JP5442004B2 - Novel triarylmethane compounds - Google Patents

Description

  The present invention relates to a novel triarylmethane compound.

  Triarylmethane dyes are very clear and have high color developability, and are used in a wide range of violet, blue or green color materials such as various paints, water-based inks, oil-based inks, inkjet inks, and color filter inks. Used in. In general, the characteristics required of color materials differ depending on the application, but the hue is clear, the color is high, and the colored material is robust against light, heat, etc. . As triarylmethane dyes, there are known cationic dyes having a cation group such as quaternary nitrogen in the structure, and anionic dyes having anionic groups such as sulfone groups introduced into the cationic dye structure. However, all of them have excellent color developability, but have the disadvantage of poor fastness such as light resistance, heat resistance, moist heat resistance, and water resistance.

  For this reason, there is a demand for dyes having the sharpness and color developability of triarylmethane dyes and having high fastness, but no dyes having these performances have been found. Patent Document 1 describes a salt compound of a cationic triarylmethane compound and a chloride ion or an arylsulfonate ion. As a result of studies by the present inventors, the triarylmethane described in this patent document is disclosed. The compound was insufficient in light resistance, heat resistance and water resistance. Patent Document 2 discloses a triarylmethane-based cationic dye having a fluorinated alkylsulfonyl counter ion, but there is no specific compound exemplified, and light resistance, heat resistance, moist heat resistance, water resistance, etc. There is no mention of robustness. Further, although salt compounds of cationic triphenylmethane compounds and chloride ions or oxalate ions are commercially available, as a result of the study by the present inventors, these known triphenylmethane compounds are light resistant, heat resistant, moisture resistant. The heat resistance and water resistance were insufficient.

JP 2008-304766 A JP-A-8-253705

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

  As a result of intensive research aimed at solving the problems described above, the present inventors have found that a salt compound of a cationic triarylmethane and a specific anion maintains the sharpness and color development of a triarylmethane dye. In addition, the present inventors have found that light resistance, heat resistance, moist heat resistance, and water resistance are drastically improved as compared with the prior art, and completed the present invention.

（式（１）においてＡｒ_１、Ａｒ_２およびＡｒ_３はそれぞれ独立に炭素原子で中心炭素原子に結合している芳香族残基を表し、Ｘ⁻はビストリフルオロメタンスルホニルイミドアニオンまたはトリストリフルオロメタンスルホニルメチドアニオンを表す。）
（２）一般式（２）で表される事を特徴とする（１）に記載のトリアリールメタン化合物、

(式（２）においてＲ_１ａ〜Ｒ_６ａは、それぞれ独立に水素原子、炭素数１〜６のアルキル基、フェニル基またはベンジル基を表し、Ｒ_７ａ〜Ｒ_２０ａは、それぞれ独立に水素原子、炭素数１〜６のアルキル基、ハロゲン原子を表す。Ｘ⁻は上記式（１）と同義である。)、
（３）Ｘ⁻がトリストリフルオロメタンスルホニルメチドアニオンである事を特徴とする（２）に記載のトリアリールメタン化合物、
（４）一般式（３）で表される事を特徴とする（１）に記載のトリアリールメタン化合物、

