WO2013146218A1

WO2013146218A1 - Xanthene compound

Info

Publication number: WO2013146218A1
Application number: PCT/JP2013/056670
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: 2012-03-27
Filing date: 2013-03-11
Publication date: 2013-10-03
Also published as: JPWO2013146218A1; TW201343797A

Abstract

[Problem] To provide: a xanthene compound which has high color definition and high 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 formula (1); and an oil-based or aqueous dye composition which contains the xanthene compound. In formula (1), each of R₁-R₄ independently represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1-12 carbon atoms; and one of R₅-R₉ represents a carboxylic acid group. The oil-based dye composition contains the xanthene compound and uses an oil-based organic solvent as a solvent. The aqueous dye composition contains the xanthene compound and uses an aqueous medium as a solvent.

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

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 ₄ each independently represents a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms or a hydrogen atom, and R ₅ to R ₉ each independently represents a carboxyl group or a hydrogen atom. Wherein at least one of R ₅ to R ₉ is a carboxyl group),
(2) In the formula (1), R ₁ to R ₄ are each independently a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, an iso-pentyl group, or The xanthene compound according to (1), which is a kind selected from hydrogen atoms, and any one of R ₅ to R ₉ is a carboxyl group,
(3) In the formula (1), R ₁ to R ₄ are each independently a methyl group or a hydrogen atom, R ₅ is a carboxyl group, and R ₆ to R ₉ are hydrogen atoms The xanthene compound according to (1) or (2),
(4) An oil-based dye composition containing the compound according to any one of (1) to (3) and at least one oil-soluble organic solvent,
(5) an aqueous dye composition containing the compound according to any one of (1) to (3) 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 ₄ each independently represents a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms or a hydrogen atom, and R ₅ to R ₉ each independently represents a carboxyl group or a hydrogen atom. However, at least one of R ₅ to R ₉ is a carboxyl group.

Specific examples of the alkyl group having 1 to 12 carbon atoms in R ₁ to R ₄ 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 ₄ in Formula (1) 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 to R ₄ are preferably an 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.

R ₅ to R ₉ each independently represent a carboxyl group or a hydrogen atom, provided that at least one of R ₅ to R ₉ is a carboxyl group. It is preferable that any one of R ₅ to R ₉ is a carboxyl group and the remaining is a hydrogen atom.

In particular, it is particularly preferable that R ₁ to R _{4 in} the formula (1) are each independently a methyl group or a hydrogen atom, R ₅ is a carboxyl group, and R ₆ to R ₉ are hydrogen atoms.

The xanthene compound represented by the formula (1) of the present invention can be synthesized, for example, by reacting a condensate synthesized according to the method described in Non-Patent Document 1 with an aminobenzoic acid derivative. That is, the xanthene compound of the present invention condenses 3,6-dichlorospiro [9H-xanthene-9,3 ′-[3H] [2,1] benzooxathiol] 1 ′, 1′-dioxide and the corresponding amine. Then, it can be synthesized by reacting the obtained condensate with an aminobenzoic acid derivative.

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. In Table 1-1 to Table 1-3, Me represents a methyl group, and n-Bu represents an n-butyl group.
Table 1-1

Table 1-2

Table 1-3

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 monomers selected from maleic anhydride, maleic anhydride derivatives, itaconic acid, itaconic acid derivatives, fumaric acid, fumaric acid derivatives, etc., or random copolymers, or these And a polymer dispersant such as a salt of the above, and is preferably used in a total amount of 10 to 100% by weight based on the dye compound in which one or more of these are dispersed. In addition to these dispersants, known nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, copolymers of ethylene oxide and propylene oxide, and silicones A known acetylene-based antifoaming agent can be added at the time of pigment dispersion and / or after the pigment dispersion.

Examples of the method for dispersing the pigment into the fine particles include a method using a sand mill (bead mill), a roll mill, a ball mill, a paint shaker, an ultrasonic disperser, a microfluidizer, 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.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this 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”. In the examples, the compound obtained by synthesis was analyzed by an NMR analyzer “JNM-ECS400 manufactured by JEOL Ltd.” and a liquid chromatography-mass spectrometer “1260 Infinity manufactured by Agilent Technologies” (hereinafter abbreviated as LC-MS). Identified. The measurement conditions are as follows.
Column; Inertsil ODS-2 (5 μm, 3.0 mm × 250 mm)
Mobile phase: A solution; 5 mM aqueous ammonium acetate solution, B solution; acetonitrile gradient (solution B); 20% → (25 minutes) → 50% → (5 minutes) → 90%
Observation wavelength: 254 nm, column temperature: 40 ° C., flow rate: 0.4 ml / mim

Example 1 (Synthesis of Compound No. 1 in Table 1-1)
(Step 1-1)
A 1000 ml four-necked flask was charged with 45.9 g of a fluorane compound of the following formula (100), 450 g of methanol and 24.2 g of N-methylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.), and stirred at 50 ° C. for 1 hour. The reaction solution was concentrated under reduced pressure at 40 ° C. or lower to reduce the volume to about 100 ml. The residue was added to 400 g of 5.8% hydrochloric acid and stirred for 5 minutes, and then the precipitated crystals were filtered and dried to obtain 36.1 g of a dye intermediate.

