JP5800493B2 - Rhodamine dye - Google Patents

Description

  The present invention relates to a novel rhodamine dye.

  Rhodamine dyes such as Rhodamine B, Rhodamine 3B, and Rhodamine 6G are widely used as red or violet dyes, and are used in a wide range of applications such as various paints, water-based inks, oil-based inks, ink-jet inks, color filters, and dyes. Application has been made. In general, the characteristics required of a color material vary depending on the application, but it is particularly strongly required that the colored material is robust against light, heat, and the like.

  In general, rhodamine dyes are clear and have excellent color developability, but have the disadvantage of poor fastness such as light resistance, heat resistance, moist heat resistance, and water resistance. For this reason, there is a demand for dyes having the sharpness and color development of rhodamine dyes and having high fastness, but no rhodamine dyes having these properties have been found. Patent Document 1 describes a rhodamine dye composed of a cation moiety of a rhodamine compound, chloride ion, and further zinc chloride. As a result of the study by the present inventors, the rhodamine dye described in Patent Document 1 is light-resistant. Fastness such as heat resistance, heat resistance, water resistance, and moist heat resistance was insufficient. Further, Patent Document 2 describes a rhodamine dye having a fluorinated alkylsulfonyl counter ion, but no specific compound is exemplified, and the light resistance, heat resistance, moist heat resistance, water resistance, etc. of the dye composition are not described. There is no mention of robustness.

JP-A-5-271559 JP-A-8-253705

  An object of this invention is to provide the novel rhodamine dye excellent in fastness, such as light resistance, heat resistance, heat-and-moisture resistance, and water resistance, and the dye composition using this dye.

  As a result of intensive studies to solve the above problems, the present inventors have found that rhodamine dyes having a specific structure dramatically improve fastness such as heat resistance as compared with the conventional ones. It came to complete.

（一般式（１）においてＲ_１〜Ｒ_４はそれぞれ独立に水素原子、アルキル基またはアリール基を表し、Ｒ_５、Ｒ_６及びＲ_８はそれぞれ独立に水素原子または置換基を表す。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（１）が下記一般式（２）で表される（１）に記載のローダミン染料

（一般式（２）においてＲ_１〜Ｒ_６、及びＸ⁻は式（１）におけるのと同じ意味を表し、Ｒ_７は水素原子またはアルキル基を表す。）、
（３）一般式（１）のＲ_８がカルボアミド基及びその誘導体である（１）に記載のローダミン染料、
（４）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（１）乃至（３）のいずれか一つに記載のローダミン染料、
（５）（１）乃至（４）のいずれか一つに記載のローダミン染料と少なくとも１種以上の油性溶媒を含有する油性染料組成物、
（６）（１）乃至（４）のいずれか一つに記載のローダミン染料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) Rhodamine dye represented by the following general formula (1)

(In the general formula (1) _R 1 ~R ₄ represent each independently a hydrogen atom, an alkyl group or an aryl _group, a R 5, _{R 6} and _{R 8} each independently represents a hydrogen atom or a substituent .X ^- is Represents a bistrifluoromethanesulfonylimide anion or a tristrifluoromethanesulfonylmethide anion).
(2) The rhodamine dye according to (1), wherein the general formula (1) is represented by the following general formula (2)

(In the general formula (2), R _{1 to} R ₆ and X ⁻ represent the same meaning as in the formula (1), and R ₇ represents a hydrogen atom or an alkyl group).
(3) The rhodamine dye according to (1), wherein R _{8 in the} general formula (1) is a carboamide group or a derivative thereof,
(4) The rhodamine dye according to any one of (1) to (3), wherein X ⁻ is a tristrifluoromethanesulfonylmethide anion,
(5) An oily dye composition comprising the rhodamine dye according to any one of (1) to (4) and at least one oily solvent,
(6) An aqueous dye composition comprising the rhodamine dye according to any one of (1) to (4) and an aqueous medium,
About.

  When the rhodamine dye of the present invention is formed into an oil-based or aqueous dye composition to be processed into a dye-colored product, the rhodamine dye exhibits characteristics superior in fastness to conventional products. That is, the rhodamine dye of the present invention can be suitably used for a dye-colored product, and can be applied to a wide range of uses such as a color filter and an inkjet ink.

