JP2016065220A - Xanthene compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new xanthene compound excellent in color sharpness and color development and high in solubility to an oily solvent, and a dye composition using the compound.SOLUTION: Provided is a xanthene compound examplified by Formulae No.1 and No.2, capable of being synthesized, e.g., in such a manner that a compound obtained by condensing 3,6-dichlorospiro[9H-xanthene-9,3'-[3H][2,1]benzoxathiol]1',1'-dioxide is condensed with an amino alcohol compound and an amine compound in this order or oppositely thereto with a chloride having an ethylenic unsaturated photopolymerizable group as well, and an oily or an aqueous dye composition containing the compound.SELECTED DRAWING: None

Description

  The present invention relates to a novel xanthene compound useful as a dye.

  In general, dyes are roughly classified into dyes and pigments. Although pigments have high fastness such as light resistance and solvent resistance, they 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. On the other hand, dyes are generally soluble in solvents and are therefore easy to handle and are known to exhibit high coloring power and transparency. However, even dyes do not necessarily have good solubility in all solvents. However, most of them are hardly soluble in a specific solvent.

  As a method of coloring an object using a dye having poor solubility in a solvent, for example, a wet coloring method using an advanced dispersion technique such as the above-described pigment is used, or from a gas phase such as vacuum deposition onto the object. There is a dry coloring method in which dye molecules are deposited. The wet coloring method requires a long dispersion step in order to finely disperse a dye having poor solubility in a solvent in the solvent, and it is necessary to add various additives as a dispersion aid. Is not wide. In addition, the dry coloring method requires large equipment such as a vacuum device, and the number of durable dyes that can withstand high temperature conditions that vaporize the dye is limited, so that the range of application is not necessarily wide. I can not say.

  It is also possible to introduce a bulky substituent into a dye skeleton that is poorly soluble in a solvent to improve the solubility in the solvent, but due to the effect of the introduced substituent, the physical properties are not necessarily equal to the original compound. Is not limited.

Xanthene compounds have clear hues and high color developability, and are robust against light, heat, etc., so various dyes, water-based inks, oil-based inks, and inkjets are used as dyes for hues in the red to violet range. It is used in a wide range of applications such as for inks and color filters. As such a dye, for example, a xanthene compound represented by the following formula (100) described in Patent Document 1 (Chemical Formula 28 in Paragraph 0046) is known.
However, as a result of investigations by the present inventors, the xanthene compound represented by the following formula (100) has insufficient solubility in a specific solvent.

JP 2001-337449 A

Chemical Biology, 5 (11), 1065.

  An object of this invention is to provide the novel xanthene compound which is excellent in sharpness and coloring property, and has favorable solubility with respect to a specific solvent.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a novel xanthene compound having a specific structure is significantly more soluble in an oily medium than a conventionally known xanthene dye (compound). The inventors have found that the present invention is superior and have completed the present invention.
That is, the present invention
[1] A xanthene compound represented by the following formula (1)

(In Formula (1), R < ¹ > -R < ³ > is respectively independently C1-C6 which has a substituent chosen from the group which consists of a hydrogen atom; a halogen atom, an alkoxy group, a cyano group, an amide group, and a phenyl group. Represents an alkyl group or an unsubstituted alkyl group having 1 to 6 carbon atoms, J and Q each independently represents an unsubstituted alkylene group having 2 to 4 carbon atoms, and M represents an ethylenically unsaturated photopolymerizable group. ),
[2] The xanthene compound according to [1], wherein M is an ethylenically unsaturated photopolymerizable group represented by the following formula (2):

(In Formula (2), R ⁴ represents a hydrogen atom or an unsubstituted alkyl group having 1 to 4 carbon atoms. R ⁵ represents a hydrogen atom, an unsubstituted alkyl group having 1 to 4 carbon atoms, or an unsubstituted phenyl group. Represent),
[3] The xanthene compound according to the above [2], wherein R ⁵ in the formula (2) is a hydrogen atom or an unsubstituted alkyl group having 1 to 4 carbon atoms.
[4] The xanthene compound according to any one of [1] to [3], wherein R ^{1 to} R ³ in Formula (1) are each independently an unsubstituted alkyl group having 1 to 6 carbon atoms.
[5] An oil-based dye composition containing the xanthene compound according to any one of [1] to [4] and an oil-soluble organic solvent,
[6] An aqueous dye composition comprising the xanthene compound according to any one of [1] to [4] and an aqueous medium,
About.

  The xanthene compound of the present invention (hereinafter also simply referred to as “the compound of the present invention”) is excellent in sharpness and color developability and excellent in solubility in an oil-soluble medium, particularly an organic solvent.

The compound of the present invention is represented by the formula (1).
In formula (1), R ^{1 to} R ³ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and the alkyl group having 1 to 6 carbon atoms may have a substituent.

