WO2013089197A1

WO2013089197A1 - Xanthene compound

Info

Publication number: WO2013089197A1
Application number: PCT/JP2012/082409
Authority: WO
Inventors: 高明倉田; 彰洋三藤; 禎之出島; 比呂子樋口
Original assignee: 日本化薬株式会社
Priority date: 2011-12-14
Filing date: 2012-12-13
Publication date: 2013-06-20
Also published as: TW201331191A; JPWO2013089197A1

Abstract

[Problem] To provide: a xanthene compound which has characteristics such as high clarity and color developability, while exhibiting excellent fastness such as heat resistance; and a dye composition of the xanthene compound. [Solution] A xanthene compound which is represented by general formula (1); and an oil-based or aqueous dye composition which contains the xanthene compound. (In formula (1), each of R₁-R₆ independently represents an alkyl group having 1-12 carbon atoms; and each of R₇ and R₈ independently represents an alkyl group having 1-12 carbon atoms or a hydrogen atom.)

Description

Xanthene compounds

The present invention relates to a novel xanthene compound.

C. I. Xanthene compounds such as Acid Red 289 are widely used as red to violet dyes, and are used in a wide range of applications such as various paints, water-based inks, oil-based inks, ink-jet inks, and color filter inks. In general, the characteristics required of dyes vary depending on the application, but it is required that the hue is clear, the color is high, and the colored material is fast against light, heat, and the like.

Patent Document 1 includes C.I. I. Acid Red 289 and C.I. I. Although a dye composition containing a sulfonamide derivative of Acid Red 289 is described, as a result of the study by the present inventors, the dye composition described in Patent Document 1 has insufficient heat fastness.

JP2010-254964 JP-A 51-87534

An object of the present invention is to provide a novel xanthene compound excellent in fastness such as heat resistance and a dye composition using the compound as a dye.

As a result of intensive studies to solve the above problems, the present inventors have found that a xanthene compound having a specific structure has drastically improved fastness such as heat resistance as compared with the conventional ones. It came to complete.

That is, the present invention
(1) Xanthene compound represented by general formula (1)

(In Formula (1), R ₁ to R ₆ each independently represents a substituted or unsubstituted alkyl having 1 to 12 carbon atoms, and R ₇ and R ₈ each independently represents a substituted or unsubstituted carbon atom having 1 to 12 carbon atoms. Represents an alkyl group or a hydrogen atom of
(2) In the formula (1), R ₁ to R ₆ are each independently an unsubstituted alkyl group having 1 to 12 carbon atoms, and R ₇ and R ₈ are each independently an unsubstituted alkyl group having 1 to 12 carbon atoms. The xanthene compound according to (1), which is an alkyl group or a hydrogen atom,
(3) In the formula (1), R ₁ to R ₆ are each independently a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group or an iso-butyl group, and R ₇ and R ₈ is independently a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, or a hydrogen atom, described in (1) or (2) Xanthene compounds,
(4) In the formula (1), R ₁ and R ₂ are each independently a methyl group, ethyl group, n-propyl group, n-butyl group or iso-pentyl group, and R ₃ to R ₆ are methyl groups Xanthene compound according to any one of (1) to (3), wherein R ₇ and R ₈ are each independently a methyl group or a hydrogen atom,
(5) An oil-based dye composition containing the compound according to any one of (1) to (4) and at least one oil-soluble organic solvent,
(6) An aqueous dye composition containing the compound according to any one of (1) to (4) and an aqueous medium,
About.

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

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

In the formula (1), R ₁ to R ₆ each independently represent a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, and R ₇ and R ₈ each independently represent a substituted or unsubstituted carbon group having 1 to 12 carbon atoms. Represents an alkyl group or a hydrogen atom.

