TW201331191A - Xanthene compound - Google Patents

Abstract

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. 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

Dibenzopyran

This invention relates to a novel dibenzopyran compound.

Dibenzopyran compounds such as CIAcid Red 289 are widely used as red-purple dyes and are used in a wide variety of applications such as various coatings, water-based inks, oil-based inks, inkjet inks, and color filter inks. in. Generally, the characteristics required for the dye vary depending on the use, but it is required to have a clear hue and a high color rendering property and a tough property of the coloring matter with respect to light or heat.

In Patent Document 1, a dye composition containing a sulfonamide derivative of CIAcid Red 289 and CIAcid Red 289 is disclosed. However, according to the findings of the present inventors, the dye combination disclosed in Patent Document 1 The toughness of the object relative to heat is not sufficient.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2010-254964

[Patent Document 2] Japanese Patent Laid-Open No. 51-87534

An object of the present invention is to provide a novel dibenzopyran compound which is excellent in toughness such as heat resistance and a dye composition using the same as a dye.

In order to solve the above-mentioned problems, the inventors of the present invention have conducted intensive studies, and as a result, it has been found that a dibenzopyran compound having a specific structure is drastically improved in strength and toughness as compared with the prior art, and the present invention has been completed.

That is, the present invention relates to: (1) a dibenzopyran compound which 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 number 1 (12) an alkyl group or a hydrogen atom); (2) a benzopyran compound according to the above (1), wherein in the formula (1), R ₁ to R ₆ are each independently an unsubstituted carbon number 1~ The alkyl group of 12, R ₇ and R ₈ are each independently an unsubstituted alkyl or hydrogen atom having 1 to 12 carbon atoms; (3) a dibenzopyranium compound of the above (1) or (2), wherein In the formula (1), R ₁ to R ₆ are each independently methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl, and R ₇ and R ₈ are each independently methyl or ethyl. And a dibenzopyran compound according to any one of the above (1) to (3), wherein the formula (1) is a benzoylpyranium compound of any one of the above (1) to (3) Wherein R ₁ and R ₂ are each independently methyl, ethyl, n-propyl, n-butyl or isopentyl, R ₃ to R ₆ are methyl, and R ₇ and R ₈ are each independently methyl or hydrogen. (5) An oily dye composition comprising the compound according to any one of the above (1) to (4) and at least one oil-soluble organic solvent; (6) The aqueous dye composition, which comprises the above (1) to (4) and a compound of any one of the aqueous medium.

The compound of the present invention is excellent in clarity and color rendering property, and when it is formed into an oil-based or aqueous dye composition and processed into a dye-colored body, it exhibits characteristics superior to the former. That is, the compound of the present invention can be used in a dye coloring body, and can be applied to a wide range of applications such as ink for color filters or inks for inkjet.

The dibenzopyrazole compound of the present invention is represented by the above 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 number 1~. 12 alkyl or hydrogen atoms.

Specific examples of the alkyl group having 1 to 12 carbon atoms in R ₁ to R ₆ in the formula (1) include methyl, ethyl, n-propyl, isopropyl, n-butyl and isobutyl groups. Second butyl, tert-butyl, n-pentyl, isopentyl, third amyl, octyl, decyl, dodecyl, isopropyl, cyclopentyl, cyclohexyl, vinyl, allyl Base, propenyl, pentynyl, butenyl, hexenyl, hexadienyl, isopropenyl, isohexenyl, cyclohexenyl, cyclopentadienyl, ethynyl, propynyl, hexyne Base, isohexynyl, cyclohexynyl and the like.

Further, 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 (e.g., F, Cl, Br, etc.), a hydroxyl group, an alkoxy group (e.g., methoxy group, ethoxy group, isobutoxy group). Or an alkoxyalkoxy group (e.g., methoxyethoxy group, etc.), an aryl group (e.g., phenyl, naphthyl, etc., which may further have a substituent), an aryloxy group (e.g., phenoxy) Alkyloxy) (e.g., ethoxylated, butyloxy, hexyloxy, benzhydryloxy, etc., which may further have a substituent), an amine group, an alkyl group Substituted amine groups (e.g., methylamino, dimethylamino, etc.), cyano, nitro, carboxy, carboamine, alkoxycarbonyl (e.g., methoxycarbonyl, ethoxycarbonyl, etc.), fluorenyl, An amidino group (e.g., an ethenyl group, etc.), a sulfonylamino group (e.g., a methanesulfonylamino group, etc.), and a sulfo group.

