WO2010123071A1 - Novel triarylmethane compound - Google Patents

Novel triarylmethane compound Download PDF

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Publication number
WO2010123071A1
WO2010123071A1 PCT/JP2010/057160 JP2010057160W WO2010123071A1 WO 2010123071 A1 WO2010123071 A1 WO 2010123071A1 JP 2010057160 W JP2010057160 W JP 2010057160W WO 2010123071 A1 WO2010123071 A1 WO 2010123071A1
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group
test
value
compound
parts
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PCT/JP2010/057160
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French (fr)
Japanese (ja)
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高明 倉田
裕 石井
宜樹 赤谷
諒 寺西
あさ子 近藤
秀洋 新井
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日本化薬株式会社
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Priority to JP2011510363A priority Critical patent/JP5442004B2/en
Priority to CN201080005820.XA priority patent/CN102300938A/en
Publication of WO2010123071A1 publication Critical patent/WO2010123071A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
    • C09B11/10—Amino derivatives of triarylmethanes
    • C09B11/12—Amino derivatives of triarylmethanes without any OH group bound to an aryl nucleus
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/54—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
    • C07C211/49—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring having at least two amino groups bound to the carbon skeleton
    • C07C211/50—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring having at least two amino groups bound to the carbon skeleton with at least two amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/57—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
    • C07C211/58—Naphthylamines; N-substituted derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/24—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the same saturated acyclic carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/0084—Dispersions of dyes
    • C09B67/0085—Non common dispersing agents
    • C09B67/0086—Non common dispersing agents anionic dispersing agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/328—Inkjet printing inks characterised by colouring agents characterised by dyes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Definitions

  • the present invention relates to novel triarylmethane compounds.
  • Triarylmethane dyes are characterized by their extremely sharp color and high color developability, and they are used as a wide range of applications such as various paints, water-based inks, oil-based inks, ink-jet inks, and color filter inks as violet, blue or green color materials. Used in In general, the properties required for coloring materials are different depending on the application, but the hue is sharp, high color forming ability is required, and in many applications, it is required that the coloring matter is fast to light, heat, etc. .
  • a cationic dye having a cationic group such as quaternary nitrogen in the structure and an anionic dye having an anionic group such as a sulfone group introduced into the cationic dye structure are known. Although all of them have excellent color forming properties, they have the disadvantage that they have poor fastness such as light resistance, heat resistance, moist heat resistance, water resistance and the like.
  • Patent Document 1 describes a salt compound of a cationic triarylmethane compound and a chloride ion or an arylsulfonate ion, but as a result of studies by the present inventors, a triarylmethane disclosed in this patent document The compound was insufficient in light resistance, heat resistance and water resistance.
  • Patent Document 2 also describes a triarylmethane cationic dye having a fluorinated alkylsulfonyl counter ion, but there is no specific example of a compound, and light resistance, heat resistance, moist heat resistance, water resistance, etc. There is no mention of robustness.
  • salt compounds of a cationic triphenylmethane compound and a chloride ion or an oxalate ion are commercially available, as a result of studies by the present inventors, these known triphenylmethane compounds have light resistance, heat resistance, and moisture resistance. The heat resistance and water resistance were insufficient.
  • the present invention is a novel triarylmethane compound which has the sharpness and color forming properties of triarylmethane dyes and is excellent in fastness such as light resistance, heat resistance, moist heat resistance, water resistance, etc. It is an object of the present invention to provide an oily or aqueous dye composition used.
  • the present inventors conducted intensive studies to solve the problems as described above, and as a result, a salt compound of cationic triarylmethane and a specific anion maintains the sharpness and colorability of triarylmethane dyes. And, it has been found that the light resistance, heat resistance, moisture heat resistance and water resistance are dramatically improved as compared with the prior art, and the present invention has been completed.
  • the present invention (1) triarylmethane compounds represented by the general formula (1), (In the formula (1), Ar 1 , Ar 2 and Ar 3 each independently represent an aromatic residue bonded to a central carbon atom by a carbon atom, and X ⁇ represents a bistrifluoromethanesulfonyl imide anion or tristrifluoromethanesulfonyl Represents methide anion) (2)
  • the triarylmethane compound according to (1) which is represented by the general formula (2):
  • R 1a to R 6a each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group or a benzyl group, and R 7a to R 20a each independently represent a hydrogen atom or carbon And represents an alkyl group of 1 to 6 or a halogen atom, and X - is as defined in the above formula (1))
  • the triarylmethane compound of the present invention is excellent in sharpness and color development as described above, and when it is formed into an oil or aqueous dye composition and processed into a dye colored body, exhibits superior fastness to conventional products. It is. That is, the triarylmethane compound of the present invention can be used as a dye-colored material, and can be applied to a wide range of applications such as color filter inks and inkjet inks.
  • the triarylmethane compound of the present invention is represented by the above formula (1).
  • Ar 1 , Ar 2 and Ar 3 each independently represent an aromatic residue bonded to a central carbon atom at a carbon atom.
  • the aromatic residue in Ar 1 , Ar 2 and Ar 3 of the formula (1) is, for example, an aromatic hydrocarbon residue such as phenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group and benzopyrenyl group; And aromatic heterocyclic residues such as pyridyl group, pyrazyl group, pyrimidyl group, quinolyl group, isoquinolyl group, pyrrolyl group, indoleyl group, imidazolyl group, carbazolyl group, thienyl group, furyl group, etc.
  • a naphthyl group is preferred.
  • a phenyl group or a naphthyl group may have a substituent, and the substituent is not particularly limited, but an aliphatic hydrocarbon residue, an aromatic Group, cyano group, isocyano group, thiocyanato group, isothiocyanato group, nitro group, acyl group, halogen atom, hydroxyl group, substituted or unsubstituted amino group, alkoxyl group, alkoxyalkyl group, and substituent group Aromatic oxy group, carboxyl group, carbamoyl group, aldehyde group, alkoxycarbonyl group, aromatic oxycarbonyl group and the like can be mentioned.
  • X 2 - represents a bistrifluoromethanesulfonylimide anion or a tristrifluoromethanesulfonyl methide anion, and among these, a tristrifluoromethanesulfonyl methide anion is preferable.
  • the compound of the above formula (2) is preferable in that it is excellent in fastness such as heat resistance, moist heat resistance and water resistance.
  • 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
  • R 7a to R 20a each independently represent a hydrogen atom or a carbon number It represents an alkyl group of 1 to 6 and a halogen atom.
  • X - represents a bistrifluoromethanesulfonylimide anion or a tristrifluoromethanesulfonyl methide anion, and a tristrifluoromethanesulfonyl methide anion is particularly preferable.
  • examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a pentyl group, a cyclopentyl group, a hexyl group and a cyclohexyl group And alkyl groups such as 1-ethylpropyl group, 1-methylpropyl group and 1,2-dimethylpropyl group.
  • alkyl groups may have a substituent, and the substituent is not particularly limited, and as the alkyl group having 1 to 6 carbon atoms having a substituent, for example, hydroxyethyl group, hydroxypropyl group, Examples thereof include hydroxybutyl group, 2-sulfoethyl group, carboxyethyl group, cyanoethyl group, methoxyethyl group, ethoxyethyl group, butoxyethyl group, trifluoromethyl group, pentafluoroethyl group, phenylmethyl group and the like.
  • the phenyl group or the benzyl group may have a substituent, and examples of the substituent include a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group (C1-C5) alkyl group such as t-butyl group, pentyl group, etc., fluorine atom, halogen atom such as chlorine atom, bromine atom, iodine atom, etc., sulfonic acid group, methoxy group, ethoxy group, propoxy group, butoxy group (C1-C6) alkoxy group such as t-butoxy group and hexyloxy group; hydroxy (C1-C5) alkyl group such as hydroxyethyl group and hydroxypropyl group; methoxyethyl group, ethoxyethyl group, ethoxy (C1-C5) alkoxy (C1-
  • 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.
  • R 7a to R 20a in the formula (2) include a hydrogen atom, a halogen atom, or a C 1 to C 6 unsubstituted alkyl group.
  • examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a pentyl group, a cyclopentyl group, a hexyl group and a cyclohexyl group And alkyl groups such as.
  • These alkyl groups may have a substituent, and the substituent is not particularly limited, and examples of the alkyl group having 1 to 6 carbon atoms having a substituent include hydroxyethyl, hydroxypropyl and hydroxy.
  • Examples thereof include a butyl group, 2-sulfoethyl group, carboxyethyl group, cyanoethyl group, methoxyethyl group, ethoxyethyl group, butoxyethyl group, trifluoromethyl group and pentafluoroethyl group.
  • Examples of the halogen atom in R 7a to R 20a of the formula (2) include fluorine, chlorine, bromine and iodine.
  • 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
  • R 5b to R 16b each independently represent a hydrogen atom or a carbon number
  • R 1-7 represents an alkyl group or a halogen atom
  • R 17 b represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a halogen atom or an amino group.
  • X - represents a bistrifluoromethanesulfonylimide anion or a tristrifluoromethanesulfonyl methide anion, and a tristrifluoromethanesulfonyl methide anion is particularly preferred.
  • examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a pentyl group, a cyclopentyl group, a hexyl group and a cyclohexyl group And alkyl groups such as 1-ethylpropyl group, 1-methylpropyl group and 1,2-dimethylpropyl group.
  • alkyl groups may have a substituent, and the substituent is not particularly limited, and as the alkyl group having 1 to 6 carbon atoms having a substituent, for example, hydroxyethyl group, hydroxypropyl group, Examples thereof include hydroxybutyl group, 2-sulfoethyl group, carboxyethyl group, cyanoethyl group, methoxyethyl group, ethoxyethyl group, butoxyethyl group, trifluoromethyl group, pentafluoroethyl group, phenylmethyl group and the like.
  • the phenyl group or the benzyl group may have a substituent, and the substituent is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group and isopropyl Group, butyl group, t-butyl group, (C1 to C5) alkyl group such as pentyl group, fluorine atom, halogen atom such as chlorine atom, bromine atom or iodine atom, sulfonic acid group, methoxy group, ethoxy group, propoxy group (C1 to C6) alkoxy groups such as butoxy, t-butoxy and hexyloxy; hydroxy (C1 to C5) alkyl groups such as hydroxyethyl and hydroxypropyl; methoxyethyl, ethoxyethyl and ethoxypropyl Groups, (C1-C5) alkoxy (C1-C5) alkyl groups, (C1-C5) alk
  • R 1b to R 4b in the formula (3) a hydrogen atom, an unsubstituted alkyl group having 1 to 6 carbon atoms, an unsubstituted phenyl group, or an unsubstituted benzyl group is preferable.
  • examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a pentyl group, a cyclopentyl group, a hexyl group and a cyclohexyl group And alkyl groups such as.
  • These alkyl groups may have a substituent, and the substituent is not particularly limited, and examples of the alkyl group having 1 to 6 carbon atoms having a substituent include hydroxyethyl and hydroxypropyl.
  • Examples of the halogen atom in R 5b to R 17b of the formula (3) include fluorine, chlorine, bromine and iodine.
  • the amino group in R 17b of Formula (3) may have a substituent, and the substituent includes, for example, an alkyl group having 1 to 6 carbon atoms, a phenyl group or a benzyl group, and these are further substituted It may have a group, and the substituent is not particularly limited, and as the alkyl group having 1 to 6 carbon atoms having a substituent, for example, hydroxyethyl, hydroxypropyl, hydroxybutyl, 2-sulfoethyl Groups, carboxyethyl group, cyanoethyl group, methoxyethyl group, ethoxyethyl group, butoxyethyl group, trifluoromethyl group, pentafluoroethyl group and the like.
  • the substituent includes, for example, an alkyl group having 1 to 6 carbon atoms, a phenyl group or a benzyl group, and these are further substituted It may have a group, and the
  • examples of the substituent include a (C1 to C5) alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group and pentyl group, fluorine atom, chlorine A halogen atom such as an atom, a bromine atom and an iodine atom, a sulfonic acid group, a sulfonic acid group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a t-butoxy group and a hexyloxy group, and a (C1-C6) alkoxy group; Hydroxy (C1-C5) alkyl group such as hydroxypropyl group; (C1-C5) alkoxy (C1-C5) alkyl group such as methoxyethyl group, ethoxyethyl
  • R 5b to R 16b in the formula (3) a hydrogen atom, a chlorine atom, or an unsubstituted alkyl group having 1 to 6 carbon atoms is preferable, and R 17b is preferably a hydrogen atom or an amino group.
  • Triarylmethane compound of the present invention may, for example, obtained by a known synthesis method described in Yutaka Hosoda al, issued by Gihodo Co. "Theoretical production Dye Chemistry” (781-787 pages), X - is chlorine anion It can also be synthesized by purchasing a commercially available product, adding the corresponding salt or acid, and performing salt exchange.
  • a compound in which X ⁇ is a chloride anion is a reaction solvent (eg, water, methanol, ethanol, isopropanol, acetone, N, N-dimethylformamide) And water-soluble polar solvents such as N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP), which may be used alone or in combination, and the corresponding salts or
  • NMP N-methyl-2-pyrrolidone
  • the acid can be added by about 0.5 to 3 equivalents, stirred at a predetermined temperature (for example, 0 to 100 ° C.), easily synthesized, and obtained by filtering the precipitated crystals.
  • triarylmethane compounds represented by the formula (2) are shown in Table 1 below, and specific examples of the triarylmethane compounds represented by the formula (3) are shown in Table 2 below, but the present invention It is not limited.
  • Tables 1 and 2 for the substituent R, Me is methyl, Et is ethyl, Ph is phenyl, Bz is benzyl, CF 3 is trifluoromethyl, n-Bu is normal Sec-Bu represents a secondary butyl group, i-Pr represents an isopropyl group, and CyHex represents a cyclohexyl group.
  • X - when X - is ⁇ , it represents a tristrifluoromethanesulfonyl methide anion, and when it is a ⁇ , it represents a bistrifluoromethanesulfonyl imide anion.
  • the triarylmethane compound of the present invention is used as an oil-based dye composition, or a coloring composition such as various paints, water-based inks, oil-based inks, inks for inkjets, inks for color filters as an aqueous dye composition.
  • Oily dye compositions and aqueous dye compositions are used, for example, for colored materials such as plain paper, coated paper, plastic films, plastic substrates and the like.
  • various printing methods such as offset printing, letterpress printing, flexographic printing, ink jet printing, or coating methods using a spin coater, roll coater or the like can be mentioned.
  • the oily or aqueous dye compositions according to the invention comprise the triarylmethane compounds according to the invention and, in the case of oily dye compositions, an oil-soluble organic solvent, and in the case of aqueous dyes, an aqueous medium.