  The rhodamine dye of the present invention is represented by the general formula (1) or (2).

In the general formulas (1) and (2), X ⁻ represents a bistrifluoromethanesulfonylimide anion or a tristrifluoromethanesulfonylmethide anion, and a tristrifluoromethanesulfonylmethide anion is particularly preferable.

In the general formula (1), R _{1 to} R ₄ each independently represents a hydrogen atom, an alkyl group, or an aryl group.

Examples of the alkyl group in R _{1 to} R ₄ of the general formula (1) 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. These alkyl groups may have a substituent, and the substituent is not particularly limited. For example, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a 2-sulfoethyl group, a carboxyethyl group, a cyanoethyl group, Examples include methoxyethyl group, ethoxyethyl group, butoxyethyl group, trifluoromethyl group, pentafluoroethyl group, carbamoyl group, carboxyl group and the like.

In R _{1 to} R ₄ of the general formula (1), examples of the aryl group include aromatic hydrocarbon residues such as a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, and a benzopyrenyl group; a pyridyl group, a pyrazyl group, Examples thereof include an aromatic heterocyclic residue such as a pyrimidyl group, a quinolyl group, an isoquinolyl group, a pyrrolyl group, an indolenyl group, an imidazolyl group, a carbazolyl group, a thienyl group, and a furyl group.

In R _{1 to} R ₄ of the general formula (1), the aryl group may further have a substituent, and the substituent is not particularly limited. For example, a methyl group, an ethyl group, a propyl group, an isopropyl group, Alkyl groups such as butyl, t-butyl and pentyl; halogen atoms such as fluorine, chlorine, bromine and iodine; methoxy, ethoxy, propoxy, butoxy, t-butoxy and hexyloxy Alkoxy groups such as hydroxy groups; hydroxyalkyl groups such as hydroxyethyl groups and hydroxypropyl groups; alkoxyalkyl groups such as methoxyethyl groups, ethoxyethyl groups, ethoxypropyl groups and butoxyethyl groups; hydroxyalkoxy groups such as 2-hydroxyethoxy groups Alkoxyalkoxy groups such as 2-methoxyethoxy group and 2-ethoxyethoxy group; 2 Sulfoethyl, carboxyethyl group, a cyanoethyl group, a sulfonic acid group, and the like.

R ₅ , R ₆ and R _{8 in the} general formula (1) each independently represent a hydrogen atom or a substituent. Examples of the substituent for R ₅ , R ₆ and R ₈ include an aliphatic group, an aryl group, a heterocyclic group, an acyl group, an acyloxy group, an acylamino group, a carboamido group, an alkyl-substituted carboamido group, an aryl-substituted carboamido group, and an aliphatic group. Group oxy group, aryloxy group, heterocyclic oxy group, aliphatic oxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group, aliphatic sulfonyl group, arylsulfonyl group, heterocyclic sulfonyl group, aliphatic sulfonyl Oxy group, arylsulfonyloxy group, heterocyclic sulfonyloxy group, sulfamoyl group, aliphatic sulfonamide group, arylsulfonamide group, heterocyclic sulfonamide group, amino group, aliphatic amino group, arylamino group, heterocyclic amino group , Aliphatic oxycarboni Ruamino group, aryloxycarbonylamino group, heterocyclic oxycarbonylamino group, aliphatic sulfinyl group, arylsulfinyl group, aliphatic thio group, arylthio group, hydroxy group, cyano group, sulfo group, carboxyl group, aliphatic oxyamino group , Aryloxyamino group, carbamoylamino group, sulfamoylamino group, halogen atom, sulfamoylcarbamoyl group, carbamoylsulfamoyl group, dialiphatic oxyphosphinyl group, diaryloxyphosphinyl group, etc. It is done.

R _{1 to} R ₆ in the general formula (2) represent the same meaning as in the general formula (1), and R ₇ represents a hydrogen atom or an alkyl group.