Specific examples of the alkyl group having 1 to 12 carbon atoms in R ₁ to R ₆ in the formula (1) include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, and an iso-butyl group. , Sec-butyl group, t-butyl group, n-pentyl group, iso-pentyl group, t-pentyl group, octyl group, decyl group, dodecyl group, isopropyl group, cyclopentyl group, cyclohexyl group, vinyl group, allyl group, Propenyl, pentynyl, butenyl, hexenyl, hexadienyl, isopropenyl, isohexenyl, cyclohexenyl, cyclopentadienyl, ethynyl, propynyl, hexynyl, isohexynyl, cyclo A hexynyl group etc. are mentioned.

In addition, the alkyl group having 1 to 12 carbon atoms of R ₁ to R ₆ may have a substituent. Examples of the substituent in the alkyl group which may have a substituent include a halogen atom (eg, F, Cl, Br, etc.), a hydroxy group, an alkoxy group (eg, methoxy, ethoxy, isobutoxy, etc.), an alkoxyalkoxy group. (Eg, methoxyethoxy), aryl groups (eg, phenyl, naphthyl, etc., and these aryl groups may further have a substituent), aryloxy groups (eg, phenoxy, etc.), acyloxy groups (eg, Acetyloxy, butyryloxy, hexyloxy, benzoyloxy, etc., and these acyloxy groups may further have substituents), amino groups, alkyl-substituted amino groups (eg, methylamino, dimethylamino, etc.), Cyano group, nitro group, carboxyl group, carbonamido group, alkoxycarbonyl group ( , Methoxycarbonyl, ethoxycarbonyl, etc.), an acyl group, an amido group (e.g., acetamido, etc.), a sulfonamido group (e.g., a methanesulfonamido), and sulfo groups.

In the formula (1), R ₁ and R ₂ are preferably an unsubstituted alkyl group having 1 to 12 carbon atoms. Among them, an alkyl group having 1 to 5 carbon atoms, specifically a methyl group, an ethyl group, n- A propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, and an iso-pentyl group are preferable, and a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an iso-pentyl group are preferable. Most preferred.

In the formula (1), R ₃ to R ₆ are preferably an unsubstituted alkyl group having 1 to 12 carbon atoms, among which an alkyl group having 1 to 5 carbon atoms, specifically a methyl group, an ethyl group, n- A propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, and an iso-pentyl group are preferable, and a methyl group is most preferable.

Specific examples of the alkyl group having 1 to 12 carbon atoms in R ₇ and R ₈ in the formula (1) include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, and an iso-butyl group. , Sec-butyl group, t-butyl group, n-pentyl group, iso-pentyl group, t-pentyl group, octyl group, decyl group, dodecyl group, isopropyl group, cyclopentyl group, cyclohexyl group, vinyl group, allyl group, Propenyl, pentynyl, butenyl, hexenyl, hexadienyl, isopropenyl, isohexenyl, cyclohexenyl, cyclopentadienyl, ethynyl, propynyl, hexynyl, isohexynyl, cyclo A hexynyl group etc. are mentioned. Among these, preferred are methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, n-pentyl group, iso-pentyl group and t-pentyl group. And C1-C6 alkyl groups such as vinyl group, allyl group, propenyl group, pentynyl group, n-hexyl group, and the like, such as methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, An iso-butyl group and an iso-pentyl group are particularly preferable.

In addition, the alkyl group having 1 to 12 carbon atoms of R ₇ and R ₈ may have a substituent. Examples of the substituent in the alkyl group which may have a substituent include a halogen atom (eg, F, Cl, Br, etc.), a hydroxy group, an alkoxy group (eg, methoxy, ethoxy, isobutoxy, etc.), an alkoxyalkoxy group. (Eg, methoxyethoxy), aryl groups (eg, phenyl, naphthyl, etc., and these aryl groups may further have a substituent), aryloxy groups (eg, phenoxy, etc.), acyloxy groups (eg, Acetyloxy, butyryloxy, hexyloxy, benzoyloxy, etc., and these acyloxy groups may further have substituents), amino groups, alkyl-substituted amino groups (eg, methylamino, dimethylamino, etc.), Cyano group, nitro group, carboxyl group, carbonamido group, alkoxycarbonyl group ( , Methoxycarbonyl, ethoxycarbonyl, etc.), an acyl group, an amido group (e.g., acetamido, etc.), a sulfonamido group (e.g., a methanesulfonamido), and sulfo groups.