(Step 1-2)
In a 1000 ml four-necked flask, 35.9 g of the dye intermediate obtained in Step 1-1, 350 g of sulfolane, 12.4 g of anthranilic acid, and 10.7 g of zinc chloride were added and stirred for 5 minutes. To this, 9.5 g of soda ash was added little by little and stirred at 130 ° C. for 6 hours. When the heating was stopped and the liquid temperature dropped to 90 ° C. or lower, the reaction liquid was poured into 2500 g of 5.8% hydrochloric acid and stirred at room temperature for 15 minutes. The precipitated crystals were filtered, and the resulting crude crystals were suspended and stirred with 1400 g of 70% methanol water at 40 ° C. for 1 hour, further filtered, washed with hot water, and dried to obtain 37 g of a dye. Dark purple tea crystals. Maximum absorption wavelength: 557 nm (methanol).
1H-NMR (400 MHz, DMSO-d6) measured values: δ 10.48 (s, 1H), 7.70-7.62 (m, 2H), 7.58-7.54 (m, 3H), 7. 47-7.36 (m, 3H), 7.47-7.36 (m, 4H), 7.22-7.15 (m, 3H), 7.10-7.08 (m, 2H), 6.93-6.86 (m, 2H), 3.56 (s, 3H).
13C-NMR (400 MHz, DMSO-d6) measured values: δ 167.6, 162.0, 157.5, 157.3, 157.0, 154.3, 146.9, 144.4, 138.7, 133 .6, 133.3, 132.9, 131.8, 130.5, 129.7, 129.0, 128.7, 128.6, 128.2, 127.6, 126.6, 125.6 , 124.2, 124.0, 117.2, 116.1, 115.5, 115.4, 97.18, 97.12, 41.4.
LC-MS measured value: retention time; 11.63, calculated value (Exact Mass); 576.14, actually measured value ([M + H] ⁺ ); 577.12.

Example 2 (Synthesis of Compound No. 4 in Table 1-1)
(Process 2-1)
A 1000 ml four-necked flask was charged with 40.1 g of the fluorane compound of the above formula (100), 400 g of methanol, and 24.0 g of 2,6-dimethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.), and stirred at 50 ° C. for 2.5 hours. The reaction solution was concentrated under reduced pressure at 40 ° C. or lower to reduce the volume to about 100 ml. The residue was added to 100 g of 5.8% hydrochloric acid and suspended, and then the precipitated crystals were filtered and dried to obtain 33.6 g of a dye intermediate.

(Step 2-2)
In a 1000 ml four-necked flask, 5.0 g of the dye intermediate obtained in Step 2-1, 50 g of sulfolane, 1.7 g of anthranilic acid, 1.4 g of zinc chloride, and 1.3 g of soda ash were placed at 130 ° C. for 7 hours. Stir. When the heating was stopped and the liquid temperature dropped to 90 ° C. or lower, the reaction solution was poured into 330 g of 5.8% hydrochloric acid, and suspended and stirred at 50 ° C. for 10 minutes. The precipitated crystals were filtered, and the resulting crude crystals were suspended and stirred with 200 g of 70% methanol water at 40 ° C. for 1 hour, further filtered, washed with hot water, and dried to obtain 4.9 g of a dye. Dark green crystals. Maximum absorption wavelength: 546 nm (methanol).
1H-NMR (400 MHz, DMSO-d6) measured values: δ 10.48 (brs, 1H), 10.13 (s, 1H), 8.03-7.97 (m, 2H), 7.68-7. 56 (m, 4H), 7.35-7.08 (m, 11H), 6.00 (s, 1H), 2.21 (s, 1H), 2.15 (s, 1H).
13C-NMR (400 MHz, DMSO-d6) measured value: δ 167.7, 161.8, 158.6, 157.4, 157.1, 153.7, 146.8, 139.0, 135.5, 135 .4, 134.7, 133.6, 133.0, 131.8, 129.7, 129.2, 128.8, 128.7, 128.1, 127.6, 125.3, 123.7 123.6, 117.2, 115.9, 115.8, 97.3, 93.8, 17.7.