In the formula (1), R ₁ and R _{2 are} preferably an unsubstituted alkyl group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms, specifically methyl group, ethyl group and positive group. The propyl group, the isopropyl group, the n-butyl group, the isobutyl group and the isopentyl group are preferably a methyl group, an ethyl group, a n-propyl group, a n-butyl group or an isopentyl group.

In the formula (1), R ₃ to R _{6 are} preferably an unsubstituted alkyl group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms, specifically a methyl group or an ethyl group. , n-propyl, isopropyl, n-butyl, isobutyl, isopentyl, most preferably methyl.

Specific examples of the alkyl group having 1 to 12 carbon atoms in R ₇ and R ₈ in the formula (1) include methyl, ethyl, n-propyl, isopropyl, n-butyl and isobutyl groups. Second butyl, tert-butyl, n-pentyl, isopentyl, third amyl, octyl, decyl, dodecyl, isopropyl, cyclopentyl, cyclohexyl, vinyl, allyl Base, propenyl, pentynyl, butenyl, hexenyl, hexadienyl, isopropenyl, isohexenyl, cyclohexenyl, cyclopentadienyl, ethynyl, propynyl, hexyne Base, isohexynyl, cyclohexynyl and the like. Among these, preferred are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, tert-amyl, vinyl. a C1-C6 alkyl group such as allyl, propenyl, pentynyl or n-hexyl, and more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, isopentyl .

Further, 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 (e.g., F, Cl, Br, etc.), a hydroxyl group, an alkoxy group (e.g., methoxy group, ethoxy group, isobutoxy group). Or an alkoxyalkoxy group (e.g., methoxyethoxy group, etc.), an aryl group (e.g., phenyl, naphthyl, etc., which may further have a substituent), an aryloxy group (e.g., phenoxy) Alkyloxy) (e.g., ethoxylated, butyloxy, hexyloxy, benzhydryloxy, etc., which may further have a substituent), an amine group, an alkyl group Substituted amine groups (e.g., methylamino, dimethylamino, etc.), cyano, nitro, carboxy, carboamine, alkoxycarbonyl (e.g., methoxycarbonyl, ethoxycarbonyl, etc.), fluorenyl, An amidino group (e.g., an ethenyl group, etc.), a sulfonylamino group (e.g., a methanesulfonylamino group, etc.), and a sulfo group.

In the formula (1), R ₇ and R ₈ are an unsubstituted alkyl group having 1 to 12 carbon atoms or a hydrogen atom, and among them, an alkyl group having 1 to 5 carbon atoms is preferable, and specifically, a methyl group or an ethyl group is used. N-propyl, isopropyl, n-butyl, isobutyl, isopentyl or a hydrogen atom, most preferably a methyl or hydrogen atom.

The dibenzopyran compound represented by the formula (1) of the present invention can be synthesized, for example, according to the method disclosed in Patent Document 2. That is, the dibenzopyran compound of the present invention can be condensed by an amine corresponding to 3,6-dihalo-9-(2'-sulfonic acid phenyl)-dibenzopyran-9-ol. It is necessary to alkylate the obtained polycondensate to synthesize it.

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 Tables 1-1 to 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 in the case of an oily dye composition, contains an oil-soluble organic solvent, and in the case of an aqueous dye, contains an aqueous medium. The oily or aqueous dye composition of the present invention preferably contains 0.2 to 40% by weight, more preferably 0.5 to 20% by weight, based on the compound of the present invention. Also, the oil of the present invention In the aqueous or aqueous dye composition, in order to adjust the color, it is also possible to add a colored material other than the above formula (1) as needed. Examples of the coloring material 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; It is added in a state of being dissolved or dispersed 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. As an aqueous medium, water or a water-soluble organic solvent is mentioned. Examples of the water-soluble organic solvent include alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, pentanol, and benzyl alcohol; ethylene glycol and diethylene glycol; , triethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, 1,3-pentanediol, 1,5-pentanediol and other polyols; ethylene glycol monomethyl ether , glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, dipropylene glycol monomethyl ether and other glycol derivatives; ethanolamine , diethanolamine, triethanolamine, An amine such as a phenyl group; 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-imidazolidinone or the like.