In the formula (1), R ₇ and R ₈ are an unsubstituted alkyl group having 1 to 12 carbon atoms or a hydrogen atom. Among them, an alkyl group having 1 to 5 carbon atoms, specifically a methyl group, an ethyl group, n- A propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, an iso-pentyl group, or a hydrogen atom is preferable, and a methyl group or a hydrogen atom is most preferable.

The xanthene compound represented by the formula (1) of the present invention can be synthesized, for example, according to the method described in Patent Document 2. That is, the xanthene compound of the present invention condenses 3,6-dihalogen-9- (2′-sulfophenyl) -xanthen-9-ol and the corresponding amine, and alkylates the resulting condensate as necessary. Can be synthesized.

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

Table 1-2

Table 1-3

In Table 1-1 to Table 1-3, Et represents an ethyl group, Pr represents a propyl group, and Bu represents a butyl group.

The oily or aqueous dye composition of the present invention contains the compound of the present invention and an oil-soluble organic solvent in the case of an oily dye composition, and an aqueous medium in the case of an aqueous dye. In the oily or aqueous dye composition of the present invention, the 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. In the oily or aqueous dye composition of the present invention, a colorant other than the formula (1) may be added as necessary for the purpose of adjusting the hue. Examples of colorants that can be added include water-soluble dyes such as acid dyes, reactive dyes, direct dyes, cationic dyes, and basic dyes, oil-soluble dyes such as disperse dyes and solvent dyes, organic pigments, and carbon black. And added in a dissolved or dispersed state in a solvent.

The aqueous dye composition of the present invention can be prepared by dissolving or dispersing the compound of the present invention in an aqueous medium. Examples of the aqueous medium include water or a water-soluble organic solvent. Examples of water-soluble organic solvents include alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol, benzyl alcohol; ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol Polyhydric alcohols such as 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, tri Ethylene glycol monoethyl ether, triethylene glycol monobutyl ether Glycol derivatives such as dipropylene glycol monomethyl ether; amines such as ethanolamine, diethanolamine, triethanolamine, morpholine; 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-imidazolidinone, etc. It is done.

The oil-based dye composition of the present invention can be prepared by dissolving or dispersing the compound 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, propylene glycol monomethyl ether acetate, propylene glycol diacetate; ketones such as methyl ethyl ketone and cyclohexanone ; Butyl phenyl ether, benzine Ethers such as ether and hexyl ether; esters such as ethyl acetate, butyl acetate, ethyl benzoate, butyl benzoate, ethyl laurate, and butyl laurate; acetonitrile, N, N-dimethylformamide, dimethyl sulfoxide, sulfolane, N Examples thereof include polar organic solvents such as methyl-2-pyrrolidone and 2-pyrrolidone. These solvents may be used alone or in combination of two or more.

Examples of the dispersant used in the aqueous dye composition or oil dye composition include sodium dodecylbenzenesulfonate, sodium laurate, formalin condensate of naphthalenesulfonic acid, formalin condensate of alkylnaphthalenesulfonic acid, and creosote oil sulfonic acid. Formalin condensate, polyoxyethylene alkyl ether sulfate ammonium salt, polyoxyethylene alkyl phenyl ether sulfate ammonium salt, polyoxyalkyl ether phosphate ester known anionic surfactant, vinyl naphthalene derivative, α, β-ethylene Aliphatic alcohol esters of unsaturated carboxylic acids, styrene, styrene derivatives, acrylic acid, acrylic acid derivatives, methacrylic acid, methacrylic acid derivatives, maleic acid, maleic acid derivatives, Block copolymer consisting of at least two or more monomers selected from maleic anhydride, maleic anhydride derivatives, itaconic acid, itaconic acid derivatives, fumaric acid, fumaric acid derivatives, etc., or random copolymers, or these Polymeric dispersants such as salts of these are mentioned, and one or more of these are preferably used in a total amount of 10 to 100% by weight based on the dye compound to be dispersed. In addition to these dispersants, known nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, copolymers of ethylene oxide and propylene oxide, and silicones A known acetylene-based antifoaming agent can be added at the time of pigment dispersion and / or after the pigment dispersion.