  • the triarylmethane compound of the present invention is preferably contained in an amount of 0.2 to 40% by weight, more preferably 0.5 to 20% by weight.
  • a coloring material other than the above-mentioned formula (1) may be added as needed for the purpose of adjusting the hue and the like.
  • coloring materials examples include water-soluble dyes such as acid dyes, reactive dyes, direct dyes, cationic dyes and basic dyes, oil-soluble dyes such as disperse dyes and solvent dyes, organic pigments, carbon black and the like. And added in a state of being dissolved or dispersed in a solvent.
  • the aqueous dye composition of the present invention can be prepared by dispersing the triarylmethane compound of the formula (1) in an aqueous medium.
  • Aqueous media include water or water soluble organic solvents.
  • the water-soluble organic solvent include alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol and benzyl alcohol; ethylene ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene Polyhydric alcohols such as glycol, polypropylene glycol, glycerin, trimethylolpropane, 1,3-pentanediol and 1,5-pentanediol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, Triethylene glycol monoethyl ether, triethylene glycol
  • the oil-based dye composition of the present invention can be prepared by dissolving or dispersing the triarylmethane compound of the above formula (1) in at least one or more oil-soluble organic solvents.
  • the oil-soluble organic solvent for example, alcohols such as ethanol, pentanol, octanol, cyclohexanol, benzyl alcohol and tetrafluoropropanol; ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol mono Glycol derivatives such as ethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol diacetate, propylene glycol diacetate; ketones such as methyl ethyl ketone and cyclohexanone; butyl phenyl ether, benzyl
  • Dispersants used in the oil-based dye composition include sodium dodecylbenzene sulfonate, sodium lauryl acid, formalin condensate of naphthalene sulfonic acid, formalin condensate of alkyl naphthalene sulfonic acid, formalin condensate of creosote oil sulfonic acid, poly Well-known anionic surfactants such as ammonium salt of oxyethylene alkyl ether sulfate, ammonium salt of polyoxyethylene alkyl phenyl ether sulfate, polyoxyalkyl ether phosphate ester salt, etc., vinyl naphthalene derivative, fat of ⁇ , ⁇ -ethylenically unsaturated carboxylic acid Alcohol ester etc., styrene, styrene derivative, acrylic acid, acrylic acid derivative, methacrylic acid, methacrylic acid derivative, maleic acid, maleic acid derivative, maleic anhydride,
  • nonionic surfactants and silicones such as polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, copolymer of ethylene oxide and propylene oxide, etc. If necessary, known antifoaming agents based on acetylene may be added during and / or after pigment dispersion.
  • Examples of the method of dispersing the pigment into fine particles include a method using a sand mill (beads mill), a roll mill, a ball mill, a paint shaker, an ultrasonic disperser, a microfluidizer, etc., among which sand mills (bead mills) are preferred.
  • a sand mill beads mill
  • the dye composition of the present invention may contain, as other additives, surface conditioners, preservatives, fungicides, pH adjusters and the like.
  • Surface conditioners include polysiloxane or polydimethylsiloxane surfactants; preservatives and fungicides include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, zinc pyridinethione-1-oxide And an amine salt of 1,2-benzisothiazolin-3-one, 1-benzisothiazolin-3-one and the like, and as a pH adjuster, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, Examples thereof include tertiary amines such as triethanolamine, diethanolamine, dimethylethanolamine, diethylethanolamine and the like, and these can be added as necessary.
  • oil-based or aqueous dye composition of the present invention for the purpose of improving the fixability of the dye to the colored material, a polyamide based, polyurethane based, polyester compatible with the medium in the composition within the necessary range. It is preferable to contain a system, epoxy resin or polyacrylic resin. Further, in order to improve the fixing property, monomers, oligomers, polymerization initiators and the like having an ethylenically unsaturated group may be contained within the necessary range.
  • the oily or aqueous dye composition of the present invention can be prepared by dissolving, dispersing or mixing the above-mentioned components in a solvent.
  • Example 1 (Synthesis of Compound No. 1a in Table 1) Dissolve 2 parts of BasicBlue 7 (made by Tokyo Chemical Industry Co., Ltd., decomposition temperature: 217 ° C.) of the following formula (100) in 150 parts of water and, while stirring, add 30 parts of acetonitrile and cesium salt of tristrifluoromethanesulfonium methide 2.1. A solution in which parts were dissolved was added. After stirring for 3 hours, precipitated crystals were collected by filtration, washed with water and dried to obtain 1.5 parts of blue crystals (triarylmethane compound of the present invention). Decomposition temperature: 256 ° C
  • Example 2 Synthesis of Compound No. 2a in Table 1
  • Two parts of BasicBlue 7 of the following formula (100) were dissolved in 150 parts of water, and a solution of 1.2 parts of potassium salt of bistrifluoromethanesulfonium imide in 10 parts of water was added while stirring. After stirring for 3 hours, the precipitated crystals were collected by filtration, washed with water and dried to obtain 0.7 parts of blue crystals (the triarylmethane compound of the present invention).
  • Decomposition temperature 240 ° C
  • Example 3 Preparation of Oily Dye Composition and Dye Colored Material
  • 10 parts of tetrafluoropropanol the compound No. 1 obtained in the above example was used.
  • Compound No. 1a Each 0.5 part of 2a was dissolved to prepare an oily dye composition.
  • the obtained oily dye composition was spin-coated on a polycarbonate substrate and dried at 80 ° C. for 30 minutes to prepare a dye-colored material.
  • the comparative example 1 in the following Table 5 and Table 9 represents the test result of what prepared dye coloring matter similarly using BasicBlue7 of following formula (100).
  • Moisture and heat resistance test 1 The dye-colored material obtained by the above method was left to stand in a constant temperature and humidity chamber at 85 ° C. and 85% RH for 40 hours.
  • the dye colored materials before and after the test were measured for L value, a value and b value with a C light source as a standard light with a spectrophotometer and a viewing angle of 2 degrees as standard light, and the color difference was determined from the following formula. The smaller the color difference is, the smaller the change in hue is.
  • Color difference [(pre-test L value-post-test L value) 2 + (pre-test a value-post-test a value) 2 + (pre-test b value-post-test b value) 2 ] 1/2 Measured values of colorimetry and color differences in the moisture resistance test are shown in Tables 3 to 6 below.
  • the dye colored body of Comparative Example 1 before and after the test shows a very large value of 22.7
  • the dye colored body of the present invention has a color difference of 1.4 and 1 It shows a very small value of .6, and it can be seen that the heat and humidity resistance is extremely excellent.
  • the dye-colored product obtained by the above method was left in hot water at 70 ° C. for 5 minutes.
  • the dye colored materials before and after the test were measured for L value, a value and b value with a C light source as a standard light with a spectrophotometer and a viewing angle of 2 degrees as standard light, and the color difference was determined from the following formula. The smaller the color difference is, the smaller the change in hue is, and thus the better.
  • Color difference [(pre-test L value-post-test L value) 2 + (pre-test a value-post-test a value) 2 + (pre-test b value-post-test b value) 2 ] 1/2 Measured values of colorimetry and color differences in the water resistance test are shown in Tables 7 to 10 below.
  • Example 5 Preparation of Oily Dye Composition and Dye Colored Material
  • 10 parts of tetrafluoropropanol the compound No. 1 obtained in Example 4 was used.
  • An oil dye composition was prepared by dissolving 0.5 parts of 5a.
  • the obtained oily dye composition was spin-coated on a polycarbonate substrate and dried at 80 ° C. for 30 minutes to prepare a dye-colored material.
  • the comparative example 2 in the following Table 12 represents the evaluation result of what prepared dye coloring matter similarly using BasicBlue26 of said Formula (101).
  • Moisture and heat resistance test 2 The test method is the same as moist heat resistance test 1.
  • the colorimetric measurement values and color differences are shown in Tables 11 to 13 below.
  • Water resistance test 2 The test method is the same as water resistance test 1. Measured values of colorimetry and color differences are shown in Tables 14 to 16 below.
  • Example 6 (Synthesis of Compound No. 45a in Table 1) A cesium salt of tristrifluoromethanesulfonium methide is dissolved in a mixed solution of 2 parts of DMF and 12 parts of methanol while dissolving 2 parts of a dye of the following formula (102) in a mixed solution of 30 parts of water and 75 parts of methanol while stirring. A solution of 48 parts was added. After heating and stirring for 3 hours at 60 ° C., the precipitated crystals were collected by filtration, washed with water and dried to obtain 1.3 parts of blue crystals (triarylmethane compound of the present invention). Decomposition temperature: 262 ° C
  • Example 7 (Synthesis of Compound No. 57a in Table 1) A cesium salt of tristrifluoromethanesulfonium methide is dissolved in a mixed solution of 2 parts of DMF and 12 parts of methanol while dissolving 2.5 parts of a dye of the following formula (103) in a mixed solution of 2 parts of water and 38 parts of methanol while stirring. A solution of 2.87 parts dissolved was added. After heating and stirring for 3 hours at 60 ° C., the precipitated crystals were collected by filtration, washed with water and dried to obtain 2.8 parts of blue crystals (triarylmethane compound of the present invention). Decomposition temperature: 269 ° C
  • Example 8 (Synthesis of Compound No. 69a in Table 1) A cesium salt of tristrifluoromethanesulfonium methide is dissolved in a mixed solution of 3 parts of DMF and 25 parts of methanol while dissolving 3 parts of the dye of the following formula (104) in a mixed solution of 10 parts of water and 53 parts of methanol while stirring. A solution of 94 parts was added. After heating and stirring for 3 hours at 60 ° C., the precipitated crystals were collected by filtration, washed with water and dried to obtain 3.5 parts of blue crystals (triarylmethane compound of the present invention). Decomposition temperature: 267 ° C
  • Example 9 (Synthesis of Compound No. 1b in Table 2) In 50 parts of water, 1 part of malachite green oxalate of the following formula (105) was dissolved in 50 parts of water, and 2 parts of a cesium salt of tristrifluoromethanesulfonium methide was dissolved in 5 parts of DMF. The solution was added. After stirring for 3 hours, the precipitated crystals were collected by filtration, washed with water and dried to obtain 0.5 parts of dark green crystals (the triarylmethane compound of the present invention). Decomposition temperature: 190 ° C
  • Example 10 (synthesis of compound No. 3b in Table 2) In 500 parts of water was dissolved 5 parts of BasicBlue 1 (decomposition temperature: 190 ° C.) of the following formula (106), and a solution in which 2 parts of a cesium salt of tristrifluoromethanesulfonium methide was dissolved in 10 parts of DMF was added while stirring. . After stirring for 3 hours, the precipitated crystals were collected by filtration, washed with water and dried to obtain 0.7 parts of blue crystals (the triarylmethane compound of the present invention). Decomposition temperature: 230 ° C
  • Example 11 (synthesis of compound No. 5b in Table 2) In 500 parts of water, 5 parts of BasicViolet 3 (decomposition temperature: 205 ° C.) of the following formula (107) was dissolved, and a solution in which 1 part of a cesium salt of tristrifluoromethanesulfonium methide was dissolved in 10 parts of DMF was added while stirring. . After stirring for 3 hours, the precipitated crystals were collected by filtration, washed with water and dried to obtain 1.2 parts of purple crystals (triarylmethane compound of the present invention). Decomposition temperature: 240 ° C
  • Example 12 Preparation of Oily Dye Composition and Dye Colored Material
  • 10 parts of tetrafluoropropanol the compound No. 1 obtained in each of the above examples was used.
  • Compound No. 1b. 3b the compound No.
  • An oil dye composition was prepared by dissolving 0.5 parts of 5b.
  • the obtained oily dye composition was spin-coated on a polycarbonate substrate and dried at 80 ° C. for 30 minutes to prepare a dye-colored material.
  • Comparative Example 3 described in Tables 17 and 18 below is malachite green oxalate of the following Formula (105), Comparative Example 4 is BasicBlue 1 of the following Formula (106), and Comparative Example 5 is the following Formula (107)
  • the dye-colored bodies were similarly prepared using Basic Violet 3 of the above).
  • the dye-colored product obtained by the above method was left in warm water at 70 ° C. for 30 seconds.
  • the dye colored materials before and after the test were measured for L value, a value and b value with a C light source as a standard light with a spectrophotometer and a viewing angle of 2 degrees as standard light, and the color difference was determined from the following formula. The smaller the color difference is, the smaller the change in hue is, and thus the better.
  • Color difference [(pre-test L value-post-test L value) 2 + (pre-test a value-post-test a value) 2 + (pre-test b value-post-test b value) 2 ] 1/2 Measured values of colorimetry and color differences in the water resistance test are shown in Tables 17 to 23 below.
  • Example 13 (synthesis of compound No. 53b in Table 2) In a mixed solution of 200 parts of water and 120 parts of methanol, 2.31 parts of a dye of the following formula (108) is dissolved, and 2.30 parts of a cesium salt of tristrifluoromethanesulfonium methide is dissolved in 4.2 parts of DMF while stirring. The added solution was added. After stirring for 3 hours, precipitated crystals were collected by filtration, washed with water and dried to obtain 3.64 parts of blue crystals (Compound No. 53b). Decomposition temperature: 231 ° C
  • Example 14 (synthesis of compound No. 21b in Table 2) Dissolve 3.1 parts of the dye of the following formula (109) in a mixed solution of 150 parts of water and 72 parts of methanol, add cesium in tristrifluoromethanesulfonium methide to a mixed solution of 6.3 parts of DMF and 16 parts of methanol while stirring. A solution of 3.55 parts salt was added. After heating and stirring for 3 hours at 40 ° C., the precipitated crystals were collected by filtration, washed with water and dried to obtain 1.63 parts of blue crystals (Compound No. 21b). Decomposition temperature: 234 ° C
  • Example 15 (Synthesis of Compound No. 33b in Table 2) Dissolve 1.0 part of a dye of the following formula (110) in a mixed solution of 100 parts of water and 40 parts of methanol, add cesium in tristrifluoromethanesulfonium methide to a mixed solution of 3.2 parts of DMF and 8 parts of methanol while stirring A solution of 1.31 parts of salt was added. After heating and stirring for 3 hours at 30 ° C., the precipitated crystals were collected by filtration, washed with water and dried to obtain 0.98 parts of blue crystals (Compound No. 33b). Decomposition temperature: 232 ° C
  • Example 16 (synthesis of compound No. 69b in Table 2) Dissolve 1.0 part of the dye of the following formula (111) in a mixed solution of 100 parts of water and 40 parts of methanol, add cesium in tristrifluoromethanesulfonium methide to a mixed solution of 3.2 parts of DMF and 8 parts of methanol while stirring A solution of 0.65 parts salt was added. After heating and stirring for 3 hours at 40 ° C., the precipitated crystals were collected by filtration, washed with water and dried to obtain 0.73 parts of blue crystals (Compound No. 69b). Decomposition temperature: 277 ° C
  • the triarylmethane compound represented by the said Formula (1) of this invention is excellent in heat resistance from the comparison of the decomposition temperature, and the dye colored body has the characteristic excellent in heat-and-moisture resistance and water resistance. It has been revealed that the triarylmethane dyes of the present invention have high industrial value such as broadening the range of applications such as color filter inks and ink jet inks.

