboxyethyl group, cyanoethyl group, etc. are mentioned.

As R <_5b> -R <_16b> of general formula (3), a hydrogen atom, a chlorine atom, or a C1-C6 unsubstituted alkyl group is preferable, and _R17b has a hydrogen atom or an amino group.

Although the triarylmethane compound of this invention can be obtained by the well-known synthesis | combining method described, for example, in Hoboda Yutaka "Theory Manufacturing Dye Chemistry" issued by Jibodang Co., Ltd., pages 781 to 787, X ^- is a chlorine anion. It can also synthesize | combine by purchasing a commercial item, adding a corresponding salt or acid, and carrying out salt exchange.

When the triarylmethane compound of the present invention is synthesized by salt exchange, a compound in which X ⁻ is chlorine anion may be reacted with a reaction solvent (for example, water or methanol, ethanol, isopropanol, acetone, N, N-dimethylformamide (hereinafter referred to as Water-soluble polar solvents such as DMF abbreviation) and N-methyl-2-pyrrolidone (hereinafter referred to as NMP abbreviation), and these solvents may be dissolved alone or in combination, and corresponding salts or acids. It can be synthesize | combined easily by adding about 0.5-3 equivalents, stirring at predetermined | prescribed temperature (for example, 0-100 degreeC), and it can obtain by filtering the precipitated crystal | crystallization.

Although the specific example of the triaryl methane compound represented by General formula (2) is shown in following Table 1, the specific example of the triaryl methane compound represented by General formula (3) is shown in following Table 2, but this invention is based on these It is not limited.

In Table 1 and Table 2, 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 Normal-butyl group is represented, sec-Bu represents a secondary butyl group, i-Pr represents an isopropyl group, CyHex represents a cyclohexyl group. Moreover, when X <^-> is (alpha), a tristrifluoromethanesulfonyl met anion is shown, and (beta) shows a bistrifluoromethanesulfonyl imide anion, respectively.

The triarylmethane compound of this invention is used for coloring compositions, such as various paint, aqueous ink, oil ink, inkjet ink, and color filter ink, as an oil dye composition or an aqueous dye composition. Oily dye compositions and aqueous dye compositions are usually used for colored materials such as paper, coated paper, plastic films, plastic substrates, and the like. Moreover, as a method of providing the dye composition of this invention to a to-be-colored material, various printing methods, such as offset printing, iron plate printing, flexographic printing, and inkjet printing, or the coating method by a spin coater, a roll coater, etc. are mentioned.

The oily or aqueous dye composition of the present invention contains an oil-soluble organic solvent in the case of the triarylmethane compound and the oily dye composition of the present invention, and an aqueous solvent in the case of an aqueous dye. In the oily or aqueous dye composition of the present invention, it is preferable to contain 0.2 to 40% by weight of the triarylmethane compound of the present invention, and more preferably 0.5 to 20% by weight. Moreover, in the oily or aqueous dye composition of this invention, you may add color materials other than the said General formula (1) as needed for the purpose of color adjustment. As a coloring material which can be added, water-soluble dyes, such as an acid dye, a reactive dye, a direct dye, a cationic dye, a basic dye, oil-soluble dyes, such as a disperse dye and a solvent dye, organic pigment, carbon black, etc. are mentioned, for example, It may be added in a dissolved state or in a dispersed state.

The aqueous dye composition of the present invention can be prepared by dispersing the triarylmethane compound of formula (1) in an aqueous medium. As an aqueous medium, water or a water-soluble organic solvent is mentioned. As a water-soluble organic solvent, For example, Alcohol, such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol, benzyl alcohol; Polyhydric alcohols such as ethylene ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, 1,3-pentanediol, and 1,5-pentanediol; Glycol derivatives such as ethylene glycol monomethyl 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 ; Amines such as ethanolamine, diethanolamine, triethanolamine and morpholine; 2-pyrrolidone, NMP, 1, 3-dimethyl- imidazolidinone, etc. are mentioned.

