JP5946174B2 - Xanthene-based soluble precursor compounds and colorants - Google Patents

Description

  The present invention relates to a novel xanthene compound useful as a colorant. More specifically, the present invention relates to a method for coloring various objects using a xanthene compound having poor solvent solubility as a coloring composition without using a pigment dispersion technique.

  C. I. Acid Red 289, C.I. I. Xanthene compounds such as Acid Red 52 are widely used as red to violet dyes because of their clear hue, high color development, and robustness against light and heat. It is used in a wide range of applications such as water-based ink, oil-based ink, ink-jet ink, and color filter.

  In general, dyes are roughly classified into dyes and pigments. Since the dye is soluble in a solvent, it is easy to handle and exhibits high coloring power and transparency, but on the other hand, it is known that fastness such as light resistance, heat resistance, and oxidizing gas resistance is inferior. On the other hand, pigments have high fastness such as light resistance and solvent resistance, but are difficult to handle because they are insoluble in solvents. For example, assuming application to optical applications such as color filters, ensuring high transparency is indispensable, and technology for minimizing pigments that are insoluble in solvents and advanced dispersion technology for dispersing in solvents are necessary. It becomes.

  However, even dyes do not dissolve in all solvents and vary depending on the compound, but most of them exhibit poor solubility in a specific solvent.

  As a method of coloring an object using a dye having poor solvent solubility, for example, a wet coloring method using an advanced dispersion technique such as the above-described pigment, or a dye from a gas phase such as vacuum deposition onto the object is used. There are dry coloring methods for precipitating molecules. The wet coloring method requires a long dispersion step in order to finely disperse the dye having poor solvent solubility in the solvent, and it is necessary to add various additives as a dispersion aid. It's not wide. In addition, in order to use a volatile organic solvent, it is necessary to take measures to reduce the environmental load such as a solvent vapor recovery facility. The dry coloring method requires a large facility such as a vacuum apparatus, and furthermore, since the number of durable dyes that can withstand high temperature conditions for vaporizing the dye is limited, it cannot necessarily be said that the applicable range is wide. .

  It is also possible to introduce a bulky substituent into a dye skeleton with poor solvent solubility to obtain solvent solubility. However, since it is affected by the introduced substituent effect, the physical properties are not necessarily equal to those of the original compound. Not necessarily.

  Even when the xanthene compound is used in a certain application, it may not be dissolved in a specific solvent used there. For example, when used in color filter applications, it does not dissolve in propylene glycol monomethyl ether acetate, which is a resist solvent, and thus requires treatment such as dispersion, which takes time and costs for production. Moreover, in order to obtain solvent solubility, the method of introduce | transducing a bulky substituent is also considered, However, There exists a fault which loses the hue of the original xanthene compound by the introduced substituent effect.

  Patent Documents 1 to 5 describe techniques for synthesizing and using various dyes as soluble precursors, but do not describe xanthene compounds. Further, Patent Document 6 describes a method of coating using an ionic liquid as a method for coloring a xanthene compound having poor solvent solubility, but the ionic liquid is not a commonly used solvent and is expensive. Therefore, there is a drawback that a large cost is required for use.

Japanese Patent No. 3510927 JP2007-284665A JP2002-19261 JP 2000-28820 A JP2010-282074 JP 2006-282893 A

  The present invention is to provide a method for coloring various objects as a colorant without using a xanthene compound dispersion technique having poor solvent solubility, and to provide a dye composition suitable for the application. is there.

  As a result of intensive studies to solve the above problems, the present inventors have found that a xanthene compound having a specific substituent has drastically improved solvent solubility as compared with the prior art. Since it can be easily detached, it has been found that an object can be colored without losing the properties of the original xanthene compound, and the present invention has been completed.