(式（３）においてＲ_１ｂ〜Ｒ_４ｂは、それぞれ独立に水素原子、炭素数１〜６のアルキル基、フェニル基またはベンジル基を表し、Ｒ_５ｂ〜Ｒ_１６ｂは、それぞれ独立に水素原子、炭素数１〜６のアルキル基またはハロゲン原子を表し、Ｒ_１７ｂは水素原子、炭素数１〜６のアルキル基、ハロゲン原子またはアミノ基を表し、Ｘ⁻は上記式（１）と同義である。）、
（５）Ｘ⁻がトリストリフルオロメタンスルホニルメチドアニオンである事を特徴とする（４）に記載のトリアリールメタン化合物、
（６）（１）乃至（５）のいずれか一つに記載のトリアリールメタン化合物及び油溶性有機溶媒を含有する油性染料組成物、
（７）（１）乃至（５）のいずれか一つに記載のトリアリールメタン化合物及び水性媒体を含有する水性染料組成物、
に関する。That is, the present invention
(1) a triarylmethane compound 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 the central carbon atom with a carbon atom, and X ⁻ represents a bistrifluoromethanesulfonylimide anion or tristrifluoromethanesulfonyl. Represents the metide 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 represents 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, a carbon atom, or a carbon atom. Represents an alkyl group of formulas 1 to 6 or a halogen atom, and X ⁻ has the same meaning as in the above formula (1).
(3) The triarylmethane compound according to (2), wherein X ⁻ is a tristotrifluoromethanesulfonylmethide 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, a carbon atom, or a carbon atom. An alkyl group of 1 to 6 or a halogen atom, R _17b represents a hydrogen atom, an alkyl group of 1 to 6 carbon atoms, a halogen atom or an amino group, and X ⁻ has the same meaning as in the above formula (1). ,
(5) The triarylmethane compound according to (4), wherein X ⁻ is a tristrifluoromethanesulfonylmethide anion,
(6) An oil-based 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 containing the triarylmethane compound according to any one of (1) to (5) and an aqueous medium,
About.

  As described above, the triarylmethane compound of the present invention is excellent in sharpness and color developability, and when it is processed into a dyed colored body by forming an oily or aqueous dye composition, it exhibits characteristics superior in fastness to conventional products. It is. That is, the triarylmethane compound of the present invention can be used in dye-colored products and can be applied to a wide range of uses such as color filter inks and inkjet inks.

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

In the formula (1), Ar ₁ , Ar ₂ and Ar ₃ each independently represents an aromatic residue bonded to the central carbon atom with 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 phenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group and benzopyrenyl group; Group, pyrazyl group, pyrimidyl group, quinolyl group, isoquinolyl group, pyrrolyl group, indoleenyl group, imidazolyl group, carbazolyl group, thienyl group, furyl group and the like, particularly phenyl group, or A naphthyl group is preferred.

In Ar ₁ , Ar ₂ and Ar ₃ in formula (1), the phenyl group or naphthyl group may have a substituent, and the substituent is not particularly limited, but may be an aliphatic hydrocarbon residue, 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, may have a substituent Aromatic oxy groups, carboxyl groups, carbamoyl groups, aldehyde groups, alkoxycarbonyl groups, aromatic oxycarbonyl groups and the like can be mentioned.

X < ^- > in the formula (1) represents a bistrifluoromethanesulfonylimide anion or a tristrifluoromethanesulfonylmethide anion, and among these, a tristrifluoromethanesulfonylmethide anion is preferable.

As the triarylmethane compound of the present invention, the compound of the above formula (2) is preferable in that it has 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 or carbon number. 1-6 alkyl groups and a halogen atom are represented. In the formula (2), X ⁻ represents a bistrifluoromethanesulfonylimide anion or a tristrifluoromethanesulfonylmethide anion, and a tristrifluoromethanesulfonylmethide 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. Examples thereof include alkyl groups such as a 1-ethylpropyl group, a 1-methylpropyl group, and a 1,2-dimethylpropyl group. These alkyl groups 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, Examples 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. Examples of the substituent include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, (C1-C5) alkyl group such as t-butyl group and pentyl group, halogen atom such as fluorine atom, chlorine atom, bromine atom and iodine atom, sulfonic acid group, methoxy group, ethoxy group, propoxy group and butoxy group , T-butoxy group, hexyloxy group and the like (C1-6) alkoxy group; hydroxyethyl group, hydroxypropyl group and other hydroxy (C1-5) alkyl group; methoxyethyl group, ethoxyethyl group, ethoxy (C1-C5) alkoxy (C1-C5) alkyl groups such as propyl group and butoxyethyl group; hydroxy groups such as 2-hydroxyethoxy group (C1-C5) alkoxy group; (C1-C5) alkoxy (C1-C5) alkoxy group such as 2-methoxyethoxy group and 2-ethoxyethoxy group; 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} 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, a hexyl group, and a cyclohexyl group. , And the like. These alkyl groups 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, and a hydroxy group. A butyl group, 2-sulfoethyl group, carboxyethyl group, cyanoethyl group, methoxyethyl group, ethoxyethyl group, butoxyethyl group, trifluoromethyl group, pentafluoroethyl group and the like can be mentioned.