The oily dye composition of the present invention can be adjusted by dissolving or dispersing the triarylmethane compound of the general formula (1) in at least one oil-soluble organic solvent. As an oil-soluble organic solvent which can be used, For example, Alcohol, such as ethanol, pentanol, octanol, cyclohexanol, benzyl alcohol, tetrafluoropropanol; Ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol di Glycol derivatives such as acetate and propylene glycol diacetate; Ketones such as methyl ethyl ketone and cyclohexanone; ethers such as butyl phenyl ether, benzyl ether and hexyl ether; Esters such as ethyl acetate, butyl acetate, ethyl benzoate, butyl benzoate, ethyl laurate, and butyl laurate; And polar organic solvents such as acetonitrile, DMF, dimethyl sulfoxide, sulfolane, NMP, and 2-pyrrolidone. These solvents may be used alone or in combination of two or more thereof.

As a dispersing agent used for an oil-based dye composition, sodium dodecyl benzene sulfonate, sodium lauryl acid, the formalin condensate of naphthalene sulfonic acid, the formalin condensate of alkyl naphthalene sulfonic acid, the formalin condensate of creosote oil sulfonic acid, and polyoxyethylene Styrene, such as anionic surfactant, vinyl naphthalene derivative, and aliphatic alcohol ester of (alpha), (beta)-ethylenically unsaturated carboxylic acid, such as the ammonium salt of alkyl ether sulfate, the ammonium of polyoxyethylene alkyl phenyl ether sulfate, and the polyoxyalkyl ether phosphate ester salt At least two monomers selected from styrene derivatives, acrylic acid, acrylic acid derivatives, methacrylic acid, methacrylic acid derivatives, maleic acid, maleic acid derivatives, maleic anhydride, maleic anhydride derivatives, itaconic acid, itaconic acid derivatives, fumaric acid and fumaric acid derivatives Block copolymers, Random copolymer, or there may be mentioned a polymer dispersant such as their salts, it is preferred to use 10 to 100 weight% based on the dye compound to the dispersion thereof at least one member. In addition to these dispersants, known nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, copolymers of ethylene oxide and propylene oxide, and silicone-based and acetylene-based Known antifoaming agents can be added as necessary during pigment dispersion and / or after pigment dispersion.

 As a method of disperse | distributing a pigment to microparticles | fine-particles, the method using a sand mill (bead mill), a roll mill, a ball mill, a paint shaker, an ultrasonic disperser, a microfluidizer, etc. is mentioned, Among these, a sand mill (bead mill) is preferable. . In the grinding of the pigment in the sand mill (bead mill), it is preferable to treat the pigment in a condition of increasing the grinding efficiency by increasing the filling rate of the beads using beads having a small diameter. It is desirable to remove small particles. The dye composition of the present invention may contain, as other additives, a surface conditioner, preservative, preservative, pH adjuster, and the like. As surface-controlling agents, surfactants, preservatives and flavoring agents of polysiloxanes or polydimethylsiloxanes are sodium dehydroacetic acid, sodium benzoate, sodium pyridinethione-1-oxide, zinc pyridinethione-1-oxide, and 1,2-benziso. Amine salts of thiazolin-3-one and 1-benzisothiazolin-3-one and the like include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, triethanolamine, diethanolamine, and dimethylethanolamine. And tertiary amines such as diethylethanolamine, and the like, and each can be added as necessary.

Moreover, in the oily or aqueous dye composition of this invention, the polyamide type, polyurethane type, polyester type, epoxy type which are compatible with the medium in a composition in the required range for the purpose of improving the fixability of a pigment | dye to a to-be-adhered body. Or it is preferable to contain polyacrylic-type resin. Moreover, you may contain the monomer, oligomer, a polymerization initiator, etc. which have an ethylenically unsaturated group in a required range in order to improve fixability. 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, although an Example demonstrates this invention concretely, this invention is not limited to these Examples. In the examples, "parts" means "parts by weight" unless otherwise specified. The decomposition temperature of the various compounds obtained by the Example was measured by TG / DTA. In addition, evaluation of moisture-heat resistance, water resistance, etc. measured and evaluated the chromaticity (L value, a value, b value) of the dye color body by the following chromaticity measuring apparatus. The measurement instrument name is as follows.

