JP2013203765A - Xanthene compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a xanthene compound which is characterized in high clearness and color development and is superior in toughness such as heat resistance and to provide oil-based or aqueous dye compositions of the xanthene compound.SOLUTION: A specific xanthene compound made by causing cesium chloride to operate on an aqueous solution of, for example, Acid Red 52 (manufactured by Tokyo Chemical Industrial Company, Ltd.) and synthesizing a cesium salt pigment deposited as a crystal is provided. An oil-based dye composition is prepared as a composition containing the pigment with an oil-soluble organic solvent as a solvent, and an aqueous dye composition is prepared as a composition containing the pigment with an aqueous medium as a solvent.

Description

  The present invention relates to a novel xanthene compound.

  C. I. Acid Red 52 is widely used as a red dye, and has a wide range of applications such as various paints, water-based inks, oil-based inks, ink-jet inks, and color filters. 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.

  Non-Patent Document 1 includes C.I. I. Although it is described that Acid Red 52 is a xanthene compound of a sodium salt, as a result of studies by the present inventors, C.I. I. The dye composition using Acid Red 52 was insufficient in heat fastness.

New Edition Dye Handbook 426

  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.

（式（１）においてＲ_１〜Ｒ_４はそれぞれ独立に炭素数１〜５のアルキル基を表す）、
（２）式（１）においてＲ_１〜Ｒ_４がそれぞれ独立に無置換の炭素数１〜４のアルキル基であることを特徴とする（１）に記載の化合物、
（３）式（１）においてＲ_１〜Ｒ_４がエチル基であることを特徴とする（１）または（２）に記載の化合物、
（４）（１）乃至（３）のいずれか一つに記載の化合物と少なくとも１種類の油溶性有機溶媒を含有する油性染料組成物、
（５）(１）乃至（３）のいずれか一つに記載の化合物及び水性媒体を含有する水性染料組成物、
に関する。 That is, the present invention
(1) Xanthene compound represented by formula (1)

(In formula (1), R _{1 to} R ₄ each independently represents an alkyl group having 1 to 5 carbon atoms),
(2) The compound according to (1), wherein R _{1 to} R ₄ in formula (1) are each independently an unsubstituted alkyl group having 1 to 4 carbon atoms,
(3) The compound according to (1) or (2), wherein R _{1 to} R ₄ in the formula (1) are ethyl groups,
(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.

  As described above, the compound of the present invention is excellent in sharpness and color development, and when it is processed into a dyed colored body by forming an oily or aqueous dye composition, it exhibits characteristics excellent in fastness compared 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).

Alkyl group of 1 to 5 carbon atoms for _R 1 to R ₄ of formula (1) may have a substituent. Examples of the substituent in the aliphatic hydrocarbon residue which may have a substituent include a halogen atom (eg, F, Cl, Br), a hydroxy group, an alkoxy group (eg, methoxy, ethoxy, isobutoxy, etc.), alkoxy Alkoxy groups (eg, methoxyethoxy), aryl groups (eg, phenyl, naphthyl, etc., these aryl groups may further have a substituent), aryloxy groups (eg, phenoxy, etc.), acyloxy groups (eg, , Acetyloxy, butyryloxy, hexyloxy, benzoyloxy, etc., these aryloxy groups may further have substituents), amino groups, alkyl-substituted amino groups (eg, methylamino, dimethylamino, etc.), A cyano group, a nitro group, a carboxyl group, a carbonamido group, an alkoxycarbonyl group (eg, metho Shi and ethoxycarbonyl), acyl group, an amido group (e.g., acetamido, etc.), a sulfonamido group (e.g., a methanesulfonamido), and a sulfonic acid.

  Specific examples of the alkyl group having no substituent include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, and a t-butyl group. It is done.

In the formula (1), R _{1 to} R ₄ are preferably unsubstituted alkyl groups having 1 to 5 carbon atoms, and R _{1 to} R ₄ are particularly preferably ethyl groups.

表１−２

Specific examples of the compound represented by the above formula (1) are shown in the following Table 1-1 to Table 1-2, but the present invention is not limited thereto.
Table 1-1

Table 1-2

  The xanthene compound represented by the formula (1) of the present invention is synthesized, for example, by subjecting a condensate synthesized according to a known method described in Non-Patent Document 1 to salt exchange using commercially available cesium chloride. Can do. That is, a compound obtained by condensing and oxidizing a 4-formylbenzene-1,3-disulfonic acid derivative and the corresponding N, N-dialkylphenol can be obtained by salt exchange using cesium chloride. Moreover, it is also possible to synthesize | combine by carrying out the salt exchange of the commercially available xanthene compound to a cesium salt.