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Abstract

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

Description

新規なトリアリールメタン化合物Novel triarylmethane compounds
　本発明は新規なトリアリールメタン化合物に関する。 The present invention relates to novel triarylmethane compounds.
　トリアリールメタン系染料は非常に鮮明で発色性が高い事が特徴であり、バイオレット、ブルーあるいはグリーン色の色材として各種塗料、水性インキ、油性インキ、インクジェット用インキ、カラーフィルター用インキなど幅広い用途で使用されている。一般に色材に要求される特性はそれぞれ用途によって異なるものの色相が鮮明で、高発色性を有し、着色物が光、熱などに対し堅牢である事がどのような用途においても多く要求される。トリアリールメタン系染料としては構造中に４級窒素等のカチオン基を有するカチオン性染料と、カチオン性染料構造にスルホン基等のアニオン基を導入し、アニオン性としたアニオン染料とが知られているが、いずれも発色性が優れる反面、耐光性、耐熱性、耐湿熱性、耐水性等の堅牢性が劣るという欠点がある。 Triarylmethane dyes are characterized by their extremely sharp color and high color developability, and they are used as a wide range of applications such as various paints, water-based inks, oil-based inks, ink-jet inks, and color filter inks as violet, blue or green color materials. Used in In general, the properties required for coloring materials are different depending on the application, but the hue is sharp, high color forming ability is required, and in many applications, it is required that the coloring matter is fast to light, heat, etc. . As a triarylmethane dye, a cationic dye having a cationic group such as quaternary nitrogen in the structure and an anionic dye having an anionic group such as a sulfone group introduced into the cationic dye structure are known. Although all of them have excellent color forming properties, they have the disadvantage that they have poor fastness such as light resistance, heat resistance, moist heat resistance, water resistance and the like.
　このため、トリアリールメタン系染料の鮮明性及び発色性を有し、且つ高堅牢な染料が要望されているが、これらの性能を兼ね備えた染料は見出されていない。特許文献１にはカチオン性トリアリールメタン化合物と塩素イオンやアリールスルホン酸イオンとの塩化合物が記載されているが、本発明者らの検討の結果、この特許文献に記載されているトリアリールメタン化合物は耐光性、耐熱性、耐水性が不十分であった。また特許文献２にはフッ素化アルキルスルホニル対イオンを有するトリアリールメタン系カチオン染料についての記載はあるが、具体的な化合物の例示は無く、また耐光性、耐熱性、耐湿熱性、耐水性などの堅牢性に関する記載もなされていない。また、カチオン性トリフェニルメタン化合物と塩素イオンやシュウ酸イオンとの塩化合物が市販されているが、本発明者らの検討の結果、これら既知のトリフェニルメタン化合物は耐光性、耐熱性、耐湿熱性、耐水性が不十分であった。 Therefore, there is a demand for a dye having the sharpness and color-forming properties of a triarylmethane dye and a highly robust dye, but no dye having these properties has been found. Patent Document 1 describes a salt compound of a cationic triarylmethane compound and a chloride ion or an arylsulfonate ion, but as a result of studies by the present inventors, a triarylmethane disclosed in this patent document The compound was insufficient in light resistance, heat resistance and water resistance. Patent Document 2 also describes a triarylmethane cationic dye having a fluorinated alkylsulfonyl counter ion, but there is no specific example of a compound, and light resistance, heat resistance, moist heat resistance, water resistance, etc. There is no mention of robustness. In addition, although salt compounds of a cationic triphenylmethane compound and a chloride ion or an oxalate ion are commercially available, as a result of studies by the present inventors, these known triphenylmethane compounds have light resistance, heat resistance, and moisture resistance. The heat resistance and water resistance were insufficient.
特開２００８－３０４７６６号JP 2008-304766 特開平８－２５３７０５号JP-A-8-253705
　本発明は前記のごとく、トリアリールメタン系染料の鮮明性及び発色性を有し、且つ耐光性、耐熱性、耐湿熱性、耐水性などの堅牢性に優れる新規なトリアリールメタン化合物ならびに該化合物を用いた油性または水性染料組成物を提供する事を目的とする。 As described above, the present invention is a novel triarylmethane compound which has the sharpness and color forming properties of triarylmethane dyes and is excellent in fastness such as light resistance, heat resistance, moist heat resistance, water resistance, etc. It is an object of the present invention to provide an oily or aqueous dye composition used.
　本発明者らは前述したような課題を解決すべく、鋭意研究を行った結果、カチオン性のトリアリールメタンと特定のアニオンとの塩化合物がトリアリールメタン系染料の鮮明性及び発色性を維持し、かつ従来に比べ飛躍的に耐光性、耐熱性、耐湿熱性、耐水性が向上する事を見出し、本発明を完成させるに至った。 The present inventors conducted intensive studies to solve the problems as described above, and as a result, a salt compound of cationic triarylmethane and a specific anion maintains the sharpness and colorability of triarylmethane dyes. And, it has been found that the light resistance, heat resistance, moisture heat resistance and water resistance are dramatically improved as compared with the prior art, and the present invention has been completed.
　即ち、本発明は、
（１）一般式（１）で表されるトリアリールメタン化合物、
Figure JPOXMLDOC01-appb-C000004
 （式（１）においてＡｒ１、Ａｒ２およびＡｒ３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、
Figure JPOXMLDOC01-appb-C000005
 (式（２）においてＲ１ａ～Ｒ６ａ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、Ｒ７ａ～Ｒ２０ａ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、
Figure JPOXMLDOC01-appb-C000006
 (式（３）においてＲ１ｂ～Ｒ４ｂ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、Ｒ５ｂ～Ｒ１６ｂ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、Ｒ１７ｂ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) triarylmethane compounds represented by the general formula (1),
Figure JPOXMLDOC01-appb-C000004
 (In the formula (1), Ar 1 , Ar 2 and Ar 3 each independently represent an aromatic residue bonded to a central carbon atom by a carbon atom, and X − represents a bistrifluoromethanesulfonyl imide anion or tristrifluoromethanesulfonyl Represents methide anion)
(2) The triarylmethane compound according to (1), which is represented by the general formula (2):
Figure JPOXMLDOC01-appb-C000005
 (In formula (2), R 1a to R 6a each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group or a benzyl group, and R 7a to R 20a each independently represent a hydrogen atom or carbon And represents an alkyl group of 1 to 6 or a halogen atom, and X - is as defined in the above formula (1)),
(3) The triarylmethane compound according to (2), wherein X − is a tristrifluoromethanesulfonyl methide anion,
(4) The triarylmethane compound according to (1), which is represented by the general formula (3):
Figure JPOXMLDOC01-appb-C000006
 (In Formula (3), R 1b to R 4b each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group or a benzyl group, and R 5b to R 16b each independently represent a hydrogen atom or carbon represents a number 1-6 alkyl group or a halogen atom, R 17b represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a halogen atom or an amino group, X - is as defined in the above formula (1)). ,
(5) The triarylmethane compound according to (4), wherein X - is a tristrifluoromethanesulfonyl methide anion,
(6) An oil dye composition comprising the triarylmethane compound according to any one of (1) to (5) and an oil-soluble organic solvent,
(7) An aqueous dye composition comprising the triarylmethane compound according to any one of (1) to (5) and an aqueous medium,
About.
　本発明のトリアリールメタン化合物は、上記の通り鮮明性および発色性に優れ、油性または水性染料組成物を形成して染料着色体に加工すると、従来品よりも堅牢性に優れた特性を示すものである。すなわち、本発明のトリアリールメタン化合物は染料着色体に利用でき、カラーフィルター用インキやインクジェット用インキ等の幅広い用途に応用できる。 The triarylmethane compound of the present invention is excellent in sharpness and color development as described above, and when it is formed into an oil or aqueous dye composition and processed into a dye colored body, exhibits superior fastness to conventional products. It is. That is, the triarylmethane compound of the present invention can be used as a dye-colored material, and can be applied to a wide range of applications such as color filter inks and inkjet inks.
　本発明のトリアリールメタン化合物は、前記式（１）で表される。 The triarylmethane compound of the present invention is represented by the above formula (1).
　式（１）において、Ａｒ１、Ａｒ２及びＡｒ３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す。 In Formula (1), Ar 1 , Ar 2 and Ar 3 each independently represent an aromatic residue bonded to a central carbon atom at a carbon atom.
　式（１）の、Ａｒ１、Ａｒ２及びＡｒ３における芳香族残基としては、例えばフェニル基、ナフチル基、アンスリル基、フェナンスリル基、ピレニル基、ベンゾピレニル基などの芳香族炭化水素残基；ピリジル基、ピラジル基、ピリミジル基、キノリル基、イソキノリル基、ピロリル基、インドレニル基、イミダゾリル基、カルバゾリル基、チエニル基、フリル基などの芳香族複素環残基、等が挙げられ、特にフェニル基、またはナフチル基が好ましい。 The aromatic residue in Ar 1 , Ar 2 and Ar 3 of the formula (1) is, for example, an aromatic hydrocarbon residue such as phenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group and benzopyrenyl group; And aromatic heterocyclic residues such as pyridyl group, pyrazyl group, pyrimidyl group, quinolyl group, isoquinolyl group, pyrrolyl group, indoleyl group, imidazolyl group, carbazolyl group, thienyl group, furyl group, etc. A naphthyl group is preferred.
　式（１）の、Ａｒ１、Ａｒ２及びＡｒ３においてフェニル基、またはナフチル基は置換基を有しても良く、該置換基としては特に制限はないが、脂肪族炭化水素残基、芳香族残基、シアノ基、イソシアノ基、チオシアナト基、イソチオシアナト基、ニトロ基、アシル基、ハロゲン原子、ヒドロキシル基、置換もしくは非置換アミノ基、アルコキシル基、アルコキシアルキル基、置換基を有してもよい芳香族オキシ基、カルボキシル基、カルバモイル基、アルデヒド基、アルコキシカルボニル基、芳香族オキシカルボニル基等が挙げられる。 In Ar 1 , Ar 2 and Ar 3 of the formula (1), a phenyl group or a naphthyl group may have a substituent, and the substituent is not particularly limited, but an aliphatic hydrocarbon residue, an aromatic Group, cyano group, isocyano group, thiocyanato group, isothiocyanato group, nitro group, acyl group, halogen atom, hydroxyl group, substituted or unsubstituted amino group, alkoxyl group, alkoxyalkyl group, and substituent group Aromatic oxy group, carboxyl group, carbamoyl group, aldehyde group, alkoxycarbonyl group, aromatic oxycarbonyl group and the like can be mentioned.
　式（１）中の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し、中でもトリストリフルオロメタンスルホニルメチドアニオンが好ましい。 In the formula (1), X 2 - represents a bistrifluoromethanesulfonylimide anion or a tristrifluoromethanesulfonyl methide anion, and among these, a tristrifluoromethanesulfonyl methide anion is preferable.
　本発明のトリアリールメタン化合物としては耐熱性、耐湿熱性及び耐水性などの堅牢性に優れる点で前記式（２）の化合物が好ましい。式（２）においてＲ１ａ～Ｒ６ａ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、Ｒ７ａ～Ｒ２０ａ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。また、式（２）において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し、特にトリストリフルオロメタンスルホニルメチドアニオンが好ましい。 As the triarylmethane compound of the present invention, the compound of the above formula (2) is preferable in that it is excellent in fastness such as heat resistance, moist heat resistance and water resistance. In formula (2), R 1a to R 6a each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group or a benzyl group, and R 7a to R 20a each independently represent a hydrogen atom or a carbon number It represents an alkyl group of 1 to 6 and a halogen atom. Further, in the formula (2), X - represents a bistrifluoromethanesulfonylimide anion or a tristrifluoromethanesulfonyl methide anion, and a tristrifluoromethanesulfonyl methide anion is particularly preferable.
　式（２）のＲ１ａ～Ｒ６ａにおいて、炭素数１～６のアルキル基としては、例えばメチル基、エチル基、プロピル基、ブチル基、イソブチル基、ペンチル基、シクロペンチル基、ヘキシル基、シクロヘキシル基、１―エチルプロピル基、１―メチルプロピル基、１，２―ジメチルプロピル基等のアルキル基が挙げられる。これらのアルキル基は置換基を有しても良く、該置換基としては特に制限は無いが、置換基を有する炭素数１～６のアルキル基としては、例えば、ヒドロキシエチル基、ヒドロキシプロピル基、ヒドロキシブチル基、２－スルホエチル基、カルボキシエチル基、シアノエチル基、メトキシエチル基、エトキシエチル基、ブトキシエチル基、トリフルオロメチル基、ペンタフルオロエチル基、フェニルメチル基等が挙げられる。 In R 1a to R 6a of the formula (2), examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a pentyl group, a cyclopentyl group, a hexyl group and a cyclohexyl group And alkyl groups such as 1-ethylpropyl group, 1-methylpropyl group and 1,2-dimethylpropyl group. These alkyl groups may have a substituent, and the substituent is not particularly limited, and as the alkyl group having 1 to 6 carbon atoms having a substituent, for example, hydroxyethyl group, hydroxypropyl group, Examples thereof include hydroxybutyl group, 2-sulfoethyl group, carboxyethyl group, cyanoethyl group, methoxyethyl group, ethoxyethyl group, butoxyethyl group, trifluoromethyl group, pentafluoroethyl group, phenylmethyl group and the like.