1.TG/DTA(Simultaneous Thermal Gravimetric Measurement):

Seiko Instruments Co., Ltd. product name TG / DTA220

2. Chromaticity measuring device: UV-3150 manufactured by Shimadzu Corporation

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

Cesium salt of tristrifluoromethanesulfonium methide in 30 parts of acetonitrile, dissolved in 150 parts of water, 2 parts of Basic Blue 7 (manufactured by Tokyo Kasei Kogyosha Co., Ltd., decomposition temperature: 217 占 폚), and stirring A solution in which the parts were dissolved was added. After stirring for 3 hours, the precipitated crystals were filtered, washed with water and dried to obtain 1.5 parts of blue crystals (triarylmethane compound of the present invention). Decomposition Temperature: 256 ℃

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

2 parts of Basic Blue 7, of the following formula (100), were dissolved in 150 parts of water, and while stirring, a solution in which 1.2 parts of potassium salt of bistrifluoromethanesulfonium imide was dissolved in 10 parts of water was added. After stirring for 3 hours, the precipitated crystals were filtered, washed with water and dried to obtain 0.7 parts of blue crystals (triarylmethane compound of the present invention). Decomposition Temperature: 240 ℃

Example  3

Oil-Based Dye Compositions and Dyes Colored  Produce

To 10 parts of tetrafluoropropanol, compound No. 1a, compound No. 2a, and 0.5 part obtained in the above examples were dissolved, to prepare an oily dye composition. The resulting oil dye composition was spin coated on a polycarbonate basis and dried at 80 ° C. for 30 minutes to prepare a dye colorant.

In the following Table 5 and Table 9, the comparative example 1 shows the test result of having manufactured the dye coloring body similarly using Basic Blue7 of following General formula (100).

Moisture and Heat Resistance  Test 1

The dye color body obtained by the said method was left to stand for 40 hours in the thermo-hygrostat of 85 degreeC and 85% RH conditions. L value, a value, and b value were measured with the spectrophotometer at the C light source and 2 degree viewing angle with the spectrophotometer before and behind a test, and the color difference was calculated | required by the following formula. In addition, the smaller the color difference is, the smaller the change in color is, which is excellent.

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

The measured value and color difference of side color in a heat-and-moisture test are shown in following Tables 3-6.

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

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

The result of having calculated | required the color difference of the compound number 1a, the compound number 2a, and the comparative example 1 from the said Table 3-Table 5 is shown in following Table 6.

As is clear from the results in Table 6, the dye chromosome of the present invention exhibited very small values of color difference 1.4 and 1.6, while the color difference before and after the test of the dye colorant of Comparative Example 1 showed a very large value of 22.7. It can be seen that the thermal properties are extremely excellent.

Water resistance test 1

The dye coloring body obtained by the said method was left to stand in 70 degreeC warm water for 5 minutes. L value, a value, and b value of the dye colorant before and after the test were measured by C light source and 2 degree viewing angle as standard light, and the color difference was calculated | required by the following chemical formula. The smaller the color difference, the better because there is less change in color. Color difference = [(L value before test-L value after test) ² + (a value before test-a value after test) ² + (b value before test-b value after test) ² ] ^1/2

The measured value and color difference measured in the water resistance test are shown in Tables 7 to 10 below.

The colorimetry results of compound No. 1a are shown in Table 7 below.

The colorimetry results of compound No. 2a are shown in Table 8 below.

The colorimetry result of Comparative Example 1 is shown in Table 9 below.

The result of having calculated | required the color difference of the compound number 1a, the compound number 2a, and the comparative example 1 from the said Table 7-9 is shown in the following Table 10.