（一般式（３）において、Ｒ _１ 〜Ｒ _１０ はそれぞれ独立に炭素数１〜８のアルキル基または水素原子を表し、Ｊ _１ とＪ _２ はそれぞれ独立に水素原子または炭素数１〜４のアルキル基または下記式（２）を表す。ただし、Ｊ _１ とＪ _２ のうち少なくとも一方は、下記式（２）である。）。

（式（２）中、Ｌは炭素数１〜１０のアルキル基である。）、
（２）一般式（３）が一般式（４）で表されるキサンテン化合物である（１）に記載の前駆体化合物

（一般式（４）において、Ｒ_１〜Ｒ_１０はそれぞれ独立に炭素数１〜８のアルキル基または水素原子を表し、Ｊ_２は水素原子、メチル基、エチル基、ｎ−プロピル基またはｎ−ブチル基を表す。）、
（３）（１）または（２）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、
（４）（１）または（２）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、
（５）（３）または（４）に記載の組成物に含まれる一般式（３）の化合物より一般式（２）を脱離させる方法、
（６）（５）の方法を用いて着色した着色体、
に関する。 That is, the present invention
(1) A precursor compound characterized by being a xanthene compound represented by the general formula ( 3 )

(In General Formula ( 3 ), R _{1 to} R ₁₀ each independently represents an alkyl group having 1 to 8 carbon atoms or a hydrogen atom, and J ₁ and J ₂ are each independently a hydrogen atom or alkyl having 1 to 4 carbon atoms. Group or the following formula (2), provided that at least one of J ₁ and J ₂ is the following formula (2 ).

(In Formula (2) , L is a C1-C10 alkyl group.),
( 2 ) The precursor compound according to ( 1 ), wherein the general formula (3) is a xanthene compound represented by the general formula (4).

(In the general formula _{(4), R} 1 ~R ₁₀ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, _{J 2} represents a hydrogen atom, a methyl group, an ethyl group, n- propyl or n- Represents a butyl group),
( 3 ) an oil-based dye composition containing the compound according to (1) or ( 2 ) and at least one oil-soluble organic solvent,
( 4 ) An aqueous dye composition containing the compound according to (1) or ( 2 ) and an aqueous medium,
( 5 ) A method for desorbing the general formula (2) from the compound of the general formula ( 3 ) contained in the composition described in ( 3 ) or ( 4 ),
( 6 ) A colored product colored using the method of ( 5 ),
About.

  As described above, 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, the solvent solubility can be dramatically improved compared to conventional products. It exhibits excellent properties that can color an object without losing the properties of the original xanthene compound. 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.

1 shows compound No. 1 in Table 1. 1 is a measurement result of thermal analysis test 1.

  The compound of the present invention is represented by the general formula (1), formula (3) or formula (4).

  In Formula (1), A is a residue of a xanthene compound, and x B is a residue bonded to a nitrogen atom that is a part of A. B is a residue bonded to A and is represented by the formula (2).

  In the formula (1), x is an integer of 1 or 2, and the integer x is preferably 1.

  The xanthene compound of the formula (1) is a structure generally represented by the following formula (5) as described in, for example, Sadaharu Abeda et al. Means a compound having

  The xanthene compound of the present invention is preferably a compound represented by the following formula (6).

In Formula (6), R _{101 to} R ₁₀₄ each independently represent a hydrogen atom or a substituent, R ₁₀₅ represents a sulfo group, a carboxy group, or an alkoxycarbonyl group having 1 to 10 carbon atoms, and R ₁₀₆ represents hydrogen. R ₁₀₇ and R ₁₀₈ each independently represent a hydrogen atom or a substituent, and R ₁₀₉ ⁻ represents a counter anion. However, when the compound represented by the formula (6) forms a salt in the molecule, R ₁₀₉ ^- is absent.

The compound represented by the formula (6) has isomers having different cation positions, for example, as represented by the following formula (7) or formula (8). The “xanthene compound” of the present invention includes all such isomers. In the following formula (7) or formula (8), R _{101 to} R ₁₀₈ and R ₁₀₉ ⁻ represent the same meaning as in the formula (6).

  Of the xanthene compounds represented by the formula (6), more preferred are the compounds represented by the formula (3), and particularly preferred are the compounds represented by the formula (4).

  In Formula (2), L represents a C1-C10 alkyl group which may have a substituent.