Examples of the alkyl group for R ₇ in the general formula (2) 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. These alkyl groups may have a substituent, and the substituent is not particularly limited. For example, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a 2-sulfoethyl group, a carboxyethyl group, a cyanoethyl group, Examples include methoxyethyl group, ethoxyethyl group, butoxyethyl group, trifluoromethyl group, pentafluoroethyl group, carbamoyl group, carboxyl group and the like.

The rhodamine dye of the present invention can be synthesized by, for example, a known method described in Patent Document 1. Moreover, it can synthesize | combine by purchasing the commercial item whose X < ^- > of General formula (1) and Formula (2) is a chlorine anion, etc., adding a corresponding salt or acid, and carrying out salt exchange.

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

  Specific examples represented by the above formula (1) are shown in the following Tables 1-1 to 1-3, but the present invention is not limited to these.

表１−２

表１−３

Table 1-1

Table 1-2

Table 1-3

  The oily or aqueous dye composition of the present invention contains the rhodamine dye of the present invention and an oil-soluble organic solvent in the case of an oily dye composition, and an aqueous medium in the case of an aqueous dye. In the oily or aqueous dye composition of the present invention, the rhodamine dye of the present invention is preferably contained in an amount of 0.2 to 40% by mass, and more preferably 0.5 to 20% by mass. Further, in the oily or aqueous dye composition of the present invention, a coloring material other than the general formula (1) or the formula (2) may be added as necessary for the purpose of adjusting the hue. Examples of colorants that can be added include water-soluble dyes such as acid dyes, reactive dyes, direct dyes, cationic dyes, and basic dyes, oil-soluble dyes such as disperse dyes and solvent dyes, organic pigments, and carbon black. And added in a dissolved or dispersed state in a solvent.

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

  The oil-based dye composition of the present invention can be prepared by dissolving or dispersing the rhodamine dye of the present invention in at least one oil-soluble organic solvent. Examples of the oil-soluble organic solvent used include alcohols such as ethanol, pentanol, octanol, cyclohexanol, benzyl alcohol, and tetrafluoropropanol; ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol mono Glycol derivatives such as ethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol diacetate, ethylene glycol diacetate, propylene glycol diacetate; ketones such as methyl ethyl ketone and cyclohexanone; Butyl phenyl ether, benzyl ether, hex Ethers such as ether; Esters such as ethyl acetate, butyl acetate, ethyl benzoate, butyl benzoate, ethyl laurate, butyl laurate; polar organics such as acetonitrile, DMF, dimethyl sulfoxide, sulfolane, NMP, 2-pyrrolidone A solvent etc. are mentioned, These solvents may be used independently and may mix and use 2 or more types.

  Dispersants used in oil dye compositions include sodium dodecylbenzenesulfonate, sodium laurate, formalin condensate of naphthalene sulfonic acid, formalin condensate of alkyl naphthalene sulfonic acid, formalin condensate of creosote oil sulfonic acid, poly Known anionic surfactants such as ammonium salts of oxyethylene alkyl ether sulfates, ammonium of polyoxyethylene alkyl phenyl ether sulfates, polyoxyalkyl ether phosphate esters, vinyl naphthalene derivatives, fats of α, β-ethylenically unsaturated carboxylic acids Aromatic alcohol esters, etc., styrene, styrene derivatives, acrylic acid, acrylic acid derivatives, methacrylic acid, methacrylic acid derivatives, maleic acid, maleic acid derivatives, maleic anhydride, maleic anhydride A block copolymer consisting of at least two monomers selected from inic acid derivatives, itaconic acid, itaconic acid derivatives, fumaric acid, fumaric acid derivatives, etc., or a random copolymer, or a high salt thereof. Examples thereof include molecular dispersants, and it is preferably used in an amount of 10 to 100% by mass with respect to the dye compound in which one or more of these are dispersed. In addition to these dispersants, known nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, copolymers of ethylene oxide and propylene oxide, and silicones A known acetylene-based antifoaming agent can be added at the time of pigment dispersion and / or after the pigment dispersion.