In R _{7a to} R _20a of the formula (2), examples of the halogen atom include fluorine, chlorine, bromine, iodine and the like.

The triarylmethane compound of the present invention is also preferably a compound of the above formula (3) from the viewpoint of excellent 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 or carbon number. 1 to 6 alkyl groups or halogen atoms are represented, and R _17b 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 tristrifluoromethanesulfonylmethide anion, and a tristrifluoromethanesulfonylmethide anion is particularly preferable.

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. Examples thereof include alkyl groups such as a 1-ethylpropyl group, a 1-methylpropyl group, and a 1,2-dimethylpropyl group. These alkyl groups 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, Examples thereof include a hydroxybutyl group, 2-sulfoethyl group, carboxyethyl group, cyanoethyl group, methoxyethyl group, ethoxyethyl group, butoxyethyl group, trifluoromethyl group, pentafluoroethyl group, and fanylmethyl group.

In R _{1b to} R _4b of the formula (3), the phenyl group or benzyl group may have a substituent, and the substituent is not particularly limited, but for example, a methyl group, an ethyl group, a propyl group, isopropyl (C1-C5) alkyl groups such as butyl, t-butyl and pentyl, halogen atoms such as fluorine, chlorine, bromine and iodine, sulfonic acid, methoxy, ethoxy and propoxy (C1-C6) alkoxy groups such as butoxy group, t-butoxy group, hexyloxy group; hydroxy (C1-C5) alkyl groups such as hydroxyethyl group, hydroxypropyl group; methoxyethyl group, ethoxyethyl group, ethoxypropyl Groups, (C1-C5) alkoxy (C1-C5) alkyl groups such as butoxyethyl group; Roxy (C1-C5) alkoxy groups; 2-methoxyethoxy groups, alkoxy (C1-C5) alkoxy groups such as 2-ethoxyethoxy groups (C1-C5); 2-sulfoethyl groups, carboxyethyl groups, cyanoethyl groups, etc. It is done.

As R _<1b > -R < _4b > of 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 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 the like. These alkyl groups 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 and a hydroxypropyl group. Hydroxybutyl group, 2-sulfoethyl group, carboxyethyl group, cyanoethyl group, methoxyethyl group, ethoxyethyl group, butoxyethyl group, trifluoromethyl group, pentafluoroethyl group and the like.

In R _{5b to} R _17b in the formula (3), examples of the halogen atom include fluorine, chlorine, bromine, iodine and the like.

The amino group in R _17b of formula (3) may have a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a phenyl group, and a benzyl group. The substituent may be any group, and the substituent is not particularly limited. Examples of the substituted alkyl group having 1 to 6 carbon atoms include a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, and 2-sulfoethyl. Group, 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 (C1-C5) alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, pentyl group, fluorine atom, chlorine Halogen atoms such as atoms, bromine atoms and iodine atoms, sulfonic acid groups, methoxy groups, ethoxy groups, propoxy groups, butoxy groups, t-butoxy groups, hexyloxy groups and the like (C1-C6) alkoxy groups; hydroxyethyl groups, 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 Hydroxy (C1-C5) alkoxy group such as 2-methoxyethoxy group, 2-ethoxyethyl Alkoxy group (C1 to C5) alkoxy (C1 to C5) alkoxy group such as, 2-sulfoethyl, carboxyethyl group, cyanoethyl group and the like.

R _{5b to} R _{16b in} 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 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" (pp. 781~787), X ^- is chlorine anion It can also be synthesized by purchasing a commercially available product and adding the corresponding salt or acid to exchange the salt.