  In the formula (2), examples of the substituent that L may have include, for example, a halogen atom (eg, F, Cl, Br), a hydroxy group, an alkoxy group (eg, methoxy, ethoxy, isobutoxy, etc.), an alkoxyalkoxy 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 a substituent), amino group, alkyl-substituted amino group (eg, methylamino, dimethylamino, etc.), cyano Group, nitro group, carboxyl group, carbonamido group, alkoxycarbonyl group (eg, methoxycarbohydrate) Le, ethoxycarbonyl), acyl group, an amido group (e.g., acetamido, etc.), a sulfonamido group (e.g., a methanesulfonamido) is and sulfonic acids.

  Specific examples of the alkyl group having 1 to 10 carbon atoms in which L has no substituent in formula (2) include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, and an iso-butyl group. Group, sec-butyl group, t-butyl group, n-pentyl group, iso-pentyl group, neo-pentyl group, t-pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, isopropyl group, Cyclopentyl, cyclohexyl, vinyl, allyl, propenyl, pentynyl, butenyl, hexenyl, hexadienyl, isopropenyl, isohexenyl, cyclohexenyl, cyclopentadienyl, ethynyl, propynyl Group, hexynyl group, isohexynyl group, cyclohexynyl group and the like.

  In the formula (2), L is preferably a C 1-4 alkyl group having no substituent, and particularly preferably a t-butyl group.

In Formula (3), R _{1 to} R ₁₀ each independently represent a C 1-8 alkyl group or a hydrogen atom which may have a substituent, and J ₁ and J ₂ each independently represent a hydrogen atom or a carbon atom. The alkyl group of number 1-4 or the said Formula (2) is represented. However, at least one of J ₁ and J ₂ is the above formula (2).

In R _{1 to} R ₁₀ of formula (3), examples of the substituent that the alkyl group having 1 to 8 carbon atoms may have include a halogen atom (eg, F, Cl, Br), a hydroxy group, and an alkoxy group. (Eg, methoxy, ethoxy, isobutoxy, etc.), alkoxyalkoxy groups (eg, methoxyethoxy, etc.), aryl groups (eg, phenyl, naphthyl etc., these aryl groups may further have a substituent), aryloxy Group (eg, phenoxy, etc.), acyloxy group (eg, acetyloxy, butyryloxy, hexyloxy, benzoyloxy, etc., these aryloxy groups may further have a substituent), amino group, alkyl-substituted amino Group (eg, methylamino, dimethylamino, etc.), cyano group, nitro group, carboxyl group, carbonamido group, al Alkoxycarbonyl group (e.g., methoxycarbonyl, ethoxycarbonyl, etc.), an acyl group, an amido group (e.g., acetamido, etc.), a sulfonamido group (e.g., a methanesulfonamido), and a sulfonic acid.

In R _{1 to} R ₁₀ of the formula (3), specific examples of the alkyl group having 1 to 8 carbon atoms having no substituent include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, and an n-butyl group. , Iso-butyl group, sec-butyl group, t-butyl group, n-pentyl group, iso-pentyl group, neo-pentyl group, t-pentyl group, hexyl group, heptyl group, octyl group, isopropyl group, cyclopentyl group Cyclohexyl group, vinyl group, allyl group, propenyl group, pentynyl group, butenyl group, hexenyl group, hexadienyl group, isopropenyl, isohexenyl group, cyclohexenyl group, cyclopentadienyl group, ethynyl group, propynyl group, A hexynyl group, an isohexynyl group, a cyclohexynyl group, etc. are mentioned.

In Formula (3), R _{1 to} R ₁₀ preferably have no substituent, and among them, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, an iso- A pentyl group and a neo-pentyl group are preferable, and a methyl group, an ethyl group, and an n-propyl group are most preferable.

In the formula (3), J ₁ and J ₂ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or the above formula (2). However, at least one of J ₁ and J ₂ is the above formula (2).

In J ₁ and J ₂ of the formula (3), the alkyl group having 1 to 4 carbon atoms includes a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, t -Butyl group is mentioned, and methyl group, ethyl group, n-propyl group and n-butyl group are the most preferable among them.