Examples of the method for dispersing the pigment into the fine particles include a method using a sand mill (bead mill), a roll mill, a ball mill, a paint shaker, an ultrasonic disperser, a microfluidizer, etc. Among them, a sand mill (bead mill) is preferable. In the grinding of pigments in sand mills (bead mills), it is preferable to use beads with small diameters and to treat them under conditions that increase the grinding efficiency by increasing the filling rate of beads. It is preferable to remove the elementary particles by separation or the like.

The dye composition of the present invention may contain surface additives, antiseptic / antifungal agents, pH adjusters and the like as other additives. As surface conditioning agents, polysiloxane or polydimethylsiloxane surfactants, and as antiseptic / antifungal agents, sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, zinc pyridinethione-1-oxide 1,2-benzisothiazolin-3-one, amine salts of 1-benzisothiazolin-3-one, etc., pH adjusters include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, Tertiary amines such as triethanolamine, diethanolamine, dimethylethanolamine, diethylethanolamine and the like can be mentioned, and each can be added as necessary.

In addition, in the oily or aqueous dye composition of the present invention, 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 dye 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, oligomer, polymerization initiator or the like having an ethylenically unsaturated group may be contained within a necessary range. The oily or aqueous dye composition of the present invention can be prepared by dissolving or dispersing and mixing the above components in a solvent.

The compound of the present invention is used in various paints, water-based inks, oil-based inks, ink-jet inks, and color filter coloring compositions as oil-based dye compositions or water-based dye 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.

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. Wet heat resistance and the like were evaluated by measuring the chromaticity (L value, a value, b value) of the dyed colored product using a spectrophotometer “UV-3150 manufactured by Shimadzu Corporation”.

Example 1 (Synthesis of Compound No. 2 in Table 1-1)
(Step 1-1)
In a 200 ml four-necked flask, 8.1 g of a fluorane compound of the following formula (100), 12.1 g of 2,6-dimethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.), 4.1 g of zinc chloride (manufactured by Kanto Chemical Co., Ltd.), sulfolane ( Pure Chemical Co., Ltd. (30 g) was added and stirred at 170 ° C. for 5 hours. After completion of the reaction, the heating was stopped, and when the temperature of the reaction solution dropped to 100 ° C. or lower, the reaction solution was poured into 200 parts of 6% hydrochloric acid, and the precipitated crystals were filtered, washed with 400 g of hot water at 60 ° C., and dried. 8.5 g of dye intermediate was obtained.

(Step 1-2)
A 500 ml four-necked flask was charged with 3 g of the dye intermediate obtained in Step 1-1 and 220 g of dehydrated dimethyl sulfoxide (manufactured by Wako Pure Chemical Industries, Ltd.), and stirred at room temperature for 30 minutes. 2 g of oily sodium hydride (manufactured by Wako Pure Chemical Industries, Ltd.) was gradually added thereto and stirred at room temperature for 1.5 hours. Next, while cooling the reaction vessel in an ice bath, 11.1 g of iodomethane (manufactured by Junsei Chemical Co., Ltd.) was added dropwise and stirred overnight at room temperature. After completion of the reaction, the reaction solution was poured into a mixed aqueous solution of 750 g of water and 90 g of 35% hydrochloric acid, stirred at room temperature for 30 minutes, and the precipitated crystals were filtered to obtain crude crystals. The crude crystals were dissolved in 529 g of dichloromethane, and the organic layer was washed with 6% hydrochloric acid, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. After suspending and stirring the obtained crystal with 143 g of diethyl ether for 1 hour, the crystal was filtered, rinsed with hexane, and dried to give the compound of the present invention. 2.5 g of 2 was obtained. Maximum absorption wavelength: 542 nm (cyclohexanone).