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

表１及び表２中、置換基Ｒについて、Ｍｅはメチル基を、Ｅｔはエチル基を、Ｐｈはフェニル基を、Ｂｚはベンジル基を、ＣＦ_３はトリフロロメチル基を、ｎ−Ｂｕはノルマルブチル基を、ｓｅｃ−Ｂｕはセカンダリーブチル基を、ｉ−Ｐｒはイソプロピル基を、ＣｙＨｅｘはシクロヘキシル基をそれぞれ表す。また、Ｘ⁻がαの場合はトリストリフルオロメタンスルホニルメチドアニオンを、βの場合はビストリフルオロメタンスルホニルイミドアニオンをそれぞれ表す。Specific examples of the triarylmethane compound represented by the formula (2) are shown in the following Table 1, and specific examples of the triarylmethane compound represented by the formula (3) are shown in the following Table 2, respectively. It is not limited.

In Tables 1 and 2, for substituent R, Me is a methyl group, Et is an ethyl group, Ph is a phenyl group, Bz is a benzyl group, CF ₃ is a trifluoromethyl group, and n-Bu is normal. A butyl group, sec-Bu represents a secondary butyl group, i-Pr represents an isopropyl group, and CyHex represents a cyclohexyl group. Further, X ^- is a tris trifluoromethanesulfonyl methide anion in the case of alpha, in the case of β respectively representing bistrifluoromethanesulfonylimide anion.

  The triarylmethane compound of the present invention is used as an oil-based dye composition or a water-based dye composition for coloring compositions such as various paints, water-based inks, oil-based inks, ink-jet inks, and color filter inks. The oil-based dye composition and the aqueous dye composition are used for materials to be colored such as plain paper, coated paper, plastic film, and plastic substrate. Examples of a method for applying 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 ink jet printing, and coating methods using a spin coater, a roll coater, and the like.

  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 an aqueous medium in the case of an aqueous dye. 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, and more preferably 0.5 to 20% by weight. In the oily or aqueous dye composition of the present invention, a colorant other than the formula (1) may be added as necessary for the purpose of adjusting the hue. Examples of colorants 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, and carbon black. And added in a dissolved or dispersed state 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. Examples of the aqueous medium include water or a water-soluble organic solvent. Examples of water-soluble organic solvents include alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol, benzyl alcohol; ethylene ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene Polyhydric alcohols such as glycol, polypropylene glycol, glycerin, trimethylolpropane, 1,3-pentanediol, 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 oil-soluble organic solvent. Examples of the oil-soluble organic solvent used include 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; butylphenyl 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 oil dye compositions include sodium dodecylbenzenesulfonate, sodium laurate, formalin condensate of naphthalene sulfonic acid, formalin condensate of alkyl naphthalene sulfonic acid, formalin condensate of creosote oil sulfonic acid, poly Known anionic surfactants such as ammonium salts of oxyethylene alkyl ether sulfates, ammonium of polyoxyethylene alkyl phenyl ether sulfates, polyoxyalkyl ether phosphate esters, vinyl naphthalene derivatives, fats of α, β-ethylenically unsaturated carboxylic acids Aromatic alcohol esters, etc., styrene, styrene derivatives, acrylic acid, acrylic acid derivatives, methacrylic acid, methacrylic acid derivatives, maleic acid, maleic acid derivatives, maleic anhydride, maleic anhydride A block copolymer consisting of at least two monomers selected from inic acid derivatives, itaconic acid, itaconic acid derivatives, fumaric acid, fumaric acid derivatives, etc., or a random copolymer, or a high salt thereof. Examples thereof include molecular dispersants, and it is preferably used in an amount of 10 to 100% by weight based on the dye compound in which one or more of these are dispersed. In addition to these dispersants, known nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, copolymers of ethylene oxide and propylene oxide, and silicones A known acetylene-based antifoaming agent can be added at the time of pigment dispersion and / or after the pigment dispersion.