In _{J 1} and _{J 2} in the formula (3), the formula (2), is as defined for formula (2) in the formula (1).

In R _{1 to} R ₁₀ of the formula (4), specific examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, and iso-butyl group. , Sec-butyl group, t-butyl group, n-pentyl group, iso-pentyl group, neo-pentyl group, t-pentyl group, hexyl group, heptyl group, octyl group, isopropyl group, cyclopentyl group, cyclohexyl group, vinyl Group, allyl group, propenyl group, pentynyl group, butenyl group, hexenyl group, hexadienyl group, isopropenyl, isohexenyl group, cyclohexenyl group, cyclopentadienyl group, ethynyl group, propynyl group, hexynyl group, iso A hexynyl group, a cyclohexynyl group, etc. are mentioned.

R _{1 to} R ₁₀ in the formula (4) are, among others, 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, and a neo-pentyl group. It is preferably a methyl group, an ethyl group, or an n-propyl group.

（上記化合物（１０）〜（１３）および（１５）におけるＲ_１１およびＲ_１２は対応する置換基であり、例えば、式（１６）および（１７）である。

上記式（１４）〜（１７）におけるＬおよびＪ_１およびＪ_２およびＲ_１〜Ｒ_１０は、前記一般式（３）および（４）と同義である。） The xanthene compound represented by the formula (1) of the present invention can be produced, for example, by subjecting a xanthene compound produced by a known technique described in JP-A-2011-148973 to corresponding carboesterification. An example of the synthesis scheme is shown below.

(R ₁₁ and R ₁₂ in the above compounds (10) to (13) and (15) are the corresponding substituents, for example, the formulas (16) and (17).

L, J _1, J ₂ and R _{1 to} R ₁₀ in the above formulas (14) to (17) have the same meanings as the general formulas (3) and (4). )

  In the synthesis scheme exemplified above, the dye compound (1) of the present invention is formed by the primary condensation step shown in the first step, the secondary condensation step shown in the second step, and the carboesterification step shown in the third step. , (3) and (4).

  In the primary condensation step shown in the first step, the compound (9) and the compound (10) are heated and condensed in the presence of an organic solvent or a condensing agent. Next, in the secondary condensation step shown in the second step, the compound (11) obtained in the primary condensation step and the compound (12) are heated again and condensed to obtain the compound (13). it can. Finally, in the third step, the obtained compound (13) is carboesterified using dialkyl dicarbonate (di-t-butyl dicarbonate etc.) represented by (14) in the presence of an organic solvent or base. Can give compound (15). That is, the compound (1) of the present invention can be obtained.

  For the organic solvent used in the condensation reaction of the synthetic scheme exemplified above, in the primary condensation step shown in the first step, for example, methanol, ethanol, n-propanol, iso-propanol, n-butanol, etc. are used alone, Or it is preferable to mix and use. In the secondary condensation step shown in the second step, for example, ethylene glycol, N-methylpyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, sulfolane, chlorobenzene, dichlorobenzene, trichlorobenzene and nitrobenzene. Etc. are preferably used alone or in combination.

  The reaction temperature in the primary condensation step is preferably 50 to 100 ° C., more preferably 90 ° C. or less. The reaction temperature in the secondary condensation step is preferably 100 to 200 ° C, and more preferably 110 to 170 ° C.

When synthesizing a compound in which R _{1 to} R ₅ and R _{6 to} R _{10 in the} general formulas (3) and (4) are the same group, that is, a compound in which R ₁₁ and R ₁₂ are the same group, Compounds (10) and (12) in the above synthesis scheme can be the same. Therefore, in this case, the compound (13) can be obtained from the compound (9) by a one-step condensation process. The reaction temperature at that time is preferably 110 to 170 ° C.

  As the condensing agent, for example, zinc chloride, magnesium chloride, aluminum chloride or the like is preferably used.

  Examples of the organic solvent used for the carboesterification in the third step include water, acetonitrile, ethyl acetate, methyl acetate, tetrahydrofuran, dioxazine, dimethylacetamide, dimethylformamide, dimethyl sulfoxide, toluene, xylene, and the like. Or it can be used as a mixture.