Example 2 (Synthesis of Compound No. 3 in Table 1-1)
(Process 2-1)
In a 200 ml four-necked flask, 8.1 g of the fluorane compound of the above formula (100), 13.5 g of 2,4,6-trimethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.), 4.1 g of zinc chloride (manufactured by Kanto Chemical Co., Inc.), 30 g of sulfolane (manufactured by Junsei Kagaku) was added and stirred at 170 ° C. for 5 hours. After completion of the reaction, heating was stopped, and when the temperature of the reaction solution dropped to 100 ° C. or less, the reaction solution was poured into 400 g of 6% hydrochloric acid, and the precipitated crystals were filtered, washed with 400 g of hot water at 60 ° C. and dried. 11.1 g of intermediate was obtained.

(Step 2-2)
In a 500 ml four-necked flask, 6 g of the dye intermediate obtained in Step 2-1 and 220 g of dehydrated dimethyl sulfoxide (manufactured by Wako Pure Chemical Industries, Ltd.) were added and stirred at room temperature for 30 minutes. 2 g of oily sodium hydride (manufactured by Wako Pure Chemical Industries, Ltd.) was gradually added thereto and stirred at room temperature for 1.5 hours. Next, while cooling the reaction vessel in an ice bath, 14.2 g of iodomethane (manufactured by Junsei Chemical Co., Ltd.) was added dropwise and stirred overnight at room temperature. After completion of the reaction, the reaction solution was poured into a mixed aqueous solution of 800 g of water and 55 g of 35% hydrochloric acid, stirred at room temperature for 30 minutes, and the precipitated crystals were filtered to obtain crude crystals. The crude crystals were dissolved in 400 g of dichloromethane, and the organic layer was washed with 6% hydrochloric acid, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. After suspending and stirring the obtained crystal with 143 g of diethyl ether for 1 hour, the crystal was filtered, rinsed with hexane, and dried to give the compound of the present invention. 4.3 g of 3 was obtained. Maximum absorption wavelength: 544 nm (cyclohexanone).

Example 3 (Synthesis of Compound No. 6 in Table 1-1)
In a 500 ml four-necked flask, 4.7 g of the dye intermediate obtained in Step 2-1 of Example 2 and 176 g of dehydrated dimethyl sulfoxide (manufactured by Wako Pure Chemical Industries, Ltd.) were added and stirred at room temperature for 30 minutes. 1.6 g of oily sodium hydride (manufactured by Wako Pure Chemical Industries, Ltd.) was added little by little and stirred at room temperature for 1.5 hours. Next, while cooling the reaction vessel in an ice bath, 14.4 g of iodobutane (manufactured by Junsei Chemical Co., Ltd.) was added dropwise and stirred overnight at room temperature. After completion of the reaction, the reaction solution was poured into a mixed aqueous solution of 640 g of water and 45 g of 35% hydrochloric acid, stirred at room temperature for 30 minutes, and the precipitated crystals were filtered to obtain crude crystals. The crude crystals were dissolved in 264 g of dichloromethane, and the organic layer was washed with 6% hydrochloric acid, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained crystals were suspended and stirred with 107 g of diethyl ether for 1 hour, and then the crystals were filtered, rinsed with hexane, and dried to give the compound of the present invention. 3.5 g of 6 was obtained. Maximum absorption wavelength: 549 nm (cyclohexanone).