  As a method for dispersing the pigment into the fine particles, a sand mill (bead mill), a roll mill, a ball mill, a paint shaker, an ultrasonic disperser, a microfluidizer, or the like is used. Among them, a sand mill (bead mill) is generally used. For the grinding of pigments in sand mills (bead mills), it is necessary to use beads with small particle diameters and to process them under conditions that increase the grinding efficiency by increasing the filling rate of the beads. It is necessary to remove elementary particles by separation or the like.

  The dye composition of the present invention may contain a surface conditioner, preservative, antifungal agent, pH adjuster, etc. as other additives. As surface conditioning agents, polysiloxane or polydimethylsiloxane surfactants, and as antiseptic and mildewproofing agents, sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, zinc pyridinethione-1-oxide 1, 2-benzisothiazolin-3-one, amine salts of 1-benzisothiazolin-3-one, etc., and pH adjusters include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide And tertiary amines such as triethanolamine, diethanolamine, dimethylethanolamine and diethylethanolamine.

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

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

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples. In Examples, “part” means “part by mass” unless otherwise specified. In addition, evaluation of wet heat resistance, water resistance and the like was evaluated by measuring the chromaticity (L value, a value, b value) of the dyed colored body with a spectrophotometer “trade name UV-3150 manufactured by Shimadzu Corporation”.

Example 1
In a 100 ml beaker, 1 part of rhodamine 6G (manufactured by Tokyo Chemical Industry Co., Ltd.) of the following formula (100) and 20 parts of water were charged and stirred at room temperature for 30 minutes. A solution prepared by dissolving 1 part of a cesium salt of tristrifluoromethanesulfonium methide (manufactured by Central Glass) was added dropwise to 1 part of DMF, and the mixture was stirred for 3 hours. The precipitated dye was collected by filtration, washed with water, and dried to obtain 0.8 part of a dye (Compound No. 1 in Table 1-1). Maximum absorption wavelength: 531 nm (cyclohexanone)

Example 2
0.7 parts of the dye (Compound No. 3 in Table 1-1) was obtained in the same manner as in Example 1 except that the rhodamine dye was changed to rhodamine B (manufactured by Tokyo Chemical Industry Co., Ltd.) of the following formula (101). Maximum absorption wavelength: 560 nm (cyclohexanone)

Example 3
(Step 3-1)
A 200 ml flask was charged with 75 parts of water, 4.3 parts of a 28% aqueous sodium hydroxide solution, and 14.4 parts of rhodamine B of the above formula (101) and stirred at room temperature. To this, 28% aqueous sodium hydroxide solution was added until the pH of the reaction solution reached around 7, and 1.6 parts of sodium carbonate was further added to adjust the pH of the reaction solution to 10.3. 7.5 parts of dimethyl sulfate was added thereto and stirred at 30 ° C. for 2 hours, and then the reaction solution was transferred to a 1 L beaker. 350 parts of 50 ° C. hot water and 1 part of 98% sulfuric acid were added thereto, the pH of the reaction solution was adjusted to 2.7 to 3.0, and the reaction solution was stirred at 60 ° C. for 2 hours. Heating was stopped, 300 parts of water and 4.2 parts of zinc chloride were added thereto, 7.5 parts of sodium chloride was added little by little, and the mixture was stirred for 1 hour, 45 parts of sodium chloride was further added, and the mixture was stirred for 30 minutes. The precipitated dye was collected by filtration and dried to obtain 16 parts of an intermediate of the following formula (102). Maximum absorption wavelength: 561 nm (cyclohexanone)

(Step 3-2)
1.4 parts of a dye (Compound No. 7 in Table 1-1) were obtained in the same manner as in Example 1 except that Rhodamine 6G in Example 1 was changed to the intermediate (102). Maximum absorption wavelength: 561 nm (cyclohexanone)

Example 4
(Step 4-1)
In a 50 ml flask, 1.2 parts of rhodamine B of the above formula (101) and 5 parts of (R)-(−)-2-amino-1-propanol (manufactured by Tokyo Chemical Industry Co., Ltd.) were charged and stirred at 160 ° C. for 6 hours. did. To this was added 150 parts of saturated brine at room temperature, extracted with dichloromethane, washed with 5% hydrochloric acid, water, and saturated brine, and then the organic layer was concentrated under reduced pressure. The obtained residue was dissolved in a minimum amount of dichloromethane, an excess amount of hexane was added, and the mixture was allowed to stand at 0 ° C. overnight. The precipitated reddish purple crystals were collected by filtration and dried to obtain 0.6 parts of an intermediate of the following formula (103).