　式（２）のＲ１ａ～Ｒ６ａにおいてフェニル基、またはベンジル基は置換基を有していても良く、該置換基としては、例えばメチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ｔ－ブチル基、ペンチル基等の（炭素数１～５）アルキル基、フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子、スルホン酸基、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、ｔ－ブトキシ基、ヘキシルオキシ基等の（炭素数１～６）アルコキシ基；ヒドロキシエチル基、ヒドロキシプロピル基等のヒドロキシ（炭素数１～５）アルキル基；メトキシエチル基、エトキシエチル基、エトキシプロピル基、ブトキシエチル基等の（炭素数１～５）アルコキシ（炭素数１～５）アルキル基；２―ヒドロキシエトキシ基等のヒドロキシ（炭素数１～５）アルコキシ基；２－メトキシエトキシ基、２－エトキシエトキシ基等の（炭素数１～５）アルコキシ（炭素数１～５）アルコキシ基；２－スルホエチル基、カルボキシエチル基、シアノエチル基等が挙げられる。 In R 1a to R 6a of the formula (2), the phenyl group or the benzyl group may have a substituent, and examples of the substituent include a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group (C1-C5) alkyl group such as t-butyl group, pentyl group, etc., fluorine atom, halogen atom such as chlorine atom, bromine atom, iodine atom, etc., sulfonic acid group, methoxy group, ethoxy group, propoxy group, butoxy group (C1-C6) alkoxy group such as t-butoxy group and hexyloxy group; hydroxy (C1-C5) alkyl group such as hydroxyethyl group and hydroxypropyl group; methoxyethyl group, ethoxyethyl group, ethoxy (C1-C5) alkoxy (C1-C5) alkyl group such as propyl group and butoxyethyl group; hydroxyl group such as 2-hydroxyethoxy group (C1-C5) alkoxy group; (C1-C5) alkoxy (C1-C5) alkoxy group such as 2-methoxyethoxy group, 2-ethoxyethoxy group etc .; 2-sulfoethyl group, carboxyethyl group, A cyanoethyl group etc. are mentioned.
　式（２）のＲ１ａ～Ｒ６ａにおいて、水素原子、無置換の炭素数１～６のアルキル基、無置換のフェニル基、または無置換のベンジル基が好ましい。 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.
　式（２）のＲ７ａ～Ｒ２０ａとしては水素原子、ハロゲン原子、または炭素数１～６の無置換アルキル基が挙げられる。 Examples of R 7a to R 20a in the formula (2) include a hydrogen atom, a halogen atom, or a C 1 to C 6 unsubstituted alkyl group.
　式（２）のＲ７ａ～Ｒ２０ａにおいて、炭素数１～６のアルキル基としては、例えばメチル基、エチル基、プロピル基、ブチル基、イソブチル基、ペンチル基、シクロペンチル基、ヘキシル基、シクロヘキシル基、等のアルキル基が挙げられる。これらのアルキル基は置換基を有して良く、該置換基としては特に制限は無いが、置換基を有する炭素数１～６のアルキル基としては、例えば、ヒドロキシエチル基、ヒドロキシプロピル基、ヒドロキシブチル基、２－スルホエチル基、カルボキシエチル基、シアノエチル基、メトキシエチル基、エトキシエチル基、ブトキシエチル基、トリフルオロメチル基、ペンタフルオロエチル基等が挙げられる。 In R 7a to R 20a of the formula (2), examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a pentyl group, a cyclopentyl group, a hexyl group and a cyclohexyl group And alkyl groups such as. These alkyl groups may have a substituent, and the substituent is not particularly limited, and examples of the alkyl group having 1 to 6 carbon atoms having a substituent include hydroxyethyl, hydroxypropyl and hydroxy. Examples thereof include a butyl group, 2-sulfoethyl group, carboxyethyl group, cyanoethyl group, methoxyethyl group, ethoxyethyl group, butoxyethyl group, trifluoromethyl group and pentafluoroethyl group.
　式（２）のＲ７ａ～Ｒ２０ａにおいてハロゲン原子としては、フッ素、塩素、臭素、ヨウ素等が挙げられる。 Examples of the halogen atom in R 7a to R 20a of the formula (2) include fluorine, chlorine, bromine and iodine.
　また、本発明のトリアリールメタン化合物としては耐熱性、耐湿熱性及び耐水性などの堅牢性に優れる点で前記式（３）の化合物も好ましい。式（３）においてＲ１ｂ～Ｒ４ｂ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、Ｒ５ｂ～Ｒ１６ｂ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、Ｒ１７ｂ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す。また、式（３）において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し、特にトリストリフルオロメタンスルホニルメチドアニオンが好ましい。 Moreover, as a triarylmethane compound of this invention, the compound of said Formula (3) is also preferable at the point which is excellent in fastnesses, such as heat resistance, wet heat resistance, and water resistance. In formula (3), R 1b to R 4b each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group or a benzyl group, and R 5b to R 16b each independently represent a hydrogen atom or a carbon number R 1-7 represents an alkyl group or a halogen atom, and R 17 b represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a halogen atom or an amino group. In the formula (3), X - represents a bistrifluoromethanesulfonylimide anion or a tristrifluoromethanesulfonyl methide anion, and a tristrifluoromethanesulfonyl methide anion is particularly preferred.
　式（３）のＲ１ｂ～Ｒ４ｂにおいて、炭素数１～６のアルキル基としては、例えばメチル基、エチル基、プロピル基、ブチル基、イソブチル基、ペンチル基、シクロペンチル基、ヘキシル基、シクロヘキシル基、１―エチルプロピル基、１―メチルプロピル基、１，２―ジメチルプロピル基等のアルキル基が挙げられる。これらのアルキル基は置換基を有しても良く、該置換基としては特に制限は無いが、置換基を有する炭素数１～６のアルキル基としては、例えば、ヒドロキシエチル基、ヒドロキシプロピル基、ヒドロキシブチル基、２－スルホエチル基、カルボキシエチル基、シアノエチル基、メトキシエチル基、エトキシエチル基、ブトキシエチル基、トリフルオロメチル基、ペンタフルオロエチル基、ファニルメチル基等が挙げられる。 In R 1b to R 4b of the formula (3), examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a pentyl group, a cyclopentyl group, a hexyl group and a cyclohexyl group And alkyl groups such as 1-ethylpropyl group, 1-methylpropyl group and 1,2-dimethylpropyl group. These alkyl groups may have a substituent, and the substituent is not particularly limited, and as the alkyl group having 1 to 6 carbon atoms having a substituent, for example, hydroxyethyl group, hydroxypropyl group, Examples thereof include hydroxybutyl group, 2-sulfoethyl group, carboxyethyl group, cyanoethyl group, methoxyethyl group, ethoxyethyl group, butoxyethyl group, trifluoromethyl group, pentafluoroethyl group, phenylmethyl group and the like.
　式（３）のＲ１ｂ～Ｒ４ｂにおいてフェニル基、またはベンジル基は置換基を有していても良く、該置換基としては特に制限は無いが、例えばメチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ｔ－ブチル基、ペンチル基等の（Ｃ１～Ｃ５）アルキル基、フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子、スルホン酸基、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、ｔ－ブトキシ基、ヘキシルオキシ基等の（Ｃ１～Ｃ６）アルコキシ基；ヒドロキシエチル基、ヒドロキシプロピル基等のヒドロキシ（Ｃ１～Ｃ５）アルキル基；メトキシエチル基、エトキシエチル基、エトキシプロピル基、ブトキシエチル基等の（Ｃ１～Ｃ５）アルコキシ（Ｃ１～Ｃ５）アルキル基；２―ヒドロキシエトキシ基等のヒドロキシ（Ｃ１～Ｃ５）アルコキシ基；２－メトキシエトキシ基、２－エトキシエトキシ基（Ｃ１～Ｃ５）等のアルコキシ（Ｃ１～Ｃ５）アルコキシ基；２－スルホエチル基、カルボキシエチル基、シアノエチル基等が挙げられる。 In R 1b to R 4b of formula (3), the phenyl group or the benzyl group may have a substituent, and the substituent is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group and isopropyl Group, butyl group, t-butyl group, (C1 to C5) alkyl group such as pentyl group, fluorine atom, halogen atom such as chlorine atom, bromine atom or iodine atom, sulfonic acid group, methoxy group, ethoxy group, propoxy group (C1 to C6) alkoxy groups such as butoxy, t-butoxy and hexyloxy; hydroxy (C1 to C5) alkyl groups such as hydroxyethyl and hydroxypropyl; methoxyethyl, ethoxyethyl and ethoxypropyl Groups, (C1-C5) alkoxy (C1-C5) alkyl groups such as butoxyethyl group; and 2-hydroxyethoxy groups And alkoxy (C1 to C5) alkoxy groups such as 2-methoxyethoxy group and 2-ethoxyethoxy group (C1 to C5); 2-sulfoethyl group, carboxyethyl group, cyanoethyl group and the like. Be
　式（３）のＲ１ｂ～Ｒ４ｂとしては、水素原子、無置換の炭素数１～６のアルキル基、無置換のフェニル基、または無置換のベンジル基が好ましい。 As R 1b to R 4b in the formula (3), a hydrogen atom, an unsubstituted alkyl group having 1 to 6 carbon atoms, an unsubstituted phenyl group, or an unsubstituted benzyl group is preferable.
　式（３）のＲ５ｂ～Ｒ１７ｂにおいて、炭素数１～６のアルキル基としては、例えばメチル基、エチル基、プロピル基、ブチル基、イソブチル基、ペンチル基、シクロペンチル基、ヘキシル基、シクロヘキシル基、等のアルキル基が挙げられる。これらのアルキル基は置換基を有していても良く、該置換基としては特に制限は無いが、置換基を有する炭素数１～６のアルキル基としては、例えば、ヒドロキシエチル基、ヒドロキシプロピル基、ヒドロキシブチル基、２－スルホエチル基、カルボキシエチル基、シアノエチル基、メトキシエチル基、エトキシエチル基、ブトキシエチル基、トリフルオロメチル基、ペンタフルオロエチル基等が挙げられる。 In R 5b to R 17b of formula (3), examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a pentyl group, a cyclopentyl group, a hexyl group and a cyclohexyl group And alkyl groups such as. These alkyl groups may have a substituent, and the substituent is not particularly limited, and examples of the alkyl group having 1 to 6 carbon atoms having a substituent include hydroxyethyl and hydroxypropyl. And hydroxybutyl group, 2-sulfoethyl group, carboxyethyl group, cyanoethyl group, methoxyethyl group, ethoxyethyl group, butoxyethyl group, trifluoromethyl group, pentafluoroethyl group and the like.
　式（３）のＲ５ｂ～Ｒ１７ｂにおいてハロゲン原子としては、フッ素、塩素、臭素、ヨウ素等が挙げられる。 Examples of the halogen atom in R 5b to R 17b of the formula (3) include fluorine, chlorine, bromine and iodine.
　式（３）のＲ１７ｂにおけるアミノ基は置換基を有していても良く、該置換基としては、炭素数１～６のアルキル基、フェニル基またはベンジル基が挙げられるが、これらはさらに置換基を有しても良く、該置換基としては特に制限は無いが、置換基を有する炭素数１～６のアルキル基としては、例えばヒドロキシエチル基、ヒドロキシプロピル基、ヒドロキシブチル基、２－スルホエチル基、カルボキシエチル基、シアノエチル基、メトキシエチル基、エトキシエチル基、ブトキシエチル基、トリフルオロメチル基、ペンタフルオロエチル基等が挙げられる。フェニル基またはベンジル基の場合は、置換基として、例えばメチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ｔ－ブチル基、ペンチル基等の（Ｃ１～Ｃ５）アルキル基、フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子、スルホン酸基、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、ｔ－ブトキシ基、ヘキシルオキシ基等の（Ｃ１～Ｃ６）アルコキシ基；ヒドロキシエチル基、ヒドロキシプロピル基等のヒドロキシ（Ｃ１～Ｃ５）アルキル基；メトキシエチル基、エトキシエチル基、エトキシプロピル基、ブトキシエチル基等の（Ｃ１～Ｃ５）アルコキシ（Ｃ１～Ｃ５）アルキル基；２―ヒドロキシエトキシ基等のヒドロキシ（Ｃ１～Ｃ５）アルコキシ基；２－メトキシエトキシ基、２－エトキシエトキシ基（Ｃ１～Ｃ５）等のアルコキシ（Ｃ１～Ｃ５）アルコキシ基；２－スルホエチル基、カルボキシエチル基、シアノエチル基等が挙げられる。 The amino group in R 17b of Formula (3) may have a substituent, and the substituent includes, for example, an alkyl group having 1 to 6 carbon atoms, a phenyl group or a benzyl group, and these are further substituted It may have a group, and the substituent is not particularly limited, and as the alkyl group having 1 to 6 carbon atoms having a substituent, for example, hydroxyethyl, hydroxypropyl, hydroxybutyl, 2-sulfoethyl Groups, carboxyethyl group, cyanoethyl group, methoxyethyl group, ethoxyethyl group, butoxyethyl group, trifluoromethyl group, pentafluoroethyl group and the like. In the case of a phenyl group or a benzyl group, examples of the substituent include a (C1 to C5) alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group and pentyl group, fluorine atom, chlorine A halogen atom such as an atom, a bromine atom and an iodine atom, a sulfonic acid group, a sulfonic acid group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a t-butoxy group and a hexyloxy group, and a (C1-C6) alkoxy group; Hydroxy (C1-C5) alkyl group such as hydroxypropyl group; (C1-C5) alkoxy (C1-C5) alkyl group such as methoxyethyl group, ethoxyethyl group, ethoxypropyl group, butoxyethyl group; 2-hydroxyethoxy group And the like hydroxy (C1-C5) alkoxy group such as Alkoxy group (C1 ~ C5) alkoxy (C1 ~ C5) alkoxy group such as, 2-sulfoethyl, carboxyethyl group, cyanoethyl group and the like.
　式（３）のＲ５ｂ～Ｒ１６ｂとしては、水素原子、塩素原子、または炭素数１～６の無置換のアルキル基が好ましく、Ｒ１７ｂは水素原子またはアミノ基が好ましい。 As R 5b to R 16b in the formula (3), a hydrogen atom, a chlorine atom, or an unsubstituted alkyl group having 1 to 6 carbon atoms is preferable, and R 17b is preferably a hydrogen atom or an amino group.
　本発明のトリアリールメタン化合物は、例えば、株式会社技報堂発行の細田豊著「理論製造染料化学」（７８１～７８７頁）に記載された公知の合成法で得られるが、Ｘ－が塩素アニオンである市販品を購入し、対応する塩または酸を加えて塩交換する事により合成する事もできる。 Triarylmethane compound of the present invention may, for example, obtained by a known synthesis method described in Yutaka Hosoda al, issued by Gihodo Co. "Theoretical production Dye Chemistry" (781-787 pages), X - is chlorine anion It can also be synthesized by purchasing a commercially available product, adding the corresponding salt or acid, and performing salt exchange.
　本発明のトリアリールメタン化合物を塩交換により合成する場合は、Ｘ－が塩素アニオンである化合物を反応溶媒（例えば、水、またはメタノール、エタノール、イソプロパノール、アセトン、Ｎ，Ｎ－ジメチルホルアミド（以下ＤＭＦと略記）、Ｎ－メチル－２－ピロリドン（以下ＮＭＰと略記）等の水溶性極性溶媒が挙げられ、これらの溶媒は単独、または混合してもよい。）に溶解し、対応する塩または酸を０．５～３等量程度加え、所定温度（例えば０～１００℃）で攪拌し、容易に合成でき、析出した結晶をろ取する事により得られる。 When the triarylmethane compound of the present invention is synthesized by salt exchange, a compound in which X − is a chloride anion is a reaction solvent (eg, water, methanol, ethanol, isopropanol, acetone, N, N-dimethylformamide) And water-soluble polar solvents such as N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP), which may be used alone or in combination, and the corresponding salts or The acid can be added by about 0.5 to 3 equivalents, stirred at a predetermined temperature (for example, 0 to 100 ° C.), easily synthesized, and obtained by filtering the precipitated crystals.