As is apparent from the results in Table 10, the dye colorants of the present invention showed very small values of color differences 2.0 and 7.4, while the color difference before and after the test of the dye colorant of Comparative Example 1 showed a very large value of 36.7. It can be seen that this is extremely excellent.

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

Cesium salt of tristrifluoromethanesulfonium methoxide in 20 parts of DMF was dissolved in 2 parts of Basic Blue 26 (manufactured by Tokyo Kasei Kogyosha Co., Ltd., decomposition temperature: 223 ° C) of 20 parts of DMF and stirred, and stirred. A solution in which the parts were dissolved was added. After stirring for 2 hours, the mixture was filtered and water was added to the filtrate obtained. Precipitated crystals were filtered, washed with water and dried to obtain 1.1 parts of purple crystals (triarylmethane compound of the present invention). Decomposition Temperature: 267 ℃

Example  5

Oil-Based Dye Compositions and Dyes Colored  Produce

An oil dye composition was prepared by dissolving 0.5 parts of Compound No. 5a obtained in Example 4 in 10 parts of tetrafluoropropanol. The resulting oil dye composition was spin coated on a polycarbonate basis and dried at 80 ° C. for 30 minutes to prepare a dye colorant.

In the following Table 12, the comparative example 2 shows the evaluation result of having manufactured the dye coloring body similarly using Basic Blue26 of the said General formula (101).

Moisture and Heat Resistance  Test 2

The test method is the same as that of the moist heat resistance test 1. The measured value and color difference of side color are shown to the following Tables 11-13.

The colorimetry results of compound number 5a are shown in Table 11 below.

The colorimetry result of Comparative Example 2 is shown in Table 12 below.

The result of having calculated | required the color difference of the compound number 5a and a comparative example from the said Table 11 and Table 12 is shown in following Table 13.

As apparent from the results in Table 13, the color difference before and after the test of the dye colorant of Comparative Example 2 exhibited a very large value of 6.6, whereas the dye colorant of the present invention exhibited a very small value of color difference 0.3 of It can be seen that it is extremely excellent.

Water resistance test 2

The test method is the same as the water resistance test 1. The measured value and color difference of side color are shown to the following Tables 14-16.

The colorimetry results of compound number 5a are shown in Table 14 below.

The colorimetry result of Comparative Example 2 is shown in Table 15 below.

The result of having calculated | required the color difference of the compound number 5a and the comparative example 2 from the said Table 14 and Table 15 is shown in the following Table 16.

As is clear from the results in Table 16, the color difference before and after the test of the dye colorant of Comparative Example 2 exhibited a very large value of 25.5, whereas the dye colorant of the present invention exhibited a very small value of color difference of 9.2, resulting in extremely high water resistance. It can be seen that it is excellent.

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

2.48 parts of cesium salt of tristrifluoromethanesulfonium methide in a mixed solution of 2 parts of DMF and 12 parts of methanol while dissolving 2 parts of dyes of the formula (102) in a mixed solution of 30 parts of water and 75 parts of methanol The dissolved solution was added. After heating and stirring at 60 degreeC for 3 hours, the precipitated crystal | crystallization was filtered, washed with water, and dried, and 1.3 parts of blue crystals (triaryl methane compound of this invention) were obtained. Decomposition Temperature: 262 ℃

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

2.5 parts of the dye of the formula (103) was dissolved in a mixed solution of 2 parts of water and 38 parts of methanol, and 2.87 parts of cesium salt of tristrifluoromethanesulfonium methoxide in a mixed solution of 2 parts of DMF and 12 parts of methanol while stirring. The dissolved solution was added. After heating and stirring at 60 degreeC for 3 hours, the precipitated crystal | crystallization was filtered, washed with water, and dried, and 2.8 parts of blue crystals (triaryl methane compound of this invention) were obtained. Decomposition Temperature: 269 ℃