  Examples of the base used for carboesterification in the third step include inorganic bases such as lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium hydride, sodium hydride, and potassium hydride. , T-butoxypotassium, pyridine, N, N-dimethylaminopyridine, triethylamine, organic bases such as 1,8-diazabicyclo [5.4.0] -7-undecene, and these may be used alone or in combination. Can be used.

表１−２

表１−３

表１−３において、Ｍｅはメチル基を、Ｅｔはエチル基を、ｎ−Ｐｒはノルマルプロピル基を、ｎ−Ｂｕはノルマルブチル基をそれぞれ表す。 Although the specific example of a compound represented by the said Formula (1) is shown to the following Table 1-1-Table 1-3, this invention is not limited to this.
Table 1-1

Table 1-2

Table 1-3

In Table 1-3, Me represents a methyl group, Et represents an ethyl group, n-Pr represents a normal propyl group, and n-Bu represents a normal 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 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 above 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. .

  The oil-based dye composition of the present invention can be prepared by dissolving or dispersing the xanthene 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 include polar organic solvents such as methyl-2-pyrrolidone and 2-pyrrolidone, and these solvents may be used alone or in combination 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.

  Next, the soluble precursor compound of the present invention represented by the following formula (1) is decarboesterified using chemical means, photolytic means and / or thermal means, and dissolved in the solvent shown by the following scheme. A method for converting to a xanthene compound (18) having poor properties will be described.

（化合物（１８）において、ｘは化合物（１）のそれと同じ整数を表し、Ａは化合物（１）のそれと同じ意味を表し、Ｈは水素原子であり、Ａの一部である窒素原子を介してｘ個の水素原子が結合していることを表す。）

(In the compound (18), x represents the same integer as that of the compound (1), A represents the same meaning as that of the compound (1), H is a hydrogen atom, and through a nitrogen atom which is a part of A. Represents that x hydrogen atoms are bonded.)

  The chemical means is a method for producing the xanthene compound (18) with a catalyst such as an acid or a base. The preferred catalyst is an acid, and examples include acetic acid, trifluoroacetic acid, propionic acid, acrylic acid, benzoic acid, hydrochloric acid, sulfuric acid, boric acid, p-toluenesulfonic acid, salicylic acid and the like.

  The photolytic means can be used as long as the xanthene compound represented by the formula (1) has absorption light. Specifically, a high-pressure or low-pressure mercury lamp, a tungsten lamp, an LED lamp, a laser light source, or the like is raised.

  The thermal means is a method of converting to a xanthene compound (18) by heating to 50 to 300 ° C. in the absence of a solvent or in the presence of a solvent. Among them, the heating temperature is preferably 70 to 250 ° C. Furthermore, a plurality of methods can be preferably used in combination among the thermal means, the chemical means, and the photolytic means.

  Among these, the thermal means generally used also as a solvent removal method for the coating film is preferable in that the solvent removal of the coating film and the decarboesterification of the xanthene compound (1) can be performed simultaneously. As a thermal means, it is carried out by heating from the coating surface side or the conductive support side using a gas such as air, nitrogen, steam, various heat media, infrared rays or electromagnetic waves. The heating temperature is preferably equal to or higher than the boiling point of the solvent used in the coating film, although it depends on other conditions such as heating time, presence / absence of electromagnetic wave irradiation, presence / absence of a decomposition catalyst.