Synthesis Example 1 (Synthesis of binder resin (copolymer))
A 500 ml four-necked flask was charged with 160 g of methyl ethyl ketone, 10 g of methacrylic acid, 33 g of benzyl methacrylate, and 1 g of α, α′-azobis (isobutyronitrile), and nitrogen gas was allowed to flow into the flask for 30 minutes while stirring. Thereafter, the temperature was raised to 80 ° C., and the mixture was stirred at 80 to 85 ° C. for 4 hours. After completion of the reaction, the reaction mixture was cooled to room temperature to obtain a colorless, transparent and uniform copolymer solution. This was precipitated in a 1: 1 mixed solution of isopropyl alcohol and water, filtered, the solid content was taken out, and dried to obtain a copolymer (A). The obtained copolymer (A) had a polystyrene equivalent weight average molecular weight of 18,000 and an acid value of 152 (mgKOH / g).

Example 4 Preparation of Oil-Based Dye Composition and Dye Colored Product 1 2 / Disperbyk-2001 (manufactured by Big Chemie Japan) / PGMEA (propylene glycol monomethyl ether acetate) / ethoxypropanol / binder resin obtained in Synthesis Example 1 = 0.3 g / 1.0 g / 16.0 g / 2.0 g / After mixing at a composition ratio of 1.0 g, add 20 g of 0.3 mm zirconia beads, treat with a paint shaker for 60 minutes, filter, and add 20 g of the binder resin obtained in Synthesis Example 1 to the resulting solution. An oil dye composition was prepared by stirring. The obtained oil-based dye composition was spin-coated on a glass substrate and dried at 200 ° C. for 20 minutes to prepare a dye-colored product 1.

Example 5
Compound No. 1 in Table 1-1 2 is shown in Table 1-1. Except having changed to 3, it carried out similarly to Example 4, and obtained the dye coloring body 2 of this invention.

Example 6
Compound No. 1 in Table 1-1 2 is shown in Table 1-1. Except having changed to 6, it carried out similarly to Example 4, and obtained the dye coloring body 3 of this invention.

Comparative Example 1
Compound No. 1 in Table 1-1 1 and C.I. I. Except having changed to Acid Red 289, it carried out similarly to Example 4, and obtained the dye coloring material 1 for a comparison of this invention.

Comparative Example 2
Compound No. 1 in Table 1-1 A comparative dye colored body 2 of the present invention was obtained in the same manner as in Example 4 except that 1 was changed to the dye A1 described in Patent Document 1 (the compound of Synthesis Example 1 of Patent Document 1).

Heat resistance test The dyed colored bodies obtained in Examples 4 to 6 were left in an oven at 230 ° C for 3 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 in fastness, so that there are few changes 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
The measured values and color difference of the colorimetry in the heat resistance test are shown in Tables 2 to 4 below.

For comparison, a heat resistance test was also conducted on the comparative dyed colored bodies 1 and 2 in the same manner. The results are shown in Tables 5 and 6 below.

Table 2 below shows the colorimetric results of dye-colored product 1 (Compound No. 2).
Table 2
L value a value b value Before test 74.84 58.92 -33.37
After the test 75.14 56.62 -31.36
Difference before and after test -0.30 2.30 -2.01

The color measurement results of the dye-colored product 2 (Compound No. 3) are shown in Table 3 below.
Table 3
L value a value b value Before test 72.98 60.96 -35.63
After the test 73.54 56.63 -32.34
Difference before and after test -0.56 4.33 -3.29

The color measurement results of the dye-colored product 3 (Compound No. 6) are shown in Table 4 below.
Table 4
L value a value b value Before test 76.48 46.08 -31.06
After the test 77.40 42.58 -27.29
Difference before and after test -0.92 3.50 -3.77

The color measurement results of the comparative dye-colored product 1 are shown in Table 5 below.
Table 5
L value a value b value Before test 81.30 32.09 -20.74
After the test 82.97 24.05 -17.10
Difference before and after test -1.67 8.04 -3.64

The colorimetric results of the comparative dyed colored body 2 are shown in Table 6 below.
Table 6
L value a value b value Before test 86.25 23.12 -15.07
After the test 87.33 16.91-12.47
Difference before and after test -1.08 6.21 -2.60

Table 7 below shows the results of determining the color differences of the dye-colored materials 1 to 3 and Comparative Examples 1 and 2 from Tables 2 to 6 above.
Table 7
Color difference dye colored body 1 3.01
Dye-colored product 2 5.47
Dye-colored product 3 5.23
Dye-colored product for comparison 1 8.98
Dye coloring body for comparison 2 6.82

As is clear from the above results, comparing the color difference before and after the test of the dye-colored body of the comparative example with the dye-colored body of the present invention, the color difference shows a low value, indicating that the heat resistance is extremely excellent.