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

3.94 parts of cesium salts of tristrifluoromethanesulfonium methoxide were added to a mixed solution of 3 parts of DMF and 25 parts of methanol while dissolving 3 parts of dyes of the following formula (104) in a mixed solution of 10 parts of water and 53 parts of methanol. The dissolved solution was added. After heating and stirring at 60 degreeC for 3 hours, the precipitated crystal | crystallization was filtered, washed with water, and dried, and 3.5 parts of blue crystals (triaryl methane compound of this invention) were obtained. Decomposition Temperature: 267 ℃

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

Dissolve 1 part of maracaite green oxalic acid salt of formula (105) (decomposition temperature: 175 ° C) in 50 parts of water, and dissolve the cesium salt of tristrifluoromethanesulfonium methoxide in 5 parts of DMF while stirring. The solution was added. After stirring for 3 hours, the precipitated crystals were filtered, washed with water and dried to obtain 0.5 parts of dark green crystals (triarylmethane compound of the present invention). Decomposition Temperature: 190 ℃

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

5 parts of Basic Blue 1 of formula (106) (decomposition temperature: 190 ° C.) was dissolved in 500 parts of water, and a solution obtained by dissolving 2 parts of cesium salt of tristrifluoromethanesulfonium methoxide in 10 parts of DMF was stirred. Added. After stirring for 3 hours, the precipitated crystals were filtered, washed with water and dried to obtain 0.7 parts of blue crystals (triarylmethane compound of the present invention). Decomposition Temperature: 230 ℃

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

5 parts of Basic Violet 3 (decomposition temperature: 205 DEG C) of the formula (107) was dissolved in 500 parts of water, and while stirring, a solution obtained by dissolving 1 part of cesium salt of tristrifluoromethanesulfonium methoxide was added to 10 parts of DMF. It was. After stirring for 3 hours, the precipitated crystals were filtered, washed with water and dried to obtain 1.2 parts of purple crystals (triarylmethane compound of the present invention). Decomposition Temperature: 240 ℃

Example  12

Oil-Based Dye Compositions and Dyes Colored  Produce

To 10 parts of tetrafluoropropanol, Compound No. 1b, Compound No. 3b, Compound No. 5b, and 0.5 parts respectively obtained in the above Examples were dissolved to prepare an oily dye composition. The resulting oil dye composition was spin coated on a polycarbonate basis and dried at 80 ° C. for 30 minutes to prepare a dye colorant.

Comparative Example 3 described in Table 17 and Table 18 uses a marachite green oxalate of Formula 105, Comparative Example 4 uses Basic Blue 1 of Formula 106, and Comparative Example 5 Dye colorants were prepared in the same manner using Basic Violet 3 of 107).

Water resistance test 3

The dye coloring body obtained by the said method was left to stand for 30 second in 70 degreeC warm water. L-value, a-value, and b-value were measured by the spectrophotometer before and after the test at the C light source and 2 degree viewing angle as a standard light, and the color difference was calculated | required from the following chemical formula. The smaller the color difference, the better because there is little change in color. Color difference = [(L value before test-L value after test) ² + (a value before test-a value after test) ² + (b value before test-b value after test) ² ] ^1/2

The measured value and color difference of side color in a water resistance test are shown in following Tables 17-23.

The colorimetry results of compound No. 1b are shown in Table 17 below.

The colorimetry results of compound number 3b are shown in Table 18 below.

The measurement result of compound No. 5b is shown in Table 19 below.

The colorimetry result of Comparative Example 3 is shown in Table 20 below.

The colorimetry result of Comparative Example 4 is shown in Table 21 below.

The colorimetry result of Comparative Example 5 is shown in Table 22 below.

The result of having calculated | required the color difference of the compound number 1b, the number 3b, the number 5b, the comparative examples 3, 4, and 5 from the said Table 17-22 is shown in the following Table 23.