  The oil-soluble dye composition or the aqueous dye composition can also be used for the coating film. For example, a colored body colored with a coating film or the like using the oil-soluble dye composition or the aqueous dye composition is decarboesterified using the chemical means, photolytic means and / or thermal means. Thereby, the colored body converted into the xanthene compound (18) can be obtained.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples. The thermal analysis test was measured and evaluated with a simultaneous differential thermothermal gravimetric measuring device “TG / DTA6200 manufactured by SII Nanotechnology Co., Ltd.”. Moreover, the compound obtained by the synthesis | combination in the Example was identified with the liquid chromatography-mass spectrometer "ACQUITY UPLC / LCT Premier XE made from Waters" (henceforth LC-MS). The liquid chromatography measurement conditions are as follows.
Column; Inertsil ODS-2 (5 μm, 3.0 mm × 250 mm)
Mobile phase: Liquid A; 5 mM ammonium acetate, liquid B; acetonitrile gradient (liquid B); 50% → (25 minutes) → 90% → (5 minutes) → 99%
Observation wavelength: 254 nm, column temperature: 40 ° C., flow rate: 0.4 ml / mim

Example 1 (Synthesis of Compound No. 1 in Table 1)
(Step 1-1)
In a 200 ml four-necked flask, 8.1 g of a fluorane compound of the following formula (100), 30 g of sulfolane, 12.1 g of 2,6-dimethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) and 4.1 g of zinc chloride are placed at 100 ° C. The mixture was stirred for 1 hour and further at 170 ° C. for 4 hours. When the heating was stopped and the liquid temperature dropped to 90 ° C. or lower, the reaction liquid was poured into 400 g of 5.8% hydrochloric acid and stirred at room temperature for 15 minutes. The precipitated crystals were filtered, washed with hot water, and dried to obtain 8.5 g of a dye intermediate (101).

(Step 1-2)
Into a 100 ml four-necked flask, 2.5 g of the dye intermediate (101) obtained in Step 1-1, 55 g of dimethyl sulfoxide, and 0.7 g of oily sodium hydride (manufactured by Wako Pure Chemical Industries, Ltd.) were added little by little at room temperature. For 1 hour. To this reaction solution, 1.9 g of di-t-butyl dicarbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) was dropped, followed by dropwise addition of 2.2 g of triethylamine, and 4-dimethylaminopyridine (manufactured by Tokyo Chemical Industry Co., Ltd.). 03 g was added and stirred at room temperature for 2 hours. The reaction mixture is poured into 400 g of water, stirred for 5 minutes, extracted with ethyl acetate, washed with water and saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to give the soluble precursor compound 1 of the present invention. .3 g was obtained. Red brown crystal. Maximum absorption wavelength: 513 nm (methanol).
LC-MS measured value: Retention time; 19.2, calculated value (Exact Mass) 674.25; measured value ([M + H] +); 675.17.

Example 2 (Synthesis of Compound No. 3 in Table 1)
In a 200 ml four-necked flask, 4 g of Acid Red 289 (manufactured by Tokyo Chemical Industry Co., Ltd.), 44 g of dimethyl sulfoxide and 1.1 g of oily sodium hydride (manufactured by Wako Pure Chemical Industries, Ltd.) were added little by little and stirred at room temperature for 1 hour. To this reaction solution, 3.1 g of di-t-butyl dicarbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise, followed by dropwise addition of 3.6 g of triethylamine, and further, 4-dimethylaminopyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) 0. 04 g was added and stirred at room temperature for 2 hours. The reaction solution was poured into 200 g of 2.9% hydrochloric acid in water, stirred for 10 minutes, extracted with dichloromethane, washed with water and saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. 0.5 g of precursor compound was obtained. Red brown crystal. Maximum absorption wavelength: 515 nm (methanol).

Example 3 (Solubility test in various solvents)
In the sample bottle, the dye compound No. 10 mg of 1 or 10 mg of the compound of the above formula (101) was weighed, and a single solvent was added little by little until the dye compound was completely dissolved. By measuring the weight at this time, the solubility of each dye compound in various solvents (weight percent concentration: abbreviated as wt%) was calculated.

The results of Example 3 are shown in Table 2 below. In Table 2, PGMEA represents propylene glycol monomethyl ether acetate.
Table 2
Compound Solubility in PGMEA Solubility in cyclohexanone Compound no. 1 1.15 wt% or more 1.38 wt% or more Compound (101) 0.1 wt% or less 0.1 wt% or less

  From the results of Example 3 above, Compound No. It is clear that the solvent solubility of No. 1 is higher than that of the comparative compound (101).