The oily 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 to be used include alcohols such as ethanol, pentanol, octanol, cyclohexanol, benzyl alcohol, and tetrafluoropropanol; ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, and Ethylene glycol monobutyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol diacetate Ethylene glycol derivative Ketones such as methyl ethyl ketone and cyclohexanone; ethers such as butyl phenyl ether, benzyl ether and hexyl ether; ethyl acetate, butyl acetate, ethyl benzoate, butyl benzoate, lauric acid Esters such as ethyl ester and butyl laurate; polar organic solvents such as acetonitrile, N,N-dimethylformamide, dimethyl hydrazine, cyclobutyl hydrazine, N-methyl-2-pyrrolidone and 2-pyrrolidone Etc.; these solvents may be used singly or in combination of two or more.

Examples of the dispersing agent used in the aqueous dye composition or the oil-based dye composition include sodium dodecylbenzenesulfonate, sodium laurate, a formaldehyde polycondensate of naphthalenesulfonic acid, and a formaldehyde polycondensate of alkylnaphthalenesulfonic acid. Known anionic interface of formaldehyde condensate of cresy oil sulfonic acid, ammonium salt of polyoxyethylene alkyl ether sulfate, ammonium salt of polyoxyethylene alkyl phenyl ether sulfate, polyoxyethylene alkyl ether phosphate salt, etc. An active agent; comprising an aliphatic alcohol ester selected from the group consisting of vinyl naphthalene derivatives, α,β-unsaturated ethylene carboxylic acids, styrene, styrene derivatives, acrylic acid, acrylic acid derivatives, methacrylic acid, methacrylic acid derivatives , maleic acid, maleic acid derivative, maleic anhydride, maleic anhydride derivative, itaconic acid, itaconic acid derivative, fumaric acid, antibutene a block copolymer, a random copolymer or a polymer dispersant such as a salt of at least two of the acid derivatives and the like; preferably a total of 10% with respect to the dispersed dye compound. One or more of these are used in the range of 100% by weight. Further, it may be necessary to add a polyoxyethylene sorbitan fatty acid ester, a polyoxyethylene alkyl ether, a polyoxyethylene alkylphenyl ether, or a ring together with the dispersing agent at the time of pigment dispersion and/or pigment dispersion. A known nonionic surfactant such as a copolymer of oxyethane and propylene oxide, or a well-known antifoaming agent of an oxime type or an acetylene type.

Examples of the method of dispersing the pigment in the fine particles include a sand mill (bead mill), a roll mill, a ball mill, a paint shaker, an ultrasonic disperser, a micro-jet homogenizer, and the like, and preferably sand. Mill (bead mill). Further, the pulverization of the pigment in the sand mill (bead mill) is preferably carried out under the condition of improving the pulverization efficiency by a method of using beads having a smaller diameter or a method of increasing the filling ratio of the beads. The treatment is carried out, and it is preferred to remove the elementary particles by filtration, centrifugation or the like after the pulverization treatment.

The dye composition of the present invention may further contain a surface conditioner, an antiseptic/mold inhibitor, a pH adjuster or the like as another additive. Examples of the surface conditioning agent include a polyoxyalkylene-based or polydimethylsiloxane-based surfactant; examples of the antiseptic/mold inhibitor include sodium dehydroacetate, sodium benzoate, and sodium pyrithione-1. - an amine salt of zinc oxide, pyrithione-1-oxide, 1,2-benzisothiazol-3-one or 1-benzisothiazol-3-one; and examples of the pH adjuster: An alkali metal hydroxide such as sodium hydroxide, potassium hydroxide or lithium hydroxide; a tertiary amine such as triethanolamine, diethanolamine, dimethylethanolamine or diethylethanolamine, and may be added as needed.