As is apparent from the results in Table 23, the dye colorants of compound No. 1b of the present invention having the same cation moiety had a small color difference of 2.3 as compared with the color difference before and after the test of the dye colorant of Comparative Example 3 showing a large value of 15.5. A value is shown and it turns out that water resistance is extremely excellent. Similarly, while the color difference before and after the test of the dye colorants of Comparative Examples 4 and 5 exhibits a large value of 10.0 and 46.1, the color difference of the dye colorants of Compound Nos. 3b and 5b of the present invention is very high at 2.0 and 4.6. It shows a small value.

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

2.31 parts of the dye of the following formula (108) were dissolved in a mixed solution of 200 parts of water and 120 parts of methanol, and while stirring, a solution obtained by dissolving 2.30 parts of cesium salt of tristrifluoromethanesulfonium methoxide was added to 4.2 parts of DMF. After stirring for 3 hours, the precipitated crystals were filtered, washed with water and dried to obtain 3.64 parts of blue crystals (Compound No. 53b). Decomposition Temperature: 231 ℃

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

3.1 parts of the dye of formula (109) are dissolved in a mixed solution of 150 parts of water and 72 parts of methanol, and 3.55 parts of cesium salt of tristrifluoromethanesulfonium methoxide is dissolved in a mixed solution of 6.3 parts of DMF and 16 parts of methanol while stirring. The solution was added. After heating and stirring at 40 ° C for 3 hours, the precipitated crystals were filtered, washed with water and dried to obtain 1.63 parts of blue crystals (Compound No. 21b). Decomposition Temperature: 234 ℃

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

1.0 part of the dye of formula (110) was dissolved in a mixed solution of 100 parts of water and 40 parts of methanol, and 1.31 parts of a cesium salt of tristrifluoromethanesulfonium methoxide was dissolved in a mixed solution of 3.2 parts of DMF and 8 parts of methanol while stirring. The solution was added. After heating and stirring at 30 ° C for 3 hours, the precipitated crystals were filtered, washed with water and dried to obtain 0.98 parts of blue crystals (Compound No. 33b). Decomposition Temperature: 232 ℃

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

1.0 part of the dye of formula (111) was dissolved in a mixed solution of 100 parts of water and 40 parts of methanol, and 0.65 parts of cesium salt of tristrifluoromethanesulfonium methoxide was dissolved in a mixed solution of 3.2 parts of DMF and 8 parts of methanol while stirring. The solution was added. After heating and stirring at 40 ° C for 3 hours, the precipitated crystals were filtered, washed with water and dried to obtain 0.73 parts of blue crystals (Compound No. 69b). Decomposition Temperature: 277 ℃

As described above, the triarylmethane compound represented by the formula (1) of the present invention is excellent in heat resistance from the comparison of its decomposition temperature, and its dye colorant is excellent in moist heat resistance and water resistance. It was clear that the arylmethane dye had high industrial value, such as wide application range, such as ink for color filters and inkjet inks.

Claims (7)

Triarylmethane compounds represented by the formula (1):

Ar ₁ , Ar ₂ in Formula (1) And Ar ₃ each independently represents an aromatic moiety bonded to a central carbon atom at a carbon atom, and X ⁻ represents a bistrifluoromethanesulfonyl imide anion or a tristrifluoromethanesulfonylmethide anion. The triarylmethane compound of claim 1, represented by the following 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, an alkyl group having 1 to 6 carbon atoms, Represents a halogen atom and X <^-> has the same meaning as the said General formula (1). 3. A triarylmethane compound according to claim 2, wherein X ^- is a tristrifluoromethanesulfonylmethed anion. The triarylmethane compound of claim 1, wherein the triarylmethane compound is represented by the following 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, an alkyl group having 1 to 6 carbon atoms, 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, and X ⁻ has the same meaning as in the above formula (1). The triarylmethane compound according to claim 4, wherein X ⁻ is a tristrifluoromethanesulfonylmethed anion. An oil-based dye composition comprising the triarylmethane compound according to any one of claims 1 to 5 and at least one oil soluble organic solvent. An aqueous dye composition containing the triarylmethane compound according to any one of claims 1 to 5 and an aqueous medium.