(Step 4-2)
In a 500 ml beaker, 0.4 part of the intermediate (103), 70 parts of acetic acid and 70 parts of water were charged and stirred at room temperature for 10 minutes. A solution prepared by dissolving 0.5 part of a cesium salt of tristrifluoromethanesulfonium methide in 3 parts of DMF was added dropwise thereto, and stirred at room temperature for 2 hours. To this reaction solution, 300 parts of saturated aqueous sodium hydrogen carbonate was added little by little, and the precipitated dye was collected by filtration. The obtained wet cake was washed with water overnight, filtered and dried to obtain 0.4 parts of a dye (Compound No. 13 in Table 1-2). Maximum absorption wavelength: 558 nm (cyclohexanone)

Example 5
A 300 ml beaker was charged with 1.5 parts of intermediate (102) and 125 parts of water and stirred at room temperature for 30 minutes. A solution in which 0.9 part of potassium salt of bistrifluoromethanesulfonylimide (manufactured by Morita Chemical Co., Ltd.) was dissolved in 2 parts of DMF was added dropwise thereto and stirred for 3 hours. The precipitated dye was collected by filtration, washed with water, and dried to obtain 1.7 parts of a dye (Compound No. 14 in Table 1-2). Maximum absorption wavelength: 560 nm (cyclohexanone)

Example 6
(Step 6-1)
Except that (R)-(−)-2-amino-1-propanol in Step 4-1 of Example 4 was changed to benzylamine, the same formula (104) was used as in Step 4-1 of Example 4. ) 2 parts of the intermediate was obtained.

(Step 6-2)
A dye (compound No. 15 in Table 1-3) was prepared in the same manner as in Step 4-2 of Example 4 except that the intermediate (103) in Step 4-2 of Example 4 was changed to the above formula (104). ) 1.3 parts were obtained. Maximum absorption wavelength: 559 nm (cyclohexanone)

Example 7
A 300 ml beaker was charged with 6 parts of an intermediate of the following formula (105) synthesized by the method described in non-patent literature (Organic Letters, 2003, Vol. 5, 3245-3248) and 170 parts of water, and stirred at room temperature for 10 minutes. did. A solution obtained by dissolving 5.5 parts of a cesium salt of tristrifluoromethanesulfonium methide in 5.5 parts of DMF was added dropwise thereto, and the mixture was stirred at room temperature for 1 hour. The precipitated dye was collected by filtration, washed with water, and dried to obtain 7 parts of a dye (Compound No. 16 in Table 1-3). Maximum absorption wavelength: 585 nm (cyclohexanone)

Example 8
(Process 8-1)
In a 100 ml flask, 5 parts of N, N-diethyl-3-aminophenol (manufactured by Tokyo Chemical Industry), 10.6 parts of tetrachlorophthalic anhydride (manufactured by Tokyo Chemical Industry), p-toluenesulfonic acid monohydrate 6 parts and 18 parts of propionic acid were added, and the mixture was refluxed for 12 hours while being protected from light. Toluene was added to the reaction solution, washed with 0.1 M hydrochloric acid at 80 ° C., the organic layer was concentrated under reduced pressure, 300 parts of 18% aqueous ammonia was added, and the mixture was stirred overnight at room temperature. Again, the dye in the reaction solution was extracted with toluene, washed with water until the aqueous layer became transparent, further washed several times with 0.1 M hydrochloric acid at 80 ° C., and the organic layer was concentrated under reduced pressure to obtain the following: 1 part of an intermediate of formula (106) was obtained.