  Examples of the method for dispersing the pigment into the fine particles include a method using a sand mill (bead mill), a roll mill, a ball mill, a paint shaker, an ultrasonic disperser, a microfluidizer, and the like. Among these, a sand mill (bead mill) is preferable. In the grinding of pigments in sand mills (bead mills), it is preferable to use beads with small diameters and to treat them under conditions that increase the grinding efficiency by increasing the filling rate of beads. It is preferable to remove the elementary particles by separation or the like. The dye composition of the present invention may contain a surface adjusting agent, an antiseptic, an antifungal agent, a pH adjusting agent and the like as other additives. As surface conditioning agents, polysiloxane or polydimethylsiloxane surfactants, and as antiseptic / antifungal agents, sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, zinc pyridinethione-1-oxide 1,2-benzisothiazolin-3-one, amine salts of 1-benzisothiazolin-3-one, etc., as pH adjusters, alkali hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, Tertiary amines such as triethanolamine, diethanolamine, dimethylethanolamine, diethylethanolamine and the like can be mentioned, and each can be added as necessary.

  In addition, in the oily or aqueous dye composition of the present invention, for the purpose of improving the fixability of the pigment to the object to be colored, a polyamide system, a polyurethane system, or a polyester that is compatible with the medium in the composition within a necessary range. It is preferable to contain an epoxy resin, an epoxy resin, or a polyacrylic resin. Further, for the purpose of improving the fixability, a monomer, oligomer, polymerization initiator or the like having an ethylenically unsaturated group may be contained within a necessary 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.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples. In the examples, “parts” represents “parts by weight” unless otherwise specified. The decomposition temperatures of the various compounds obtained in the examples were measured by TG / DTA. In addition, evaluations such as heat resistance and water resistance were evaluated by measuring the chromaticity (L value, a value, b value) of the dyed colored body with the following chromaticity measuring device. The names of measuring instruments are as follows.
1. TG / DTA (simultaneous thermogravimetric measurement):
Product name TG / DTA220 manufactured by Seiko Instruments Inc.
2. Chromaticity measuring device: UV-3150 manufactured by Shimadzu Corporation

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

Example 2 (Synthesis of Compound No. 2a in Table 1)
7 parts of BasicBlue of the following formula (100) was dissolved in 150 parts of water, and a solution of 1.2 parts of a 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 oil-based dye composition and dye-colored product To 10 parts of tetrafluoropropanol, Compound No. 1a, compound no. 2a and 0.5 part were melt | dissolved, respectively, and the oil-based dye composition was prepared. The obtained oil dye composition was spin-coated on a polycarbonate substrate and dried at 80 ° C. for 30 minutes to prepare a dye-colored product.

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

Moist heat resistance test 1
The dyed colored product obtained by the above method was allowed to stand for 40 hours in a constant temperature and humidity chamber under conditions of 85 ° C. and 85% RH. The dye-colored product before and after the test was measured with a spectrophotometer for the L value, a value, and b value as standard light using a C light source and a viewing angle of 2 degrees, and the color difference was determined from the following formula. In addition, it shows that it is excellent because the change in hue is small as the color difference is small.
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
Tables 3 to 6 below show measured values and color differences of the colorimetry in the moisture and heat resistance test.

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

Compound No. The color measurement results of 2a are shown in Table 4 below.
(Table 4)
L value a value b value Before test 82.71 -6.45 -27.04
After the test 83.37 -7.33-25.84
Difference before and after 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 Before test 79.62 -5.19 -31.95
After the test 89.70 -4.29 -11.66
Difference before and after test -10.08 -0.90 -20.29

From Table 3 to Table 5 above, Compound No. 1a, compound no. The results of determining the color difference between 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 is apparent from the results of Table 6, the color difference before and after the test of the dye-colored product of Comparative Example 1 was as large as 22.7, whereas the dye-colored product of the present invention had a color difference of 1.4 and 1 It shows a very small value of .6, indicating that the heat and moisture resistance is extremely excellent.

Water resistance test 1
The dyed colored product obtained by the above method was left in warm water at 70 ° C. for 5 minutes. The dye-colored product before and after the test was measured with a spectrophotometer for the L value, a value, and b value as standard light using a C light source and a viewing angle of 2 degrees, and the color difference was determined from the following formula. In addition, it shows that it is excellent because the change in hue is small as the color difference is small. 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
Tables 7 to 10 below show the color measurement values and color differences in the water resistance test.