　式（２）で示されるトリアリールメタン化合物の具体例を以下の表１に、式（３）で示されるトリアリールメタン化合物の具体例を以下の表２にそれぞれ示すが、本発明はこれらに限定されない。
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-I000008
Figure JPOXMLDOC01-appb-I000009
Figure JPOXMLDOC01-appb-I000010
Figure JPOXMLDOC01-appb-I000011
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-I000013
Figure JPOXMLDOC01-appb-I000014
Figure JPOXMLDOC01-appb-I000015
Figure JPOXMLDOC01-appb-I000016
　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、ＣＦ３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 compounds represented by the formula (2) are shown in Table 1 below, and specific examples of the triarylmethane compounds represented by the formula (3) are shown in Table 2 below, but the present invention It is not limited.
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-I000008
Figure JPOXMLDOC01-appb-I000009
Figure JPOXMLDOC01-appb-I000010
Figure JPOXMLDOC01-appb-I000011
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-I000013
Figure JPOXMLDOC01-appb-I000014
Figure JPOXMLDOC01-appb-I000015
Figure JPOXMLDOC01-appb-I000016
In Tables 1 and 2, for the substituent R, Me is methyl, Et is ethyl, Ph is phenyl, Bz is benzyl, CF 3 is trifluoromethyl, n-Bu is normal Sec-Bu represents a secondary butyl group, i-Pr represents an isopropyl group, and CyHex represents a cyclohexyl group. In addition, when X - is α, it represents a tristrifluoromethanesulfonyl methide anion, and when it is a β, it represents a bistrifluoromethanesulfonyl imide anion.
　本発明のトリアリールメタン化合物は、油性染料組成物、または水性染料組成物として各種塗料、水性インキ、油性インキ、インクジェット用インキ、カラーフィルター用インキ等の着色組成物に用いられる。油性染料組成物および水性染料組成物は、例えば普通紙、コート紙、プラスチックフィルム、プラスチック基板などの被着色材料に用いられる。また、本発明の染料組成物を被着色材料に付与する方法としては、オフセット印刷、凸版印刷、フレキソ印刷、インクジェット印刷などの各種印刷方法あるいはスピンコーター、ロールコーター等による塗工方法が挙げられる。 The triarylmethane compound of the present invention is used as an oil-based dye composition, or a coloring composition such as various paints, water-based inks, oil-based inks, inks for inkjets, inks for color filters as an aqueous dye composition. Oily dye compositions and aqueous dye compositions are used, for example, for colored materials such as plain paper, coated paper, plastic films, plastic substrates and the like. Moreover, as a method of applying the dye composition of the present invention to a material to be colored, various printing methods such as offset printing, letterpress printing, flexographic printing, ink jet printing, or coating methods using a spin coater, roll coater or the like can be mentioned.
　本発明の油性または水性染料組成物は、本発明のトリアリールメタン化合物及び、油性染料組成物の場合は油溶性有機溶媒を、水性染料の場合は水性媒体を含有する。本発明の油性または水性染料組成物においては、本発明のトリアリールメタン化合物を０．２～４０重量％含有させるのが好ましく、さらには０．５～２０重量％含有させるのがより好ましい。また本発明の油性または水性染料組成物において、色相の調整などの目的で必要に応じて前記式（１）以外の色材を添加してもよい。添加できる色材としては、例えば酸性染料、反応性染料、直接性染料、カチオン染料、塩基性染料などの水溶性染料、分散染料、ソルベント染料等の油溶性染料、有機顔料、カーボンブラック等が挙げられ、溶媒に溶解した状態あるいは分散した状態で添加される。 The oily or aqueous dye compositions according to the invention comprise the triarylmethane compounds according to the invention and, in the case of oily dye compositions, an oil-soluble organic solvent, and in the case of aqueous dyes, an aqueous medium. In the oily or aqueous dye composition of the present invention, the triarylmethane compound of the present invention is preferably contained in an amount of 0.2 to 40% by weight, more preferably 0.5 to 20% by weight. Further, in the oil-based or aqueous dye composition of the present invention, a coloring material other than the above-mentioned formula (1) may be added as needed for the purpose of adjusting the hue and the like. Examples of coloring materials that can be added include water-soluble dyes such as acid dyes, reactive dyes, direct dyes, cationic dyes and basic dyes, oil-soluble dyes such as disperse dyes and solvent dyes, organic pigments, carbon black and the like. And added in a state of being dissolved or dispersed in a solvent.
　本発明の水性染料組成物は、水性媒体に前記式（１）のトリアリールメタン化合物を分散させて調製する事ができる。水性媒体としては、水または水溶性有機溶媒が挙げられる。水溶性有機溶媒としては、例えば、メタノール、エタノール、プロパノール、イソプロパノール、ブタノール、イソブタノール、t-ブタノール、ペンタノール、ベンジルアルコールなどのアルコール類；エチレンエチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、ポリエチレングリコール、ポリプロピレングリコール、グリセリン、トリメチロールプロパン、１，３－ペンタンジオール、１，５－ペンタンジオール等の多価アルコール類；エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノブチルエーテル、トリエチレングリコールモノエチルエーテル、トリエチレングリコールモノブチルエーテル、ジプロピレングリコールモノメチルエーテル等のグリコール誘導体；エタノールアミン、ジエタノールアミン、トリエタノールアミン、モルホリンなどのアミン類；２－ピロリドン、ＮＭＰ、１，３－ジメチル－イミダゾリジノン等が挙げられる。 The aqueous dye composition of the present invention can be prepared by dispersing the triarylmethane compound of the formula (1) in an aqueous medium. Aqueous media include water or water soluble organic solvents. Examples of the water-soluble organic solvent include alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol and benzyl alcohol; ethylene ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene Polyhydric alcohols such as glycol, polypropylene glycol, glycerin, trimethylolpropane, 1,3-pentanediol and 1,5-pentanediol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, Triethylene glycol monoethyl ether, triethylene glycol monobutyl Ether, glycol derivatives such as dipropylene glycol monomethyl ether; ethanolamine, diethanolamine, triethanolamine, amines such as morpholine; 2-pyrrolidone, NMP, 1,3-dimethyl - imidazolidinone.
　本発明の油性染料組成物は、少なくとも１種以上の油溶性有機溶媒に前記式（１）のトリアリールメタン化合物を溶解または分散させて調整する事ができる。用いられる油溶性有機溶媒としては、例えば、エタノール、ペンタノール、オクタノール、シクロヘキサノール、ベンジルアルコール、テトラフルオロプロパノールなどのアルコール類；エチレングリコールモノエチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノエチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、トリエチレングリコールモノエチルエーテル、エチレングリコールジアセテート、プロピレングリコールジアセテート等のグリコール誘導体；メチルエチルケトン、シクロヘキサノン等のケトン類；ブチルフェニルエーテル、ベンジルエーテル、ヘキシルエーテル等のエーテル類；酢酸エチル、酢酸ブチル、安息香酸エチル、安息香酸ブチル、ラウリン酸エチル、ラウリン酸ブチル等のエステル類；アセトニトリル、ＤＭＦ、ジメチルスルホキシド、スルホラン、ＮＭＰ、２－ピロリドンなどの極性有機溶媒等が挙げられる。これらの溶媒は単独で使用してもよいし、２種以上を混合して用いてもよい。 The oil-based dye composition of the present invention can be prepared by dissolving or dispersing the triarylmethane compound of the above formula (1) in at least one or more oil-soluble organic solvents. As the oil-soluble organic solvent to be used, for example, alcohols such as ethanol, pentanol, octanol, cyclohexanol, benzyl alcohol and tetrafluoropropanol; ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol mono Glycol derivatives such as ethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol diacetate, propylene glycol diacetate; ketones such as methyl ethyl ketone and cyclohexanone; butyl phenyl ether, benzyl Ethers such as ether and hexyl ether; acetic acid Chill, butyl acetate, ethyl benzoate, butyl benzoate, ethyl laurate, esters such as butyl laurate; acetonitrile, DMF, dimethyl sulfoxide, sulfolane, NMP, polar organic solvents such as 2-pyrrolidone. These solvents may be used alone or in combination of two or more.
　油性染料組成物に用いられる分散剤としては、ドデシルベンゼンスルホン酸ナトリウム、ラウリル酸ナトリウム、ナフタレンスルホン酸のホルマリン縮合物、アルキルナフタレンスルホン酸のホルマリン縮合物、クレオソート油スルホン酸のホルマリン縮合物、ポリオキシエチレンアルキルエーテルサルフェートのアンモニウム塩、ポリオキシエチレンアルキルフェニルエーテルサルフェートのアンモニウム、ポリオキシアルキルエーテル燐酸エステル塩等公知のアニオン界面活性剤、ビニルナフタレン誘導体、α、β－エチレン性不飽和カルボン酸の脂肪族アルコールエステル等、スチレン、スチレン誘導体、アクリル酸、アクリル酸誘導体、メタクリル酸、メタクリル酸誘導体、マレイン酸、マレイン酸誘導体、無水マレイン酸、無水マレイン酸誘導体、イタコン酸、イタコン酸誘導体、フマール酸、フマール酸誘導体等から選ばれた少なくとも２つ以上の単量体からなるブロック共重合体、或いはランダム共重合体、またはこれらの塩等の高分子分散剤等が挙げられ、これらの１種以上を分散する色素化合物に対して１０～１００重量％で使用するのが好ましい。またこれらの分散剤と併せて、ポリオキシエチレンソルビタン脂肪酸エステル、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、エチレンオキサイドとプロピレンオキサイドの共重合物等の公知のノニオン系の界面活性剤やシリコーン系、アセチレン系の公知の消泡剤を必要に応じ、顔料分散時及び／または顔料分散化後に添加する事ができる。 Dispersants used in the oil-based dye composition include sodium dodecylbenzene sulfonate, sodium lauryl acid, formalin condensate of naphthalene sulfonic acid, formalin condensate of alkyl naphthalene sulfonic acid, formalin condensate of creosote oil sulfonic acid, poly Well-known anionic surfactants such as ammonium salt of oxyethylene alkyl ether sulfate, ammonium salt of polyoxyethylene alkyl phenyl ether sulfate, polyoxyalkyl ether phosphate ester salt, etc., vinyl naphthalene derivative, fat of α, β-ethylenically unsaturated carboxylic acid Alcohol ester etc., styrene, styrene derivative, acrylic acid, acrylic acid derivative, methacrylic acid, methacrylic acid derivative, maleic acid, maleic acid derivative, maleic anhydride, maleic anhydride Block copolymers comprising at least two or more monomers selected from leic acid derivatives, itaconic acid, itaconic acid derivatives, fumaric acid, fumaric acid derivatives, etc., or random copolymers, or salts thereof Molecular dispersants and the like can be mentioned, and it is preferable to use at 10 to 100% by weight with respect to the dye compound for dispersing one or more of these. In addition to these dispersants, known nonionic surfactants and silicones such as polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, copolymer of ethylene oxide and propylene oxide, etc. If necessary, known antifoaming agents based on acetylene may be added during and / or after pigment dispersion.
　顔料を微粒子に分散する方法としては、サンドミル（ビーズミル）、ロールミル、ボールミル、ペイントシェーカー、超音波分散機、マイクロフルイダイザー等を用いる方法が挙げられるが、これらの中でもサンドミル（ビーズミル）が好ましい。またサンドミル（ビーズミル）における顔料の粉砕においては、径の小さいビーズを使用する、ビーズの充填率を大きくする事等により粉砕効率を高めた条件で処理することが好ましく、更に粉砕処理後に濾過、遠心分離などで素粒子を除去することが好ましい。本発明の染料組成物にはその他の添加剤として表面調整剤、防腐剤、防黴剤、ｐＨ調整剤などを含んでも良い。表面調整剤としては、ポリシロキサン系あるいはポリジメチルシロキサン系の界面活性剤、防腐・防黴剤としてはデヒドロ酢酸ナトリウム、安息香酸ナトリウム、ソジウムピリジンチオン－１－オキサイド、ジンクピリジンチオン－１－オキサイド、１，２－ベンズイソチアゾリン－３－オン、１－ベンズイソチアゾリン－３－オンのアミン塩等を、ｐＨ調整剤としては水酸化ナトリウム、水酸化カリウム、水酸化リチウム等の水酸化アルカリ金属類、トリエタノールアミン、ジエタノールアミン、ジメチルエタノールアミン、ジエチルエタノールアミン等の３級アミン類等が挙げられ、それぞれ必要に応じて添加する事ができる。 Examples of the method of dispersing the pigment into fine particles include a method using a sand mill (beads mill), a roll mill, a ball mill, a paint shaker, an ultrasonic disperser, a microfluidizer, etc., among which sand mills (bead mills) are preferred. In the grinding of the pigment in the sand mill (bead mill), it is preferable to use a small diameter bead, to increase the packing ratio of the beads, etc., and to treat under conditions that increase the grinding efficiency. It is preferable to remove elementary particles by separation or the like. The dye composition of the present invention may contain, as other additives, surface conditioners, preservatives, fungicides, pH adjusters and the like. Surface conditioners include polysiloxane or polydimethylsiloxane surfactants; preservatives and fungicides include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, zinc pyridinethione-1-oxide And an amine salt of 1,2-benzisothiazolin-3-one, 1-benzisothiazolin-3-one and the like, and as a pH adjuster, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, Examples thereof include tertiary amines such as triethanolamine, diethanolamine, dimethylethanolamine, diethylethanolamine and the like, and these can be added as necessary.
　また、本発明の油性または水性染料組成物中には被着色体への色素の定着性を向上させる目的で、必要な範囲内で組成中の媒体と相溶性のあるポリアミド系、ポリウレタン系、ポリエステル系、エポキシ系又はポリアクリル系樹脂を含有させる事が好ましい。また定着性を向上させる目的で、必要な範囲内でエチレン性不飽和基を有するモノマー、オリゴマーや重合開始剤などを含有させてもよい。本発明の油性または水性染料組成物は上記各成分を溶媒に溶解あるいは分散及び混合する事によって調製することができる。 Moreover, in the oil-based or aqueous dye composition of the present invention, for the purpose of improving the fixability of the dye to the colored material, a polyamide based, polyurethane based, polyester compatible with the medium in the composition within the necessary range. It is preferable to contain a system, epoxy resin or polyacrylic resin. Further, in order to improve the fixing property, monomers, oligomers, polymerization initiators and the like having an ethylenically unsaturated group may be contained within the necessary range. The oily or aqueous dye composition of the present invention can be prepared by dissolving, dispersing or mixing the above-mentioned components in a solvent.