Example 7 Preparation of aqueous dye composition (preparation of test dyeing cloth)
The compound Nos. In Table 1-1 at the respective component ratios in Table 8 below. The aqueous dye composition No. 2 was prepared, and silk and nylon cloths were printed by screen printing. These printed fabrics were steamed at 100 ° C. for 20 minutes, then washed with water and dried to obtain dyed cloth 1-1 (silk dyed cloth) and dyed cloth 1-2 (nylon dyed cloth). .

Table 8 Compound No. 2 aqueous dye composition component table compound No. 2 2 0.8g
Paste (Maypro Gum NP) 50.0g
Ammonium sulfate 1.0 g
Urea 5.0g
2-pyrrolidone 16.0g
27.2g of water

Hue evaluation of each dyed cloth Colorimetric evaluation was performed on the hue of each test dyed cloth obtained as described above. For color measurement, L ^* , a ^* , and b ^* were measured by measuring the color of the dyed cloth using a colorimeter manufactured by GRETAG-MACBETH, trade name: SpectroEye. Further, the saturation C ^* was determined from the following formula based on the value. The evaluation results are shown in Table 9 below. As the saturation C ^* is larger, the clearer the better.
C ^* = [(a ^* ) ² + (b ^* ) ² ] ^1/2

The color measurement evaluation results of Example 7 are shown in Table 9 below.
Table 9
L ^* a ^* b ^* C ^*
Dyeing cloth 1-1 (magenta) 43.1 70.8 -11.0 71.6
Dyed fabric 1-2 (magenta) 42.1 77.9 -7.1 78.2

From Table 9, the present compound No. It was confirmed that the dyed fabrics 1-1 and 1-2 using No. 2 had a clear magenta dyeing property. From this, it was found that the dye of the present invention is also useful as a dye for dyeing in textile printing as an aqueous dye composition.

As described above, the compound of the present invention and the dye-colored product thereof have excellent heat resistance and high fastness, and have a wide range of applications such as color filter ink, inkjet ink, and dye for dyeing. It became clear that it was highly valuable.

Claims

Xanthene compounds represented by general formula (1):

(In Formula (1), R 1 to R 6 each independently represents a substituted or unsubstituted alkyl having 1 to 12 carbon atoms, and R 7 and R 8 each independently represents a substituted or unsubstituted carbon atom having 1 to 12 carbon atoms. Represents an alkyl group or a hydrogen atom.
In the formula (1), R 1 to R 6 are each independently an unsubstituted alkyl group having 1 to 12 carbon atoms, and R 7 and R 8 are each independently an unsubstituted alkyl group having 1 to 12 carbon atoms or The xanthene compound according to claim 1, which is a hydrogen atom.
In the formula (1), R 1 to R 6 are each independently a methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group or iso-butyl group, and R 7 and R 8 are each The xanthene compound according to claim 1 or 2, which is independently a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group or a hydrogen atom.
In the formula (1), R 1 and R 2 are each independently a methyl group, an ethyl group, an n-propyl group, an n-butyl group or an iso-pentyl group, R 3 to R 6 are methyl groups, The xanthene compound according to claim 1, wherein 7 and R 8 are each independently a methyl group or a hydrogen atom.
An oil-based dye composition comprising the compound according to any one of claims 1 to 4 and at least one oil-soluble organic solvent.
An aqueous dye composition comprising the compound according to any one of claims 1 to 4 and an aqueous medium.