Further, in the oily or aqueous dye composition of the present invention, in order to improve the fixability of the dye to the colored body, it is preferred to contain a polyamine or a polyamine which is compatible with the medium in the composition within a desired range. A urethane type, a polyester type, an epoxy type or a polypropylene type resin. Further, in order to improve the fixability, a monomer having an unsaturated vinyl group, an oligomer, a polymerization initiator, or the like may be contained in a desired range. The oily or aqueous dye composition of the present invention can be prepared by dissolving or dispersing the above components and mixing them in a solvent.

a compound of the invention as an oily dye composition or an aqueous dye composition It is used in various coloring compositions for water-based inks, oil-based inks, inkjet inks, and color filters. The oily dye composition and the aqueous dye composition are used, for example, in pigmented materials such as plain paper, coated paper, plastic film, and plastic substrate. Moreover, as a method of providing the dye composition of the present invention to a coloring material, various printing methods such as lithography, letterpress printing, flexographic printing, and inkjet printing may be mentioned, or by spin coater or roll coating. Coating method of machine.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the examples. The chromaticity (L value, a value, and b value) of the dye colored body was measured by a spectrophotometer "UV-3150 manufactured by Shimadzu Corporation" to evaluate the moist heat resistance and the like.

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 fluoran compound of the following formula (100), 2,6-dimethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.), 12.1 g, zinc chloride (manufactured by Kanto Chemical Co., Ltd.) 4.1 were placed. g, cyclobutyl hydrazine (manufactured by Junsei Chemical Co., Ltd.) 30 g, and stirred at 170 ° C for 5 hours. After the completion of the reaction, the heating was stopped. When the temperature of the reaction liquid dropped to 100 ° C or lower, the reaction liquid was poured into 200 parts of 6% hydrochloric acid, and the precipitated crystal was filtered, washed with 400 g of hot water at 60 ° C, and dried. This gave a dye intermediate of 8.5 g.

[Chemical 2]

(Step 1-2)

Into a 500 ml four-necked flask, 3 g of the dye intermediate obtained in the step 1-1, dehydrated dimethyl hydrazine (manufactured by Wako Pure Chemical Industries, Ltd.), 220 g, was placed, and stirred at room temperature for 30 minutes. 2 g of an oily sodium hydride (manufactured by Wako Pure Chemical Industries, Ltd.) was placed little by little, and stirred at room temperature for 1.5 hours. Then, while cooling the reaction vessel by an ice bath, 11.1 g of methyl iodide (manufactured by Junsei Chemical Co., Ltd.) was added dropwise, and the mixture was stirred at room temperature overnight. 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, and the mixture was stirred at room temperature for 30 minutes, and the precipitated crystal was filtered to obtain a crude crystal. The crude crystals were dissolved in 529 g of dichloromethane, and the organic layer was washed with 5% hydrochloric acid and dried over anhydrous sodium sulfate. The crystal obtained was suspended by stirring 143 g of diethyl ether for 1 hour, and the crystals were filtered, washed with n-hexane and dried, whereby 2.5 g of the present compound No. 2 was obtained. Maximum absorption wavelength: 542 nm (cyclohexanone).

Example 2 (Synthesis of Compound No. 3 in Table 1-1) (Step 2-1)

Into a 200 ml four-necked flask, 8.1 g of a fluoran compound of the above formula (100), 2,4,6-trimethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.), 13.5 g, zinc chloride (manufactured by Kanto Chemical Co., Ltd.) was placed. 4.1 g, ring 碸 碸 (made by Pure Chemical Co., Ltd. 30 g was made and stirred at 170 ° C for 5 hours. After the completion of the reaction, the heating was stopped. When the temperature of the reaction liquid dropped to 100 ° C or lower, the reaction solution was poured into 400 g of 6% hydrochloric acid, and the precipitated crystal was filtered, washed with 400 g of hot water at 60 ° C, and dried. This gave the dye intermediate 11.1 g.

(Step 2-2)

In a 500 ml four-necked flask, 6 g of the dye intermediate obtained in the step 2-1, dehydrated dimethyl hydrazine (manufactured by Wako Pure Chemical Industries, Ltd.), 220 g were placed, and stirred at room temperature for 30 minutes. 2 g of an oily sodium hydride (manufactured by Wako Pure Chemical Industries, Ltd.) was placed little by little, and stirred at room temperature for 1.5 hours. Then, while cooling the reaction vessel by an ice bath, 14.2 g of methyl iodide (manufactured by Junsei Chemical Co., Ltd.) was added dropwise, and the mixture was stirred at room temperature overnight. 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, and the mixture was stirred at room temperature for 30 minutes, and the precipitated crystals were filtered to obtain a crude crystal. The crude crystals were dissolved in 400 g of dichloromethane, and the organic layer was washed with 6% hydrochloric acid and dried over anhydrous sodium sulfate. The crystal obtained was suspended by stirring 143 g of diethyl ether for 1 hour, and the crystals were filtered, washed with n-hexane and dried, whereby 4.3 g of the present compound No. 3 was obtained. Maximum absorption wavelength: 544 nm (cyclohexanone).