　以下、本発明を実施例により具体的に説明するが、本発明は、これらの実施例に限定されるものでは無い。尚、実施例中、「部」は特定しない限り「重量部」を表す。実施例にて得られた各種化合物の分解温度は、ＴＧ／ＤＴＡにより測定した。また、耐湿熱性や耐水性等の評価は染料着色体の色度（Ｌ値、ａ値、ｂ値）を下記の色度測定装置により測定し評価した。測定機器名は以下の通りである。
１．ＴＧ／ＤＴＡ（示唆熱重量同時測定）：
セイコーインスツル（株）製商品名ＴＧ／ＤＴＡ２２０
２．色度測定装置：（株）島津製作所製ＵＶ－３１５０  EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. In the examples, "parts" means "parts by weight" unless specified. The decomposition temperatures of various compounds obtained in the examples were measured by TG / DTA. Moreover, evaluation of moisture-heat resistance, water resistance, etc. measured and evaluated the chromaticity (L value, a value, b value) of the dye colored body with the following chromaticity measurement apparatus. The measuring instrument names are as follows.
1. TG / DTA (simulated thermogravimetry simultaneous measurement):
Seiko Instruments Inc. trade name TG / DTA 220
2. Color measurement device: UV-3150 manufactured by Shimadzu Corporation
実施例１（表１における化合物Ｎｏ．１ａの合成）
　下記式（１００）のＢａｓｉｃＢｌｕｅ７（東京化成工業社製、分解温度：２１７℃）２部を水１５０部に溶解し、攪拌しながら、アセトニトリル３０部にトリストリフルオロメタンスルホニウムメチドのセシウム塩２．１部を溶解させた溶液を加えた。３時間攪拌した後、析出した結晶をろ取、水洗、乾燥し、青色の結晶（本発明のトリアリールメタン化合物）１．５部を得た。分解温度：２５６℃ Example 1 (Synthesis of Compound No. 1a in Table 1)
Dissolve 2 parts of BasicBlue 7 (made by Tokyo Chemical Industry Co., Ltd., decomposition temperature: 217 ° C.) of the following formula (100) in 150 parts of water and, while stirring, add 30 parts of acetonitrile and cesium salt of tristrifluoromethanesulfonium methide 2.1. A solution in which parts were dissolved was added. After stirring for 3 hours, precipitated crystals were collected by filtration, washed with water and dried to obtain 1.5 parts of blue crystals (triarylmethane compound of the present invention). Decomposition temperature: 256 ° C
実施例２（表１における化合物Ｎｏ．２ａの合成）
　下記式（１００）のＢａｓｉｃＢｌｕｅ７、２部を水１５０部に溶解し、攪拌しながら、水１０部にビストリフルオロメタンスルホニウムイミドのカリウム塩１．２部を溶解させた溶液を加えた。３時間攪拌した後、析出した結晶をろ取、水洗、乾燥し、青色の結晶（本発明のトリアリールメタン化合物）０．７部を得た。分解温度：２４０℃ Example 2 (Synthesis of Compound No. 2a in Table 1)
Two parts of BasicBlue 7 of the following formula (100) were dissolved in 150 parts of water, and a solution of 1.2 parts of potassium salt of bistrifluoromethanesulfonium imide in 10 parts of water was added while stirring. After stirring for 3 hours, the precipitated crystals were collected by filtration, washed with water and dried to obtain 0.7 parts of blue crystals (the triarylmethane compound of the present invention). Decomposition temperature: 240 ° C
実施例３
油性染料組成物及び染料着色体の調製
　テトラフルオロプロパノール１０部に、前記実施例で得られた、化合物Ｎｏ．１ａ、化合物Ｎｏ．２ａ、０．５部をそれぞれ溶解し、油性染料組成物を調製した。得られた油性染料組成物をポリカーボネート基盤にスピンコートし、８０℃で３０分乾燥し、染料着色体を調製した。 Example 3
Preparation of Oily Dye Composition and Dye Colored Material In 10 parts of tetrafluoropropanol, the compound No. 1 obtained in the above example was used. Compound No. 1a. Each 0.5 part of 2a was dissolved to prepare an oily dye composition. The obtained oily dye composition was spin-coated on a polycarbonate substrate and dried at 80 ° C. for 30 minutes to prepare a dye-colored material.
　なお、以下の表５及び表９における比較例１は、下記式（１００）のＢａｓｉｃＢｌｕｅ７を使用し、同様に染料着色体を調製したものの試験結果を表す。
Figure JPOXMLDOC01-appb-C000017
 In addition, the comparative example 1 in the following Table 5 and Table 9 represents the test result of what prepared dye coloring matter similarly using BasicBlue7 of following formula (100).
Figure JPOXMLDOC01-appb-C000017
耐湿熱性試験１
　上記の方法で得られた染料着色体を、８５℃、８５％ＲＨの条件の恒温恒湿機中４０時間放置した。試験前後の染料着色体を分光光度計でＬ値、ａ値、ｂ値を、標準光としてＣ光源、２度視野角で測色し、下記式より色差を求めた。尚、色差が小さいほど、色相の変化が少ないため優れている事を示す。
色差＝［（試験前Ｌ値－試験後Ｌ値）２＋（試験前ａ値－試験後ａ値）２＋（試験前ｂ値－試験後ｂ値）２］１／２
耐湿熱試験における測色の測定値及び色差を以下の表３乃至表６に示す。 Moisture and heat resistance test 1
The dye-colored material obtained by the above method was left to stand in a constant temperature and humidity chamber at 85 ° C. and 85% RH for 40 hours. The dye colored materials before and after the test were measured for L value, a value and b value with a C light source as a standard light with a spectrophotometer and a viewing angle of 2 degrees as standard light, and the color difference was determined from the following formula. The smaller the color difference is, the smaller the change in hue is.
Color difference = [(pre-test L value-post-test L value) 2 + (pre-test a value-post-test a value) 2 + (pre-test b value-post-test b value) 2 ] 1/2
Measured values of colorimetry and color differences in the moisture resistance test are shown in Tables 3 to 6 below.
　化合物Ｎｏ．１ａの測色結果を以下の表３に示す。
（表３）
　　　　　　　　　Ｌ値　　　　　ａ値　　　　　　ｂ値
試験前　　　　８４．１５　　－６．２３　　－２４．４３
試験後　　　　８４．９０　　－６．３７　　－２３．２６
試験前後差　　－０．７５　　　０．１４　　　－１．１７ Compound No. The color measurement results of 1a are shown in Table 3 below.
(Table 3)
Before the L value a value b value test 84.15 -6.23 -24.43
After the test 84.90 -6.37 -23.26
Difference before and after the test -0.75 0.14 -1.17
　化合物Ｎｏ．２ａの測色結果を以下の表４に示す。
（表４）
　　　　　　　　　Ｌ値　　　　　ａ値　　　　　　ｂ値
試験前　　　　８２．７１　　－６．４５　　－２７．０４
試験後　　　　８３．３７　　－７．３３　　－２５．８４
試験前後差　　－０．６６　　　０．８８　　　－１．２０ Compound No. The measurement results of 2a are shown in Table 4 below.
(Table 4)
L value a value b value test 82.71-6.45-27.04
After the test 83.37 -7.33 -25.84
Difference before and after the test -0.66 0.88 -1.20
　比較例１の測色結果を以下の表５に示す。
（表５）
　　　　　　　　　　Ｌ値　　　　　ａ値　　　　　　ｂ値
試験前　　　　　７９．６２　　－５．１９　　－３１．９５
試験後　　　　　８９．７０　　－４．２９　　－１１．６６
試験前後差　　－１０．０８　　－０．９０　　－２０．２９ The color measurement results of Comparative Example 1 are shown in Table 5 below.
(Table 5)
L value a value b value test before 79.62 -5.19 -31.95
After the test 89.70-4.29-11.66
Difference before and after the test -10.08 -0.90 -20.29
　上記の表３乃至表５から化合物Ｎｏ．１ａ、化合物Ｎｏ．２ａ及び比較例１の色差を求めた結果を下表６に示す。
（表６）
　　　　　　　　　　　色　差
化合物Ｎｏ．１ａ　　　１．４
化合物Ｎｏ．２ａ　　　１．６
比較例１　　　　　　２２．７ Compound No. 1 from Table 3 to Table 5 above. Compound No. 1a. The results of determination of color differences of 2a and Comparative Example 1 are shown in Table 6 below.
(Table 6)
Color difference compound No. 1a 1.4
Compound No. 2a 1.6
Comparative Example 1 22.7
　表６の結果から明らかなように、比較例１の染料着色体の試験前後の色差が２２．７と非常に大きな値を示すのに対し、本発明の染料着色体は色差１．４及び１．６と非常に小さな値を示し、耐湿熱性に極めて優れていることがわかる。 As apparent from the results of Table 6, while the color difference between the dye colored body of Comparative Example 1 before and after the test shows a very large value of 22.7, the dye colored body of the present invention has a color difference of 1.4 and 1 It shows a very small value of .6, and it can be seen that the heat and humidity resistance is extremely excellent.
耐水性試験１
　上記の方法で得られた染料着色体を、７０℃の温水中に５分間放置した。試験前後の染料着色体を分光光度計でＬ値、ａ値、ｂ値を、標準光としてＣ光源、２度視野角で測色し、下記式より色差を求めた。尚、色差が小さいほど、色相の変化が少ないため優れていることを示す。色差＝［（試験前Ｌ値－試験後Ｌ値）２＋（試験前ａ値－試験後ａ値）２＋（試験前ｂ値－試験後ｂ値）２］１／２
耐水性試験における測色の測定値及び色差を以下の表７乃至表１０に示す。 Water resistance test 1
The dye-colored product obtained by the above method was left in hot water at 70 ° C. for 5 minutes. The dye colored materials before and after the test were measured for L value, a value and b value with a C light source as a standard light with a spectrophotometer and a viewing angle of 2 degrees as standard light, and the color difference was determined from the following formula. The smaller the color difference is, the smaller the change in hue is, and thus the better. Color difference = [(pre-test L value-post-test L value) 2 + (pre-test a value-post-test a value) 2 + (pre-test b value-post-test b value) 2 ] 1/2
Measured values of colorimetry and color differences in the water resistance test are shown in Tables 7 to 10 below.
　化合物Ｎｏ．１ａの測色結果を以下の表７に示す。
（表７）
　　　　　　　　　　Ｌ値　　　　　ａ値　　　　　　ｂ値
試験前　　　　　８４．１５　　－６．２３　　－２４．４３
試験後　　　　　８４．９６　　－６．１２　　－２２．６０
試験前後差　　　－０．８１　　－０．１１　　　－１．８３ Compound No. The measurement results of 1a are shown in Table 7 below.
(Table 7)
Before the L value a value b value test 84.15 -6.23 -24.43
After the test 84.96 -6.12 -22.60
Difference before and after the test -0.81 -0.11 -1.83
　化合物Ｎｏ．２ａの測色結果を以下の表８に示す。
（表８）
　　　　　　　　　Ｌ値　　　　　ａ値　　　　　　ｂ値
試験前　　　　８２．７１　　－６．４５　　－２７．０４
試験後　　　　８６．４３　　－６．０８　　－２０．６７
試験前後差　　－３．７２　　－０．３７　　　－６．３７ Compound No. The colorimetric results of 2a are shown in Table 8 below.
(Table 8)
L value a value b value test 82.71-6.45-27.04
After the test 86.43 -6.08 -20.67
Difference before and after the test -3.72 -0.37 -6.37
　比較例１の測色結果を以下の表９に示す。
（表９）
　　　　　　　　　　Ｌ値　　　　　ａ値　　　　　　ｂ値
試験前　　　　　７９．６２　　－５．１９　　－３１．９５
試験後　　　　　９９．２６　　－０．５８　　　－１．５３
試験前後差　　－１９．６４　　－４．６１　　－３０．４２ The color measurement results of Comparative Example 1 are shown in Table 9 below.
(Table 9)
L value a value b value test before 79.62 -5.19 -31.95
After the test 99.26-0.58-1.53
Difference before and after the test -19.64 -4.61 -30.42
　上記の表７乃至表９から化合物Ｎｏ．１ａ、化合物Ｎｏ．２ａ及び比較例１の色差を求めた結果を以下の表１０に示す。
（表１０）
　　　　　　　　　　　色　差
化合物Ｎｏ．１ａ　　　２．０
化合物Ｎｏ．２ａ　　　７．４
比較例１　　　　　　３６．７ Compound No. 1 from Table 7 to Table 9 above. Compound No. 1a. The results of determination of color differences of 2a and Comparative Example 1 are shown in Table 10 below.
(Table 10)
Color difference compound No. 1a 2.0
Compound No. 2a 7.4
Comparative Example 1 36.7
　表１０の結果から明らかなように、比較例１の染料着色体の試験前後の色差が３６．７と非常に大きな値を示すのに対し、本発明の染料着色体は色差２．０及び７．４と非常に小さな値を示し、耐水性にきわめて優れている事がわかる。 As is clear from the results in Table 10, the color difference between the dye colored body of Comparative Example 1 before and after the test shows a very large value of 36.7, while the dye colored body of the present invention has a color difference of 2.0 and 7 It shows a very small value of .4, indicating that it is extremely excellent in water resistance.
実施例４（表１における化合物Ｎｏ．５ａの合成）
　下記式（１０１）のＢａｓｉｃＢｌｕｅ２６（東京化成工業社製、分解温度：２２３℃）２部をＤＭＦ２０部に溶解し、攪拌しながら、ＤＭＦ２０部にトリストリフルオロメタンスルホニウムメチドのセシウム塩２．５部を溶解させた溶液を加えた。２時間攪拌した後、液ろ過し、得られたろ液に水を加えた。析出した結晶をろ取、水洗、乾燥し、紫色の結晶（本発明のトリアリールメタン化合物）１．１部を得た。分解温度：２６７℃
Figure JPOXMLDOC01-appb-C000018
 Example 4 (Synthesis of Compound No. 5a in Table 1)
2 parts of BasicBlue 26 (manufactured by Tokyo Chemical Industry Co., Ltd., decomposition temperature: 223 ° C.) of the following formula (101) is dissolved in 20 parts of DMF, and 2.5 parts of cesium salt of tristrifluoromethanesulfonium methide is added to 20 parts of DMF while stirring. The dissolved solution was added. After stirring for 2 hours, liquid filtration was performed, and water was added to the obtained filtrate. The precipitated crystals were collected by filtration, washed with water and dried to obtain 1.1 parts of purple crystals (triarylmethane compound of the present invention). Decomposition temperature: 267 ° C
Figure JPOXMLDOC01-appb-C000018
実施例５
油性染料組成物及び染料着色体の調製
　テトラフルオロプロパノール１０部に、前記実施例４で得られた化合物Ｎｏ．５ａ、０．５部を溶解し、油性染料組成物を調製した。得られた油性染料組成物をポリカーボネート基盤にスピンコートし、８０℃で３０分乾燥し、染料着色体を調製した。 Example 5
Preparation of Oily Dye Composition and Dye Colored Material In 10 parts of tetrafluoropropanol, the compound No. 1 obtained in Example 4 was used. An oil dye composition was prepared by dissolving 0.5 parts of 5a. The obtained oily dye composition was spin-coated on a polycarbonate substrate and dried at 80 ° C. for 30 minutes to prepare a dye-colored material.