Example 4 (thermal analysis test)
In an aluminum pan container, the dye compound No. 5 mg of 1 or 5 mg of the compound of the formula (101) was weighed as a comparison target, and the thermal weight loss rate was measured for each. A measurement chart is shown in FIG.

Measurement program conditions:
Start temperature: 40 ° C, end temperature 250 ° C,
Temperature rising rate 10 ° C / 10mim, hold time 30mim

  As a result of Example 4 above, Compound No. For 1, a weight loss of 19.2% was observed around 150 ° C. This is compound no. This almost coincides with the theoretical value of 14.8% of the weight reduction rate associated with the elimination of one carboester group. However, in the comparative compound (101), such weight reduction was not observed.

In addition, Compound No. 1 of the present invention. The compound after the thermal analysis test of 1 was measured by LC-MS. The measurement conditions are the same as above.
LC-MS measured value: Retention time; 13.1, calculated value (Exact Mass) 574.19; measured value ([M + H] +); 575.13.

  Therefore, from the above results, the compound No. 1 of the present invention was It is clear that 1 was converted to compound (101) which is a decarboester by proceeding the decarboesterification reaction by applying heat of 150 ° C. or higher.

Example 5 (Preparation of oil-based dye composition and dyed colored body 1)
A 500 ml four-necked flask was charged with 160 g of propylene glycol monomethyl ether acetate, 6.6 g of methacrylic acid, 30 g of cyclohexyl methacrylate, 6 g of 2-hydroxyethyl methacrylate, and 2 g of α, α′-azobis (isobutyronitrile) while stirring. After flowing nitrogen gas into the flask for 30 minutes, 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 mixture was cooled to room temperature to obtain a colorless transparent and uniform liquid, that is, a copolymer solution. The polystyrene-reduced weight average molecular weight was 12000, and the acid value was 100.
Compound No. 1 obtained in Example 1 above was prepared by adding 1 g of propylene glycol monomethyl ether acetate to 0.8 g of the obtained copolymer. 1 was dissolved to prepare an oily dye composition. The obtained oil-based dye composition was spin-coated on a glass substrate, dried at 200 ° C. for 20 minutes, and the carboester group was eliminated simultaneously with the removal of the solvent, thereby preparing the dyed colored product of the present invention.

Comparative Example 1
Compound No. 1 in Table 1-1 A comparative dye-colored product 1 of the present invention was prepared in the same manner as in Example 5 except that 1 was changed to the above formula (101). As a result, the compound of the above formula (101) was propylene glycol monomethyl ether acetate. Solubility was poor, and a colored product could not be obtained by spin coating.

  As described above, the xanthene compound of the present invention can form an oily or aqueous dye composition to be processed into a dyed colored body. At this time, various substances can be colored as a colorant without using a dispersion technique. Is possible. For this reason, it has become clear that industrial value such as color filter ink and ink-jet ink has a wide range of applications.

Claims (6)

A precursor compound characterized by being a xanthene compound represented by the general formula ( 3 )

(In General Formula ( 3 ), R _{1 to} R ₁₀ each independently represents an alkyl group having 1 to 8 carbon atoms or a hydrogen atom, and J ₁ and J ₂ are each independently a hydrogen atom or alkyl having 1 to 4 carbon atoms. Group or the following formula (2), provided that at least one of J ₁ and J ₂ is the following formula (2 ).

(In Formula (2) , L is a C1-C10 alkyl group.). The precursor compound according to claim 1 , wherein the general formula (3) is a xanthene compound represented by the general formula (4).

(In the general formula _{(4), R} 1 ~R ₁₀ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, _{J 2} represents a hydrogen atom, a methyl group, an ethyl group, n- propyl or n- Represents a butyl group). An oil-based dye composition comprising the compound according to claim 1 or 2 and at least one oil-soluble organic solvent. An aqueous dye composition comprising the compound according to claim 1 or 2 and an aqueous medium. A method for desorbing the general formula (2) from the compound of the general formula ( 3 ) contained in the composition according to claim 3 or 4 . The colored body colored using the method of Claim 5 .

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