Example 3 (Synthesis of Compound No. 6 in Table 1-1)

4.7 g of the dye intermediate obtained in the step 2-1 of Example 2, 176 g of dehydrated dimethyl hydrazine (manufactured by Wako Pure Chemical Industries, Ltd.), and stirred at room temperature were placed in a 500 ml four-necked flask. 30 minutes. To the above, 1.6 g of an oily sodium hydride (manufactured by Wako Pure Chemical Industries, Ltd.) was placed and stirred at room temperature for 1.5 hours. Then, while cooling the reaction vessel by means of an ice bath, it is dripped Iodine (manufactured by Junsei Chemical Co., Ltd.) 14.4 g, and stirred at room temperature for one night. 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, and the mixture was stirred at room temperature for 30 minutes, and the precipitated crystals were filtered to obtain a crude crystal. The crude crystals were dissolved in 264 g of methylene chloride, and the organic layer was washed with 6% hydrochloric acid, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The obtained crystals were suspended by stirring for 1 hour with 107 g of diethyl ether, and the crystals were filtered, washed with n-hexane and dried, whereby 3.5 g of the present compound No. 6 was obtained. Maximum absorption wavelength: 549 nm (cyclohexanone).

Synthesis Example 1 (Composition of a binder resin (copolymer))

160 g of methyl ethyl ketone, 10 g of methacrylic acid, 33 g of benzyl methacrylate and 1 g of α,α'-azobisisobutyronitrile were added to a 500 ml four-alkaline flask, and the mixture was stirred while stirring. Nitrogen gas was allowed to flow into the flask for 30 minutes. Thereafter, the temperature was raised to 80 ° C and stirred at 80 to 85 ° C for 4 hours. After completion of the reaction, the 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, and filtered, and the solid component 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 Production of Oily Dye Composition and Dye Colorant 1

It is obtained in the compound No. 2/Disperbyk-2001 (BYK-Chemie. Japan) / PGMEA (propylene glycol monomethyl ether acetate) / ethoxypropanol / synthesis example 1 of the present invention in Table 1-1. After the binder resin = 0.3 g / 1.0 g / 16.0 g / 2.0 g / 1.0 g composition ratio was mixed, 20 g of 0.3 mm zirconia beads was added, treated by a coating shaker for 60 minutes and filtered, and obtained. To the solution, 20 g of the binder resin obtained in Synthesis Example 1 was added and stirred, whereby an oily dye composition was produced. The obtained oil-based dye composition was spin-coated on a glass base and dried at 200 ° C for 20 minutes to prepare a dye-colored body 1.

Example 5

The dye coloring body 2 of the present invention was obtained in the same manner as in Example 4 except that the compound No. 2 in Table 1-1 was changed to the compound No. 3 of the present invention in Table 1-1.

Example 6

The dye colored body 3 of the present invention was obtained in the same manner as in Example 4 except that the compound No. 2 in Table 1-1 was changed to the compound No. 6 of the present invention in Table 1-1.

Comparative example 1

The comparative dye colored body 1 of the present invention was obtained in the same manner as in Example 4 except that the compound No. 1 in Table 1-1 was changed to C.I. Acid Red 289.

Comparative example 2

Coloring of the comparative dye of the present invention was obtained in the same manner as in Example 4, except that the compound No. 1 in Table 1-1 was changed to the dye A1 disclosed in Patent Document 1 (the compound of Synthesis Example 1 of Patent Document 1). Body 2.