　なお、以下の表１２における比較例２は、上記式（１０１）のＢａｓｉｃＢｌｕｅ２６を使用し、同様に染料着色体を調製したものの評価結果を表す。 In addition, the comparative example 2 in the following Table 12 represents the evaluation result of what prepared dye coloring matter similarly using BasicBlue26 of said Formula (101).
耐湿熱性試験２
　試験方法は耐湿熱性試験１に同じ。測色の測定値及び色差を以下の表１１乃至１３に示す。 Moisture and heat resistance test 2
The test method is the same as moist heat resistance test 1. The colorimetric measurement values and color differences are shown in Tables 11 to 13 below.
　化合物Ｎｏ．５ａの測色結果を以下の表１１に示す。
（表１１）
　　　　　　　　　　Ｌ値　　　　　ａ値　　　　　　ｂ値
試験前　　　　　８６．０８　　－６．８７　　－２１．１５
試験後　　　　　８６．２４　　－６．８６　　－２０．８４
試験前後差　　　－０．１６　　－０．０１　　　－０．３１ Compound No. The color measurement results of 5a are shown in Table 11 below.
(Table 11)
L value a value b value before the test 86.08-6.87-21.15
After the test 86.24-6.86-20.84
Difference before and after test -0.16 -0.01 -0.31
　比較例２の測色結果を以下の表１２に示す。
（表１２）
　　　　　　　　　　Ｌ値　　　　　ａ値　　　　　　ｂ値
試験前　　　　　８５．５４　　－９．１７　　－２１．２５
試験後　　　　　８８．６０　　　８．４０　　－１５．４２
試験前後差　　　－３．０６　　－０．７７　　　－５．８３ The colorimetric results of Comparative Example 2 are shown in Table 12 below.
(Table 12)
L value a value b value test 85.54-9.17-21.25
After the test 88.60 8.40-15.42
Difference before and after test -3.06 -0.77 -5.83
　上記の表１１及び表１２から化合物Ｎｏ．５ａ及び比較例の色差を求めた結果を以下の表１３に示す。
（表１３）
　　　　　　　　　　　色　差
化合物Ｎｏ．５ａ　　　０．３
比較例２　　　　　　　６．６ Compound No. 1 from Table 11 and Table 12 above. The results of determination of color differences of 5a and the comparative example are shown in Table 13 below.
(Table 13)
Color difference compound No. 5a 0.3
Comparative example 2 6.6
　表１３の結果から明らかなように、比較例２の染料着色体の試験前後の色差が６．６と非常に大きな値を示すのに対し、本発明の染料着色体は色差０．３と非常に小さな値を示し、耐湿熱性にきわめて優れていることがわかる。 As is clear from the results in Table 13, the color difference between the dye-colored product of Comparative Example 2 before and after the test shows a very large value of 6.6, while the dye-colored product of the present invention is very good with a color difference of 0.3. It is understood that the heat and humidity resistance is extremely excellent.
耐水性試験２
　試験方法は耐水性試験１に同じ。測色の測定値及び色差を以下の表１４乃至表１６に示す。 Water resistance test 2
The test method is the same as water resistance test 1. Measured values of colorimetry and color differences are shown in Tables 14 to 16 below.
　化合物Ｎｏ．５ａの測色結果を以下の表１４に示す。
（表１４）
　　　　　　　　　　Ｌ値　　　　　ａ値　　　　　　ｂ値
試験前　　　　　８６．６６　　－６．７８　　－２０．３４
試験後　　　　　８８．６２　　－３．６４　　－１１．８９
試験前後差　　　－１．９６　　－３．１４　　　－８．４５ Compound No. The color measurement results of 5a are shown in Table 14 below.
(Table 14)
L value a value b value test 86.66-6.78-20.34
After the test 88.62 -3.64 -11.89
Difference before and after the test -1.96 -3.14 -8.45
　比較例２の測色結果を以下の表１５に示す。
（表１５）
　　　　　　　　　　Ｌ値　　　　　ａ値　　　　　　ｂ値
試験前　　　　　８５．５７　　－９．１７　　－２１．２５
試験後　　　　　９４．５５　　　３．９２　　　－１．２８
試験前後差　　　－８．９８　－１３．０９　　－１９．９７ The measurement results of Comparative Example 2 are shown in Table 15 below.
(Table 15)
L value a value b value before the test 85.57-9.17-21.25
After the test 94.55 3.92 -1.28
Before and after the test -8.98-13.09-19.97
　上記の表１４及び表１５から化合物Ｎｏ．５ａ及び比較例２の色差を求めた結果を以下の表１６に示す。
（表１６）
　　　　　　　　　　　色　差
化合物Ｎｏ．５ａ　　　９．２
比較例２　　　　　　２５．５ Compound No. 1 from Table 14 and Table 15 above. The results of determining the color difference of 5a and Comparative Example 2 are shown in Table 16 below.
(Table 16)
Color difference compound No. 5a 9.2
Comparative example 2 25.5
　表１６の結果から明らかなように、比較例２の染料着色体の試験前後の色差が２５．５と非常に大きな値を示すのに対し、本発明の染料着色体は色差９．２と非常に小さな値を示し、耐水性にきわめて優れていることがわかる。 As apparent from the results in Table 16, while the color difference between before and after the test of the dye colored body of Comparative Example 2 shows a very large value of 25.5, the dye colored body of the present invention is very high with a color difference of 9.2. Small value, it is understood that the water resistance is extremely excellent.
実施例６（表１における化合物Ｎｏ．４５ａの合成）
下記式（１０２）の染料２部を、水３０部とメタノール７５部の混合溶液に溶解し、攪拌しながら、ＤＭＦ２部とメタノール１２部の混合溶液にトリストリフルオロメタンスルホニウムメチドのセシウム塩２．４８部を溶解させた溶液を加えた。３時間、６０℃で加熱撹拌した後、析出した結晶をろ取、水洗、乾燥し、青色の結晶（本発明のトリアリールメタン化合物）１．３部を得た。分解温度：２６２℃ Example 6 (Synthesis of Compound No. 45a in Table 1)
A cesium salt of tristrifluoromethanesulfonium methide is dissolved in a mixed solution of 2 parts of DMF and 12 parts of methanol while dissolving 2 parts of a dye of the following formula (102) in a mixed solution of 30 parts of water and 75 parts of methanol while stirring. A solution of 48 parts was added. After heating and stirring for 3 hours at 60 ° C., the precipitated crystals were collected by filtration, washed with water and dried to obtain 1.3 parts of blue crystals (triarylmethane compound of the present invention). Decomposition temperature: 262 ° C
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
実施例７（表１における化合物Ｎｏ．５７ａの合成）
下記式（１０３）の染料２．５部を、水２部とメタノール３８部の混合溶液に溶解し、攪拌しながら、ＤＭＦ２部とメタノール１２部の混合溶液にトリストリフルオロメタンスルホニウムメチドのセシウム塩２．８７部を溶解させた溶液を加えた。３時間、６０℃で加熱撹拌した後、析出した結晶をろ取、水洗、乾燥し、青色の結晶（本発明のトリアリールメタン化合物）２．８部を得た。分解温度：２６９℃ Example 7 (Synthesis of Compound No. 57a in Table 1)
A cesium salt of tristrifluoromethanesulfonium methide is dissolved in a mixed solution of 2 parts of DMF and 12 parts of methanol while dissolving 2.5 parts of a dye of the following formula (103) in a mixed solution of 2 parts of water and 38 parts of methanol while stirring. A solution of 2.87 parts dissolved was added. After heating and stirring for 3 hours at 60 ° C., the precipitated crystals were collected by filtration, washed with water and dried to obtain 2.8 parts of blue crystals (triarylmethane compound of the present invention). Decomposition temperature: 269 ° C
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
実施例８（表１における化合物Ｎｏ．６９ａの合成）
下記式（１０４）の染料３部を、水１０部とメタノール５３部の混合溶液に溶解し、攪拌しながら、ＤＭＦ３部とメタノール２５部の混合溶液にトリストリフルオロメタンスルホニウムメチドのセシウム塩２．９４部を溶解させた溶液を加えた。３時間、６０℃で加熱撹拌した後、析出した結晶をろ取、水洗、乾燥し、青色の結晶（本発明のトリアリールメタン化合物）３．５部を得た。分解温度：２６７℃ Example 8 (Synthesis of Compound No. 69a in Table 1)
A cesium salt of tristrifluoromethanesulfonium methide is dissolved in a mixed solution of 3 parts of DMF and 25 parts of methanol while dissolving 3 parts of the dye of the following formula (104) in a mixed solution of 10 parts of water and 53 parts of methanol while stirring. A solution of 94 parts was added. After heating and stirring for 3 hours at 60 ° C., the precipitated crystals were collected by filtration, washed with water and dried to obtain 3.5 parts of blue crystals (triarylmethane compound of the present invention). Decomposition temperature: 267 ° C
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
実施例９（表２における化合物Ｎｏ．１ｂの合成）
　下記式（１０５）のマラカイトグリーンシュウ酸塩1部（分解温度：１７５℃）を水５０部に溶解し、攪拌しながら、ＤＭＦ５部にトリストリフルオロメタンスルホニウムメチドのセシウム塩２部を溶解させた溶液を加えた。３時間攪拌した後、析出した結晶をろ取、水洗、乾燥し、暗緑色の結晶（本発明のトリアリールメタン化合物）０．５部を得た。分解温度：１９０℃ Example 9 (Synthesis of Compound No. 1b in Table 2)
In 50 parts of water, 1 part of malachite green oxalate of the following formula (105) was dissolved in 50 parts of water, and 2 parts of a cesium salt of tristrifluoromethanesulfonium methide was dissolved in 5 parts of DMF. The solution was added. After stirring for 3 hours, the precipitated crystals were collected by filtration, washed with water and dried to obtain 0.5 parts of dark green crystals (the triarylmethane compound of the present invention). Decomposition temperature: 190 ° C
実施例１０（表２における化合物Ｎｏ．３ｂの合成）
　下記式（１０６）のＢａｓｉｃＢｌｕｅ１（分解温度：１９０℃）５部を水５００部に溶解し、攪拌しながら、ＤＭＦ１０部にトリストリフルオロメタンスルホニウムメチドのセシウム塩２部を溶解させた溶液を加えた。３時間攪拌した後、析出した結晶をろ取、水洗、乾燥し、青色の結晶（本発明のトリアリールメタン化合物）０．７部を得た。分解温度：２３０℃ Example 10 (synthesis of compound No. 3b in Table 2)
In 500 parts of water was dissolved 5 parts of BasicBlue 1 (decomposition temperature: 190 ° C.) of the following formula (106), and a solution in which 2 parts of a cesium salt of tristrifluoromethanesulfonium methide was dissolved in 10 parts of DMF was added while stirring. . After stirring for 3 hours, the precipitated crystals were collected by filtration, washed with water and dried to obtain 0.7 parts of blue crystals (the triarylmethane compound of the present invention). Decomposition temperature: 230 ° C
実施例１１（表２における化合物Ｎｏ．５ｂの合成）
　下記式（１０７）のＢａｓｉｃＶｉｏｌｅｔ３（分解温度：２０５℃）５部を水５００部に溶解し、攪拌しながら、ＤＭＦ１０部にトリストリフルオロメタンスルホニウムメチドのセシウム塩１部を溶解させた溶液を加えた。３時間攪拌した後、析出した結晶をろ取、水洗、乾燥し、紫色の結晶（本発明のトリアリールメタン化合物）１．２部を得た。分解温度：２４０℃ Example 11 (synthesis of compound No. 5b in Table 2)
In 500 parts of water, 5 parts of BasicViolet 3 (decomposition temperature: 205 ° C.) of the following formula (107) was dissolved, and a solution in which 1 part of a cesium salt of tristrifluoromethanesulfonium methide was dissolved in 10 parts of DMF was added while stirring. . After stirring for 3 hours, the precipitated crystals were collected by filtration, washed with water and dried to obtain 1.2 parts of purple crystals (triarylmethane compound of the present invention). Decomposition temperature: 240 ° C
実施例１２
油性染料組成物及び染料着色体の調製
　テトラフルオロプロパノール１０部に、それぞれ前記各実施例で得られた、化合物Ｎｏ．１ｂ、化合物Ｎｏ．３ｂ、化合物Ｎｏ．５ｂ、０．５部を溶解し、油性染料組成物を調製した。得られた油性染料組成物をポリカーボネート基盤にスピンコートし、８０℃で３０分乾燥し、染料着色体を調製した。 Example 12
Preparation of Oily Dye Composition and Dye Colored Material In 10 parts of tetrafluoropropanol, the compound No. 1 obtained in each of the above examples was used. Compound No. 1b. 3b, the compound No. An oil dye composition was prepared by dissolving 0.5 parts of 5b. The obtained oily dye composition was spin-coated on a polycarbonate substrate and dried at 80 ° C. for 30 minutes to prepare a dye-colored material.
　下記の表１７および表１８に記載の比較例３は、下記式（１０５）のマラカイトグリーンシュウ酸塩を、比較例４は、下記式（１０６）のＢａｓｉｃＢｌｕｅ１を、比較例５は下記式（１０７）のＢａｓｉｃＶｉｏｌｅｔ３をそれぞれ使用し、同様に染料着色体を調製した。
Figure JPOXMLDOC01-appb-C000022
 Comparative Example 3 described in Tables 17 and 18 below is malachite green oxalate of the following Formula (105), Comparative Example 4 is BasicBlue 1 of the following Formula (106), and Comparative Example 5 is the following Formula (107) The dye-colored bodies were similarly prepared using Basic Violet 3 of the above).