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

Compound No. The color measurement results of 2a are shown in Table 8 below.
(Table 8)
L value a value b value Before test 82.71 -6.45 -27.04
After the test 86.43 -6.08 -20.67
Difference before and after 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 Before test 79.62 -5.19 -31.95
After the test 99.26 -0.58 -1.53
Difference before and after test -19.64 -4.61 -30.42

From Table 7 to Table 9 above, Compound No. 1a, compound no. The results of determining the color difference between 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 apparent from the results of Table 10, the color difference before and after the test of the dye-colored product of Comparative Example 1 was as large as 36.7, whereas the dye-colored product of the present invention had a color difference of 2.0 and 7 .4 shows a very small value, indicating that the water resistance is extremely excellent.

Example 4 (Synthesis of Compound No. 5a in Table 1)
2 parts of BasicBlue 26 of the following formula (101) (manufactured by Tokyo Chemical Industry Co., Ltd., decomposition temperature: 223 ° C.) is dissolved in 20 parts of DMF, and 2.5 parts of cesium salt of tristrifluoromethanesulfonium metide 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 (the triarylmethane compound of the present invention). Decomposition temperature: 267 ° C

Example 5
Preparation of oil-based dye composition and dye-colored product To 10 parts of tetrafluoropropanol, compound No. obtained in Example 4 was added. 5a, 0.5 part was melt | dissolved and the oil-based dye composition was prepared. The obtained oil dye composition was spin-coated on a polycarbonate substrate and dried at 80 ° C. for 30 minutes to prepare a dye-colored product.

  In addition, the comparative example 2 in the following Table 12 represents the evaluation result of using the BasicBlue 26 of the above formula (101) and preparing a dye-colored body in the same manner.

Moist heat resistance test 2
The test method is the same as the wet heat resistance test 1. The measured values of colorimetry and the color difference 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 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 color measurement results of Comparative Example 2 are shown in Table 12 below.
(Table 12)
L value a value b value Before 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

From Table 11 and Table 12 above, Compound No. The results of determining the color difference 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 apparent from the results of Table 13, the color difference before and after the test of the dye-colored product of Comparative Example 2 was as large as 6.6, whereas the dye-colored product of the present invention had an extremely large color difference of 0.3. A small value is shown, indicating that the heat and moisture resistance is extremely excellent.

Water resistance test 2
The test method is the same as the water resistance test 1. The measured values of colorimetry and the color difference 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 Before test 86.66 -6.78 -20.34
After the test 88.62 -3.64 -11.89
Difference before and after test -1.96 -3.14 -8.45

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

From Table 14 and Table 15 above, Compound No. The results of determining the color difference between 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 is apparent from the results of Table 16, the color difference before and after the test of the dye-colored product of Comparative Example 2 showed a very large value of 25.5, whereas the dye-colored product of the present invention had an extremely large color difference of 9.2. A small value is shown, indicating that the water resistance is extremely excellent.

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

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

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

Example 9 (Synthesis of Compound No. 1b in Table 2)
1 part of malachite green oxalate of the following formula (105) (decomposition temperature: 175 ° C.) was dissolved in 50 parts of water, and 2 parts of cesium salt of tristrifluoromethanesulfonium methide was dissolved in 5 parts of DMF while stirring. 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 (triarylmethane compound of the present invention). Decomposition temperature: 190 ° C

Example 10 (Synthesis of Compound No. 3b in Table 2)
5 parts of BasicBlue 1 (decomposition temperature: 190 ° C.) of the following formula (106) was dissolved in 500 parts of water, and with stirring, a solution of 2 parts of cesium salt of tristrifluoromethanesulfonium methide was added to 10 parts of DMF. . 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)
5 parts of BasicViolet 3 (decomposition temperature: 205 ° C.) of the following formula (107) was dissolved in 500 parts of water, and with stirring, a solution of 1 part of cesium salt of tristrifluoromethanesulfonium metide was dissolved in 10 parts of DMF. . 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 (the triarylmethane compound of the present invention). Decomposition temperature: 240 ° C

Example 12
Preparation of oil-based dye composition and dye-colored product In 10 parts of tetrafluoropropanol, each of the compound No. 1b, Compound No. 1 3b, compound no. 5b, 0.5 part was melt | dissolved and the oil-based dye composition was prepared. The obtained oil dye composition was spin-coated on a polycarbonate substrate and dried at 80 ° C. for 30 minutes to prepare a dye-colored product.