(Step 8-2)
A 1 L beaker was charged with 0.6 part of the intermediate (106), 200 parts of water and 360 parts of methanol, and stirred at 40 ° C. for 30 minutes. The heating was stopped, and a solution obtained by dissolving 0.6 parts of a cesium salt of tristrifluoromethanesulfonium methide in 2.1 parts of DMF was added dropwise thereto, followed by stirring at room temperature for 4 hours. Methanol was evaporated under reduced pressure until the dye was precipitated, and then the deposited dye was collected by filtration, washed with water, and dried to obtain 0.4 parts of the dye (Compound No. 17 in Table 1-3). Maximum absorption wavelength: 587 nm (cyclohexanone)

Example 9
(Step 9-1)
A 50 ml flask was charged with 0.7 part of the intermediate (106) and 5 parts of 2-amino-1-propanol and stirred at 160 ° C. for 4 hours. To this was added 150 parts of saturated brine at room temperature, extracted with dichloromethane, washed with 5% hydrochloric acid, water, and saturated brine, and then the organic layer was concentrated under reduced pressure. The obtained residue was dissolved in a minimum amount of dichloromethane, an excess amount of hexane was added, and the mixture was allowed to stand at 0 ° C. overnight. The precipitated reddish purple crystals were collected by filtration and dried to obtain 0.6 parts of an intermediate of the following formula (107).

(Step 9-2)
A dye (Compound No. 18 in Table 1-3) was prepared in the same manner as in Step 4-2 of Example 4 except that the intermediate (103) in Step 4-2 of Example 4 was changed to the intermediate (107). ) 0.3 parts were obtained. Maximum absorption wavelength: 569 nm (cyclohexanone)

Example 10
(Step 10-1)
In a four-necked flask, 30 parts of DMF, 6.8 parts of benzyl bromide (manufactured by Tokyo Chemical Industry), 3.0 parts of potassium carbonate, 1,8-diazabicyclo [5,4,0] -7-undecene (manufactured by San Apro) 3 parts, 9.6 parts of rhodamine B of the above formula (101) were charged and stirred at 90 ° C. for 6 hours. After the reaction solution was filtered, water was added to the filtrate to adjust to 500 parts. To this solution, 5 parts of zinc chloride and 10 parts of sodium chloride were added little by little and stirred as it was for 1 hour. The precipitated dye was collected by filtration to obtain 8 parts of an intermediate of the following formula (108).

(Step 10-2)
1.4 parts of a dye (Compound No. 19 in Table 1-3) were obtained in the same manner as in Example 1 except that Rhodamine B in Example 1 was changed to the intermediate (108). Maximum absorption wavelength: 562 nm (cyclohexanone)

Example 11
Preparation of oil-based dye composition and dye-colored product Compound No. 1 obtained in Examples 1 to 3 above. 0.5 parts of 1, 3 and 7 were dissolved in 10 parts of tetrafluoropropanol, respectively, to prepare an oily dye composition. The obtained oil dye composition was spin-coated on a polycarbonate substrate and dried at 80 ° C. for 30 minutes to prepare a dye-colored product.

  In the following tables, Comparative Example 1 is an evaluation result of a dye-colored product prepared in the same manner using Rhodamine B of the above formula (100) and Comparative Example 2 using Rhodamine 6G of the above formula (101).

Humidity and heat resistance test The dyed colored body obtained by the above method was left in a constant temperature and humidity chamber under conditions of 85 ° C. and 85% RH for 40 hours. The dye-colored product before and after the test was measured with a spectrophotometer for the L value, a value, and b value as standard light using a C light source and a viewing angle of 2 degrees, and the color difference was determined from the following formula. In addition, it shows that it is excellent because there is little change of a hue, so that a color difference is small.
Color difference = [(L value before test−L value after test) ² + (a value before test−a value after test) ² + (b value before test−b value after test) ² ] ^1/2
Tables 2 to 7 below show the color measurement values and color differences in the wet heat resistance test.