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 3 Preparation of oil-based dye composition and dye-colored product 1 1 / 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 the dyed colored body 1 of the present invention.

Example 4 Preparation of Oily Dye Composition and Dye Colored Product 2 Compound No. 1 in Table 1-1 No. 1 of the present invention in Table 1-1. Except having changed to 4, it carried out similarly to Example 3, and obtained the dye coloring body 2 of this invention.

Comparative Example 1
Compound No. 1 in Table 1-1 1 and C.I. I. A comparative dye-colored product 1 was obtained in the same manner as in Example 3 except for changing to Acid Red 289.

Comparative Example 2
Compound No. 1 in Table 1-1 A comparative dye-colored product 2 was obtained in the same manner as in Example 3 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 1 and 2 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 6 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 4 and 5 below.

The color measurement results of the dye-colored product 1 (Compound No. 1) are shown in Table 2 below.
Table 2
L value a value b value Before test 67.09 40.46 −43.58
After the test 67.44 42.26 -42.36
Difference before and after test -0.35 1.80 -1.22

The color measurement results of the dye-colored product 2 (Compound No. 4) are shown in Table 3 below.
Table 3
L value a value b value Before test 68.39 56.12 -37.57
After the test 69.21 56.48 -35.66
Difference before and after test -0.82 -0.36 -1.91

The color measurement results of the comparative dye-colored product 1 (Comparative Example 1) are shown in Table 4 below.
Table 4
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 color measurement results of the comparative dye-colored product 2 (Comparative Example 2) are shown in Table 5 below.
Table 5
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 6 below shows the results of the determination of the color differences of the dye-colored materials 1 and 2 and Comparative Examples 1 and 2 from Tables 2 to 5 above.
Table 6
Color difference dye colored body 1 2.20
Dye-colored product 2 2.10
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 5 Preparation of aqueous dye composition (Preparation of test dyeing cloth)
The ratio of each component in Table 7 below is the compound No. in Table 1-1. A water-based dye composition No. 1 was prepared, and silk or nylon cloth was printed by a screen printing method. These printed fabrics were steamed at 100 ° C. for 20 minutes, then washed with water and dried to obtain dyed fabric 1-1 (silk dyed fabric) and dyed fabric 1-2 (nylon dyed fabric).
Table 7 Compound No. No. 1 aqueous dye composition component table Compound No. 1 1 0.8g
Paste (Maypro Gum NP) 50.0g
Ammonium sulfate 1.0 g
Urea 5.0g
Water + sodium hydroxide 43.2g

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 the following Table 8. As the saturation C ^* is larger, the clearer the better.
C ^* = [(a ^* ) ² + (b ^* ) ² ] ^1/2

The colorimetric evaluation results of Example 5 are shown in Table 8 below.
Table 8
L ^* a ^* b ^* C ^*
Dyed cloth 1-1 (violet) 25.3 23.5 -37.1 43.9
Dyed fabric 1-2 (violet) 22.3 23.7 -34.9 42.2

From the results in Table 8, the compound No. of the present invention is obtained. It was found that by using 1, clear violet dyed fabrics such as Dyed fabrics 1-1 and 1-2 were obtained. Therefore, the aqueous dye composition of the present invention is also useful as a dye for dyeing.

As described above, the compound of the present invention and the dye-colored product thereof are excellent in heat resistance, have high fastness, and have industrial value such as a wide range of applications such as color filter ink and inkjet ink. It was revealed that the price is high.

Claims

Xanthene compounds represented by general formula (1)

(In the formula (1), R 1 to R 4 each independently represents a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms or a hydrogen atom, and R 5 to R 9 each independently represents a carboxyl group or a hydrogen atom. Wherein at least one of R 5 to R 9 is a carboxyl group).
In the formula (1), R 1 to R 4 are each independently a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, an iso-pentyl group, or a hydrogen atom. 2. The xanthene compound according to claim 1, wherein the xanthene compound is one selected from R 5 to R 9 and any one of them is a carboxyl group.
2. The formula (1), wherein R 1 to R 4 are each independently a methyl group or a hydrogen atom, R 5 is a carboxyl group, and R 6 to R 9 are hydrogen atoms. Or the xanthene compound according to 2.
An oil-based dye composition comprising the compound according to any one of claims 1 to 3 and at least one oil-soluble organic solvent.
An aqueous dye composition comprising the compound according to any one of claims 1 to 3 and an aqueous medium.