Heat resistance test

The dye colored bodies obtained in Examples 4 to 6 were allowed to stand in an oven at 230 ° C for 3 hours. The L value, the a value, and the b value of the dye coloring body before and after the test were performed by a spectrophotometer and a C light source as a standard light at a viewing angle of 2 degrees. Colorimetric, the color difference was obtained according to the following formula. Further, since the change in the hue is smaller as the chromatic aberration is smaller, the characteristic of being excellent in toughness is exhibited.

Chromatic aberration = [(L value before test - L value after test) ² + (a value before test - value a after test) ² + (b value before test - b value after test) ² 〕 ^1/2

The measured values and color differences of the colorimetric in the heat resistance test are shown in Tables 2 to 4 below.

For comparison, the heat-resistant test was performed in the same manner for the above-mentioned comparative dye colored bodies 1 and 2. The results are shown in Tables 5 and 6 below.

The colorimetric result of the dye colored body 1 (Compound No. 2) is shown in Table 2 below.

The colorimetric result of the dye colored body 2 (Compound No. 3) is shown in Table 3 below.

The colorimetric result of the dye colored body 3 (Compound No. 6) is shown in Table 4 below.

The colorimetric results of the comparative dye colored body 1 are shown in Table 5 below.

The colorimetric results of the comparative dye colored body 2 are shown in Table 6 below.

The results of the color difference of the dye-colored bodies 1 to 3 and Comparative Examples 1 and 2 obtained based on the above Tables 2 to 6 are shown in Table 7 below.

As is clear from the above results, it is understood that the color difference of the dye-colored body of the comparative example before and after the test is compared with the dye-colored body of the present invention, It shows a lower value and is extremely excellent in heat resistance.

Example 7 Preparation of aqueous dye composition (preparation of test dyed fabric)

The aqueous dye composition of Compound No. 2 in Table 1-1 was adjusted according to the ratio of each component in Table 8 below, and printed on silk or nylon cloth by screen printing. The printed cloth was subjected to steam treatment at 100 ° C for 20 minutes, and then washed with water and dried to obtain a dyed fabric 1-1 (silk dyed fabric) and a dyed fabric 1-2 (nylon dyed fabric).

Hue evaluation of each dyed fabric

Colorimetric evaluation was performed on the hue of each of the test dyes obtained in the above manner. The colorimetric system measures L ^* , a ^* , b ^{* by} colorimetric dyeing using a colorimeter manufactured by GRETAG-MACBETH Corporation under the trade name SpectroEye. Further, the chroma C ^* is obtained from the value based on the following equation. The evaluation results are shown in Table 9 below, and the greater the chroma C ^* value, the clearer.

C ^* =[(a ^* ) ² +(b ^* ) ² ] ^1/2

The colorimetric evaluation results of Example 7 are shown in Table 9 below.

According to Table 9, it is considered that the dyeing property of clear dark red tone is obtained by using the dyeing fabrics 1-1 and 1-2 of the compound No. 2 of the present invention. Therefore, it is understood that the dye of the present invention is used as an aqueous dye composition or as a dye for dyeing for printing dyeing.

As described above, it has been clarified that the compound of the present invention and the dyed coloring body thereof are excellent in heat resistance, have high toughness, and have a wide range of applications such as color filter inks, inkjet inks, or dyeing dyes. The value is higher.

Claims (7)

A dibenzopyran compound which 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 number of 1 to 12; Alkyl or hydrogen atom). The benzopyrazine compound of claim 1, wherein 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 carbon. An unsubstituted alkyl or hydrogen atom of 1 to 12. The benzopyran compound of claim 1, wherein in the formula (1), R ₁ to R ₆ are each independently methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl. R ₇ and R ₈ are each independently a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group or a hydrogen atom. The benzopyrazine compound of claim 2, wherein in the formula (1), R ₁ to R ₆ are each independently methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl. R ₇ and R ₈ are each independently a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group or a hydrogen atom. The bisbenzopyran compound according to any one of claims 1 to 4, wherein, in the formula (1), R ₁ and R ₂ are each independently methyl, ethyl, n-propyl, n-butyl or isethyl Further, R ₃ to R ₆ are a methyl group, and R ₇ and R ₈ are each independently a methyl group or a hydrogen atom. An oily dye composition comprising the compound of any one of claims 1 to 5 and at least one oil-soluble organic solvent. An aqueous dye composition comprising the compound of any one of claims 1 to 5 and an aqueous medium.