Compound No. The color measurement results of 1 are shown in Table 2 below.
Table 2
L value a value b value Before test 87.49 25.80-13.48
After the test 88.43 23.62-12.22
Difference before and after test -0.94 2.18 -1.26

Compound No. The color measurement results of 3 are shown in Table 3 below.
Table 3
L value a value b value Before test 64.57 50.00 -57.90
After the test 65.18 50.64 -56.12
Difference before and after test -0.94 -0.64 -1.78

Compound No. The color measurement results of 7 are shown in Table 4 below.
Table 4
L value a value b value before test 81.6 22.73 -28.93
After the test 82.02 22.13 -28.33
Difference before and after test -0.42 -0.6 -0.6

The color measurement results of Comparative Example 1 are shown in Table 5 below.
Table 5
L value a value b value Before test 78.43 34.98 -26.84
After the test 98.35 1.36 -1.07
Difference before and after test -19.92 33.62 -25.77

The color measurement results of Comparative Example 2 are shown in Table 6 below.
Table 6
L value a value b value Before test 89.06 12.29 -14.54
After the test 95.70 5.55 -4.06
Difference before and after test -6.64 6.74-10.48

Compound Nos. Table 7 below shows the results of obtaining the color differences of Comparative Examples 1 and 2 in Tables 1, 3, and 7 and Tables 5 and 6.
Table 7
Color difference compound no. 1 2.69
Compound No. 3 1.99
Compound No. 7 4.8
Comparative Example 1 46.81
Comparative Example 2 14.12

As apparent from the above results, the color difference before and after the test of the dyed colored body of the comparative example showed a high value of 10 or more, whereas the color difference of the dyed colored body of the present invention showed a low value of 5 or less, and was resistant to moisture. It turns out that it is extremely excellent in heat property.
As described above, the rhodamine dye of the present invention and the dye-colored product thereof are excellent in moisture and heat resistance and have high fastness, and the rhodamine dye of the present invention has a wide range of applications such as color filter ink and ink jet ink. It became clear that industrial value such as spreading was high.

Claims (5)

Rhodamine dye represented by the following general formula (1)

(In the general formula (1), R _{1 to} R ₄ each independently represents a hydrogen atom, an alkyl group or an aryl group, and R ₅ , R ₆ and R ₈ each independently represent a hydrogen atom, an aliphatic group, an aryl group, hetero Ring group, acyl group, acyloxy group, acylamino group, aminocarbonyl group, alkyl-substituted aminocarbonyl group, aryl-substituted aminocarbonyl group, aliphatic oxy group, aryloxy group, heterocyclic oxy group, aliphatic oxycarbonyl group, aryloxy Carbonyl group, heterocyclic oxycarbonyl group, carbamoyl group, aliphatic sulfonyl group, arylsulfonyl group, heterocyclic sulfonyl group, aliphatic sulfonyloxy group, arylsulfonyloxy group, heterocyclic sulfonyloxy group, sulfamoyl group, aliphatic sulfonamide Group, arylsulfonamido group, Borocyclic sulfonamide group, amino group, aliphatic amino group, arylamino group, heterocyclic amino group, aliphatic oxycarbonylamino group, aryloxycarbonylamino group, heterocyclic oxycarbonylamino group, aliphatic sulfinyl group, arylsulfinyl Group, aliphatic thio group, arylthio group, hydroxy group, cyano group, sulfo group, carboxyl group, aliphatic oxyamino group, aryloxyamino group, carbamoylamino group, sulfamoylamino group, halogen atom, sulfamoylcarbamoyl A group, a carbamoylsulfamoyl group, a dialiphatic oxyphosphinyl group, a diaryloxyphosphinyl group, and X ⁻ represents a tris (trifluoromethanesulfonylmethide) anion. The rhodamine dye according to claim 1, wherein the general formula (1) is represented by the following general formula (2).

(In the general formula (2), R _{1 to} R ₆ and X ⁻ represent the same meaning as in the formula (1), and R ₇ represents a hydrogen atom or an alkyl group). The rhodamine dye according to claim 1, wherein R _{8 in the} general formula (1) is an aminocarbonyl group or a derivative thereof. An oily dye composition comprising the rhodamine dye according to any one of claims 1 to 3 and at least one oily solvent. An aqueous dye composition comprising the rhodamine dye according to any one of claims 1 to 3 and an aqueous medium.