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
耐水性試験３
　上記の方法で得られた染料着色体を、７０℃の温水中に３０秒間放置した。試験前後の染料着色体を分光光度計でＬ値、ａ値、ｂ値を、標準光としてＣ光源、２度視野角で測色し、下記式より色差を求めた。尚、色差が小さいほど、色相の変化が少ないため優れていることを示す。色差＝［（試験前Ｌ値－試験後Ｌ値）２＋（試験前ａ値－試験後ａ値）２＋（試験前ｂ値－試験後ｂ値）２］１／２
耐水性試験における測色の測定値および色差を以下の表１７乃至表２３に示す。 Water resistance test 3
The dye-colored product obtained by the above method was left in warm water at 70 ° C. for 30 seconds. The dye colored materials before and after the test were measured for L value, a value and b value with a C light source as a standard light with a spectrophotometer and a viewing angle of 2 degrees as standard light, and the color difference was determined from the following formula. The smaller the color difference is, the smaller the change in hue is, and thus the better. Color difference = [(pre-test L value-post-test L value) 2 + (pre-test a value-post-test a value) 2 + (pre-test b value-post-test b value) 2 ] 1/2
Measured values of colorimetry and color differences in the water resistance test are shown in Tables 17 to 23 below.
　化合物Ｎｏ．１ｂの測色結果を以下の表１７に示す。
（表１７）
　　　　　　　　　Ｌ値　　　　　　ａ値　　　　　ｂ値
試験前　　　　９３．２５　　－１０．９４　　－６．３７
試験後　　　　９３．５８　　　－８．７９　　－５．６２
試験前後差　　－０．３３　　　－２．１５　　－０．７５ Compound No. The measurement results of 1b are shown in Table 17 below.
(Table 17)
L value a value b value test before 93.25 -10.94 -6.37
After the test 93.58-8.79-5.62
Difference before and after test -0.33-2.15-0.75
　化合物Ｎｏ．３ｂの測色結果を以下の表１８に示す。
（表１８）
　　　　　　　　　Ｌ値　　　　　　ａ値　　　　　ｂ値
試験前　　　　９２．１２　　－１１．７３　－１０．５３
試験後　　　　９２．４４　　－１０．１６　　－９．３７
試験前後差　　－０．３２　　　－１．５７　　－１．１６ Compound No. The color measurement results of 3b are shown in Table 18 below.
(Table 18)
L value a value b value before the test 92.12 -11.73 -10.53
After the test 92.44 -10.16 -9.37
Difference before and after test -0.32 -1.57 -1.16
　化合物Ｎｏ．５ｂの測色結果を以下の表１９に示す。
（表１９）
　　　　　　　　　Ｌ値　　　　　　ａ値　　　　　　ｂ値
試験前　　　　７７．９７　　　１９．３３　　－３２．２５
試験後　　　　７９．５８　　　１６．６１　　－２８．９５
試験前後差　　－１．６１　　　　２．７２　　　－３．３０ Compound No. The color measurement results of 5b are shown in Table 19 below.
(Table 19)
L value a value b value test 77.97 19.33 -32.25
After the test 79.58 16.61 -28.95
Difference before and after test -1.61 2.72 -3.30
　比較例３の測色結果を以下の表２０に示す。
（表２０）
　　　　　　　　　　Ｌ値　　　　　ａ値　　　　　ｂ値
試験前　　　　　８９．７７　－１０．９４　　－４．４９
試験後　　　　１００．２２　　－０．２１　　－０．４１
試験前後差　　－１０．４５　－１０．７３　　－４．０８ The color measurement results of Comparative Example 3 are shown in Table 20 below.
(Table 20)
L value a value b value test 89.77 -10.94 -4.49
After the test 100.22 -0.21 -0.41
Difference before and after the test -10.45-10.73-4.08
　比較例４の測色結果を以下の表２１に示す。
（表２１）
　　　　　　　　　　Ｌ値　　　　　ａ値　　　　　ｂ値
試験前　　　　　９５．８３　　－７．２７　　－５．９３
試験後　　　　１００．１６　　－０．１３　　－０．４８
試験前後差　　　－４．３３　　－７．１４　　－５．４５ The colorimetric results of Comparative Example 4 are shown in Table 21 below.
(Table 21)
L value a value b value test 95.83 -7.27 -5.93
After the test 100.16 -0.13 -0.48
The difference before and after the test -4.33 -7.14 -5.45
　比較例５の測色結果を以下の表２２に示す。
（表２２）
　　　　　　　　　　Ｌ値　　　　　ａ値　　　　　　ｂ値
試験前　　　　　７５．１４　　１５．６２　　－３７．０６
試験後　　　　　９９．６５　　　０．２１　　　－１．１３
試験前後差　　－２４．５１　　１５．４１　　－３５．９３ The measurement results of Comparative Example 5 are shown in Table 22 below.
(Table 22)
L value a value b value test 75.14 15.62-37.06
After the test 99.65 0.21 -1.13
Difference before and after the test -24.51 15.41-35.93
　上記の表１７乃至表２２から化合物Ｎｏ．１ｂ、Ｎｏ．３ｂ、Ｎｏ．５ｂ、比較例３、４及び５の色差を求めた結果を以下の表２３に示す。
（表２３）
　　　　　　　　　　　色　差
化合物Ｎｏ．１ｂ　　　２．３
化合物Ｎｏ．３ｂ　　　２．０
化合物Ｎｏ．５ｂ　　　４．６
比較例３　　　　　　１５．５
比較例４　　　　　　１０．０
比較例５　　　　　　４６．１ Compound No. 1 from Table 17 to Table 22 above. 1b, no. 3b, no. The results of determination of color differences of 5b and Comparative Examples 3, 4 and 5 are shown in Table 23 below.
(Table 23)
Color difference compound No. 1b 2.3
Compound No. 3b 2.0
Compound No. 5b 4.6
Comparative example 3 15.5
Comparative example 4 10.0
Comparative Example 5 46.1
　表２３の結果から明らかなように、比較例３の染料着色体の試験前後の色差が１５．５と大きな値を示すのに対し、カチオン部分が同一である本発明の化合物Ｎｏ．１ｂの染料着色体は色差２．３と小さな値を示し、耐水性にきわめて優れている事がわかる。また同様に比較例４及び５の染料着色体の試験前後の色差が１０．０、４６．１と大きな値を示すのに対し、本発明の化合物Ｎｏ．３ｂ及びＮｏ．５ｂの染料着色体の色差は２．０、４．６と非常に小さい値を示している。 As is clear from the results in Table 23, the color differences of the dye-colored product of Comparative Example 3 before and after the test show a large value of 15.5, while the compound No. 1 of the present invention in which the cation portion is the same. The dye-colored product of 1b exhibits a small value of color difference of 2.3, and it can be seen that it is extremely excellent in water resistance. Similarly, while the color difference between before and after the test of the dye colored body of Comparative Examples 4 and 5 shows a large value of 10.0 and 46.1, the compound No. 1 of the present invention. 3b and no. The color difference of the dye-colored material of 5b shows very small values of 2.0 and 4.6.
実施例１３（表２における化合物Ｎｏ.５３ｂの合成）
　下記式（１０８）の染料２．３１部を水２００部とメタノール１２０部の混合溶液に溶解し、攪拌しながら、ＤＭＦ４．２部にトリストリフルオロメタンスルホニウムメチドのセシウム塩２．３０部を溶解させた溶液を加えた。３時間攪拌した後、析出した結晶をろ取、水洗、乾燥し、青色の結晶（化合物Ｎｏ.５３ｂ）３．６４部を得た。分解温度：２３１℃ Example 13 (synthesis of compound No. 53b in Table 2)
In a mixed solution of 200 parts of water and 120 parts of methanol, 2.31 parts of a dye of the following formula (108) is dissolved, and 2.30 parts of a cesium salt of tristrifluoromethanesulfonium methide is dissolved in 4.2 parts of DMF while stirring. The added solution was added. After stirring for 3 hours, precipitated crystals were collected by filtration, washed with water and dried to obtain 3.64 parts of blue crystals (Compound No. 53b). Decomposition temperature: 231 ° C
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
実施例１４（表２における化合物Ｎｏ．２１ｂの合成）
下記式（１０９）の染料３．１部を水１５０部とメタノール７２部の混合溶液に溶解し、攪拌しながら、ＤＭＦ６．３部とメタノール１６部の混合溶液にトリストリフルオロメタンスルホニウムメチドのセシウム塩３．５５部を溶解させた溶液を加えた。３時間、４０℃で加熱撹拌した後、析出した結晶をろ取、水洗、乾燥し、青色の結晶（化合物Ｎｏ．２１ｂ）１．６３部を得た。分解温度：２３４℃ Example 14 (synthesis of compound No. 21b in Table 2)
Dissolve 3.1 parts of the dye of the following formula (109) in a mixed solution of 150 parts of water and 72 parts of methanol, add cesium in tristrifluoromethanesulfonium methide to a mixed solution of 6.3 parts of DMF and 16 parts of methanol while stirring. A solution of 3.55 parts salt was added. After heating and stirring for 3 hours at 40 ° C., the precipitated crystals were collected by filtration, washed with water and dried to obtain 1.63 parts of blue crystals (Compound No. 21b). Decomposition temperature: 234 ° C
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
実施例１５（表２における化合物Ｎｏ．３３ｂの合成）
下記式（１１０）の染料１．０部を水１００部とメタノール４０部の混合溶液に溶解し、攪拌しながら、ＤＭＦ３．２部とメタノール８部の混合溶液にトリストリフルオロメタンスルホニウムメチドのセシウム塩１．３１部を溶解させた溶液を加えた。３時間、３０℃で加熱撹拌した後、析出した結晶をろ取、水洗、乾燥し、青色の結晶（化合物Ｎｏ．３３ｂ）０．９８部を得た。分解温度：２３２℃ Example 15 (Synthesis of Compound No. 33b in Table 2)
Dissolve 1.0 part of a dye of the following formula (110) in a mixed solution of 100 parts of water and 40 parts of methanol, add cesium in tristrifluoromethanesulfonium methide to a mixed solution of 3.2 parts of DMF and 8 parts of methanol while stirring A solution of 1.31 parts of salt was added. After heating and stirring for 3 hours at 30 ° C., the precipitated crystals were collected by filtration, washed with water and dried to obtain 0.98 parts of blue crystals (Compound No. 33b). Decomposition temperature: 232 ° C
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
実施例１６（表２における化合物Ｎｏ．６９ｂの合成）
下記式（１１１）の染料１．０部を水１００部とメタノール４０部の混合溶液に溶解し、攪拌しながら、ＤＭＦ３．２部とメタノール８部の混合溶液にトリストリフルオロメタンスルホニウムメチドのセシウム塩０．６５部を溶解させた溶液を加えた。３時間、４０℃で加熱撹拌した後、析出した結晶をろ取、水洗、乾燥し、青色の結晶（化合物Ｎｏ．６９ｂ）０．７３部を得た。分解温度：２７７℃ Example 16 (synthesis of compound No. 69b in Table 2)
Dissolve 1.0 part of the dye of the following formula (111) in a mixed solution of 100 parts of water and 40 parts of methanol, add cesium in tristrifluoromethanesulfonium methide to a mixed solution of 3.2 parts of DMF and 8 parts of methanol while stirring A solution of 0.65 parts salt was added. After heating and stirring for 3 hours at 40 ° C., the precipitated crystals were collected by filtration, washed with water and dried to obtain 0.73 parts of blue crystals (Compound No. 69b). Decomposition temperature: 277 ° C
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028
　以上のように本発明の前記式（１）で表されるトリアリールメタン化合物はその分解温度の比較から耐熱性に優れ、その染料着色体は耐湿熱性および耐水性に優れた特性を有するものであり、本発明のトリアリールメタン系染料はカラーフィルター用インキやインクジェット用インキ等、アプリケーションの幅が広がる等の産業的な価値が高い事が明らかとなった。 As mentioned above, the triarylmethane compound represented by the said Formula (1) of this invention is excellent in heat resistance from the comparison of the decomposition temperature, and the dye colored body has the characteristic excellent in heat-and-moisture resistance and water resistance. It has been revealed that the triarylmethane dyes of the present invention have high industrial value such as broadening the range of applications such as color filter inks and ink jet inks.

Claims (7)

  1. 　一般式（１）で表されるトリアリールメタン化合物。
    Figure JPOXMLDOC01-appb-C000001
     （式（１）においてＡｒ１、Ａｒ２及びＡｒ３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。）     The triarylmethane compound represented by General formula (1).
    Figure JPOXMLDOC01-appb-C000001
     (In the formula (1), Ar 1 , Ar 2 and Ar 3 each independently represent an aromatic residue bonded to a central carbon atom by a carbon atom, and X − represents a bistrifluoromethanesulfonyl imide anion or tristrifluoromethanesulfonyl Represents methide anion)
  2. 　一般式（２）で表される事を特徴とする請求項１に記載のトリアリールメタン化合物。
    Figure JPOXMLDOC01-appb-C000002
     (式（２）においてＲ１ａ～Ｒ６ａ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、Ｒ７ａ～Ｒ２０ａ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。)     The triarylmethane compound according to claim 1, which is represented by the general formula (2).
    Figure JPOXMLDOC01-appb-C000002
     (In formula (2), R 1a to R 6a each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group or a benzyl group, and R 7a to R 20a each independently represent a hydrogen atom or carbon And represents an alkyl group of 1 to 6 or a halogen atom, and X - is as defined in the above formula (1).
  3. 　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請求項２に記載のトリアリールメタン化合物。 The triarylmethane compound according to claim 2, wherein X - is tristrifluoromethanesulfonyl methide anion.
  4. 　一般式（３）で表される事を特徴とする請求項１に記載のトリアリールメタン化合物。
    Figure JPOXMLDOC01-appb-C000003
     (式（３）においてＲ１ｂ～Ｒ４ｂ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、Ｒ５ｂ～Ｒ１６ｂ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、Ｒ１７ｂ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。）     The triarylmethane compound according to claim 1, which is represented by the general formula (3).
    Figure JPOXMLDOC01-appb-C000003
     (In Formula (3), R 1b to R 4b each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group or a benzyl group, and R 5b to R 16b each independently represent a hydrogen atom or carbon represents a number 1-6 alkyl group or a halogen atom, R 17b represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a halogen atom or an amino group, X - is as defined in the above formula (1)).
  5. 　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請求項４に記載のトリアリールメタン化合物。 5. The triarylmethane compound according to claim 4, wherein X - is tristrifluoromethanesulfonyl methide anion.
  6. 請求項１乃至５のいずれか一項に記載のトリアリールメタン化合物と少なくとも１種以上の油溶性有機溶媒を含有する油性染料組成物。 An oil dye composition comprising the triarylmethane compound according to any one of claims 1 to 5 and at least one or more oil-soluble organic solvents.
  7. 請求項１乃至５のいずれか一項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。 An aqueous dye composition comprising the triarylmethane compound according to any one of claims 1 to 5 and an aqueous medium.
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