  As a method of salt exchange, for example, a condensate synthesized according to a known method described in Non-Patent Document 1 is dissolved in a reaction solvent, for example, water, 1 equivalent or more of cesium chloride is added, and a predetermined temperature (eg, 0 It can be easily synthesized by stirring the mixture at a temperature of from C. to 100.degree. C. and salting out the dye, and can be obtained by filtering the precipitated crystals.

  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 mass, and more preferably 0.5 to 20% by mass. 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 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 dye composition of the present invention can be prepared by dissolving or dispersing the triphenylmethane 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, 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, and these solvents may be used alone or in admixture of two or more.

  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 Ammonium salt of oxyethylene alkyl ether sulfate, ammonium salt of polyoxyethylene alkyl phenyl ether sulfate, polyoxyalkyl ether phosphate ester salt and other known anionic surfactants, vinyl naphthalene derivatives, α, β-ethylenically unsaturated carboxylic acid Aliphatic alcohol esters, 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 oleic acid derivatives, itaconic acid, itaconic acid derivatives, fumaric acid, fumaric acid derivatives, etc., or a random copolymer, or a high salt thereof. A molecular dispersant etc. are mentioned, It is preferable to use at 10-100 mass% with respect to the dye compound which disperse | distributes 1 or more of these. 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, and the like. Among these, 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 a surface adjusting agent, antiseptic / antifungal agent, pH adjusting agent 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., as pH adjusters, alkali 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 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 the examples, the maximum absorption wavelength and wet heat resistance of the compound obtained by the synthesis are the spectrophotometer “UV-3150 manufactured by Shimadzu Corporation” as the chromaticity (L value, a value, b value) of the dyed colored body. ”Was measured and evaluated.

Example 1 (Synthesis of xanthene compound of compound No. 1 in Table 1-1)
In a 500 ml beaker, 13 g of Acid Red 52 (manufactured by Tokyo Chemical Industry Co., Ltd.) and 200 g of water were added and dissolved by stirring for 30 minutes at room temperature. To this reaction solution, 21 g of cesium chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added little by little to precipitate crystals, and suspended and stirred at room temperature for 1 hour. The precipitated crystals were filtered, the obtained wet cake was suspended in 158 g of acetone, 30 g of water was further added, and the mixture was suspended and stirred at room temperature for 1 hour. The precipitated crystals were filtered and dried to obtain Compound No. 8.6 g of 1 was obtained. Green glossy crystal. Maximum absorption wavelength: 566 nm (Millipore water).

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. Then, it heated up to 80 degreeC and stirred for 4 hours as it was at 80-85 degreeC. 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, and 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 18000 and an acid value of 152 (mgKOH / g).

Example 1 Preparation of Oily Dye Composition and Dye Colored Body 1 Compound No. 1 1 xanthene compound / 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 After mixing at a composition ratio of 0.0 g / 1.0 g, 20 g of 0.3 mm zirconia beads were added, treated with a paint shaker for 60 minutes, filtered, and the binder resin obtained in Synthesis Example 1 was added to the resulting solution. An oil-based dye composition was prepared by adding 20 g and 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.

Comparative Example 1
Compound No. 1 in Table 1-1 1 and C.I. I. Except having changed to Acid Red 52, it carried out similarly to Example 1, and obtained the comparative dye coloring material 1 of this invention.

Heat Resistance Test The dyed colored product obtained in Example 1 was left in an oven at 200 ° 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 of colorimetry and the color difference in the heat resistance test are shown in Tables 2 to 4 below.

  For comparison, the heat resistance test was similarly conducted on the comparative dye-colored product 1. The results are shown in Table 3 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 65.00 63.74 -53.62
After the test 65.21 63.48-48.91
Difference before and after test -0.21 0.26 -4.71

The color measurement results of the comparative dye-colored product 1 are shown in Table 3 below.
Table 3
L value a value b value Before test 65.48 60.90 -50.36
After the test 66.27 57.28-43.86
Difference before and after test -0.79 3.62 -6.50

Table 4 below shows the results of obtaining the color difference of the dye-colored product 1 and Comparative Examples 1 and 2 from Tables 2 and 3 above.
Table 4
Color difference dye colored product 1 4.72
Dye-colored product for comparison 1 7.44

As is apparent from the above results, comparing the color difference before and after the test of the dye-colored product of the comparative example with the dye-colored product of the present invention, the color difference shows a low value and it can be seen that the heat resistance is extremely excellent.
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 became clear that the price was high.

Claims (5)

Xanthene compound represented by formula (1)

(In the formula (1), R _{1 to} R ₄ each independently represents an alkyl group having 1 to 5 carbon atoms). 2. The compound according to claim 1, wherein in the formula (1), R _{1 to} R ₄ are each independently an unsubstituted alkyl group having 1 to 4 carbon atoms. The compound according to claim 1 or 2, wherein R _{1 to} R ₄ in the formula (1) are ethyl groups. 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.