Comparative Example 3 described in Table 17 and Table 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 of the following formula (107 ) Was used in the same manner to prepare a dye-colored product.

Water resistance test 3
The dyed colored product obtained by the above method was left in warm water at 70 ° C. for 30 seconds. The dye-colored product before and after the test was measured with a spectrophotometer for the L value, a value, and b value as standard light using a C light source and a viewing angle of 2 degrees, and the color difference was determined from the following formula. In addition, it shows that it is excellent because the change in hue is small as the color difference is small. 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 values and color difference of the colorimetry in the water resistance test are shown in Tables 17 to 23 below.

Compound No. The color measurement result of 1b is shown in Table 17 below.
(Table 17)
L value a value b value Before test 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 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 Before 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 Before test 89.77 -10.94 -4.49
After test 100.22 -0.21 -0.41
Difference before and after test -10.45 -10.73 -4.08

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

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

From Table 17 to Table 22 above, Compound No. 1b, No. 1 3b, no. The results of obtaining the color difference 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 difference before and after the test of the dye-colored product of Comparative Example 3 showed a large value of 15.5, whereas the compound No. 1 of the present invention having the same cation moiety was used. The dyed colored body of 1b shows a small color difference of 2.3, indicating that the water resistance is extremely excellent. Similarly, the color difference before and after the test of the dyed colored bodies of Comparative Examples 4 and 5 showed large values of 10.0 and 46.1, whereas the compound No. 1 of the present invention. 3b and no. The color difference of the dye-colored body of 5b shows a very small value of 2.0 and 4.6.

Example 13 (Synthesis of Compound No. 53b in Table 2)
Dissolve 2.31 parts of the dye of the following formula (108) in a mixed solution of 200 parts of water and 120 parts of methanol, and dissolve 2.30 parts of the cesium salt of tristrifluoromethanesulfonium methide in 4.2 parts of DMF while stirring. The solution was added. After stirring for 3 hours, the 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)
3.1 parts of the dye of the following formula (109) is dissolved in a mixed solution of 150 parts of water and 72 parts of methanol, and while stirring, the mixed solution of 6.3 parts of DMF and 16 parts of methanol is cesium of tristrifluoromethanesulfonium methide. A solution in which 3.55 parts of salt were dissolved was added. After 3 hours of heating and stirring 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)
1.0 part of the dye of the following formula (110) is dissolved in a mixed solution of 100 parts of water and 40 parts of methanol, and while stirring, the mixed solution of 3.2 parts of DMF and 8 parts of methanol is cesium of tristrifluoromethanesulfonium methide. A solution in which 1.31 parts of salt were dissolved was added. After 3 hours of heating and stirring 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)
1.0 part of the dye of the following formula (111) is dissolved in a mixed solution of 100 parts of water and 40 parts of methanol, and while stirring, the mixed solution of 3.2 parts of DMF and 8 parts of methanol is cesium of tristrifluoromethanesulfonium methide. A solution in which 0.65 part of the salt was dissolved was added. After 3 hours of heating and stirring 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 described above, the triarylmethane compound represented by the above formula (1) of the present invention is excellent in heat resistance from the comparison of the decomposition temperatures thereof, and the dye-colored body has characteristics excellent in wet heat resistance and water resistance. The triarylmethane dyes of the present invention have been found to have high industrial value such as a wide range of applications such as color filter inks and inkjet inks.

Claims (2)

Formula (2) is represented by the belt rear triarylmethane compound.

(In Formula (2), R _{1a to} R _6a each independently represents 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, a carbon atom, or a carbon atom. Represents an alkyl group having a number of 1 to 6 or a halogen atom, and X ⁻ represents a tristotrifluoromethanesulfonylmethide anion .) An aqueous dye composition comprising the triarylmethane compound according to claim 1 and an aqueous medium.