The alkyl group having 1 to 6 carbon atoms represented by R ^{1 to} R ^{3 in the} formula (1) is not limited to any of linear, branched or cyclic as long as the alkyl group has 1 to 6 carbon atoms. Specific examples include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, t-butyl group, pentyl group, 1-methylbutyl group, 2 -Methylbutyl group, 3-methylbutyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, hexyl group, 1-methylpentyl group, 2- Methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 2, 3-di Chirubuchiru group, 3,3-dimethylbutyl group, a 1-ethyl-1-methylpropyl group and a cyclohexyl group.

Examples of the substituent that the alkyl group having 1 to 6 carbon atoms represented by R ^{1 to} R ^{3 in} Formula (1) may have include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), and an alkoxy group. (For example, methoxy group, ethoxy group, iso-propoxy group, n-propoxy group, n-butoxy group, iso-butoxy group, sec-butoxy group, t-butoxy group, etc.), cyano group, amide group (for example, acetamide) Group, ethylamide group, propylamide group, etc.) and phenyl group (for example, 2,6-dimethylphenyl group, 2,6-diethylphenyl group, 2,6-dipropylphenyl group, etc.) and the like.

As R < ¹ > -R < ³ > of Formula (1), it is preferable that it is each independently an unsubstituted C1-C6 alkyl group, and it is an unsubstituted linear C1-C4 alkyl group. Is more preferable, and an ethyl group is still more preferable.
In the present invention, the “unsubstituted alkyl group having 1 to 6 carbon atoms” means an alkyl group composed of only 1 to 6 carbon atoms and hydrogen atoms.

  In formula (1), J and Q each independently represent an unsubstituted alkylene group having 2 to 4 carbon atoms.

Specific examples of the unsubstituted C2-C4 alkylene group represented by J and Q in the formula (1) include an ethylene group, an n-propylene group, an iso-propylene group, an n-butylene group, and an iso-butylene group. , Sec-butylene group and t-butylene group are mentioned, and ethylene group is preferable.
In the present invention, the term “unsubstituted alkylene group having 2 to 4 carbon atoms” refers to a divalent linking group obtained by removing one hydrogen atom from an alkyl group having 2 to 4 carbon atoms consisting of only a carbon atom and a hydrogen atom. Means.

  In formula (1), M represents an ethylenically unsaturated photopolymerizable group.

  The ethylenically unsaturated photopolymerizable group here means a photopolymerizable substituent having a reactive C═C double bond such as a vinyl group. Examples of the ethylenically unsaturated photopolymerizable group include those in which a reactive C═C double bond is activated by bonding with an electron-withdrawing group such as a carbonyl group, that is, in the formula (2) It is preferable that it is a substituent represented.

In formula (2), R ⁴ represents a hydrogen atom or an unsubstituted alkyl group having 1 to 4 carbon atoms.

Specific examples of the unsubstituted alkyl group having 1 to 4 carbon atoms represented by R ⁴ in the 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 and t-butyl group.

R ^{4 in} formula (2) is preferably a hydrogen atom or a methyl group.

In formula (2), R ⁵ represents a hydrogen atom, an unsubstituted alkyl group having 1 to 4 carbon atoms, or an unsubstituted phenyl group.

Specific examples of the unsubstituted alkyl group having 1 to 4 carbon atoms represented by R ⁵ in formula (2) are the same as the unsubstituted alkyl group having 1 to 4 carbon atoms represented by R ^{4 in} formula (2). Can be mentioned.

R ^{5 in} formula (2) is preferably a hydrogen atom or an unsubstituted alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group, and still more preferably a hydrogen atom. .

The xanthene compound represented by the formula (1) of the present invention is preferably a combination of each of the above-mentioned R ^{1 to} R ³ , J, Q and M (R ⁴ and R ⁵ in the formula (2)). A combination of more preferable ones is more preferable.

The xanthene compound represented by the formula (1) of the present invention is, for example, a condensate 3,6-dichlorospiro [9H-xanthene-9,3 ′-[synthesized according to the method described in Non-Patent Document 1. 3H] [2,1] benzooxathiol] 1 ′, 1′-dioxide and a compound obtained by condensing an amine having a hydroxy group and the like, further condensing a chloride having an ethylenically unsaturated photopolymerizable group. Can be synthesized. An example of the synthesis scheme is shown below.
Equation (5) in ~ (9) ^R 1 ^{to R} 3 in the synthetic schemes, J, Q and M, the formula (1) or (2) in ^R 1 ^{to R} 3, J, synonymous with Q and M is there.

That is, 3,6-dichlorospiro [9H-xanthene-9,3 ′-[3H] [2,1] benzooxathiol] 1 ′, 1′-dioxide (represented by the formula (4) in the above synthesis scheme example) A compound obtained by condensing a corresponding hydroxyl group-containing amine (the compound represented by the formula (5) in the above synthesis scheme example) at a predetermined temperature (for example, 5 to 90 ° C.). A compound obtained by condensing a corresponding amine (a compound represented by the formula (7) in the above synthesis scheme example) at a predetermined temperature (for example, 40 to 130 ° C.) with a compound represented by the formula (6) in the scheme example) (Compound represented by the formula (8) in the above synthesis scheme example) is obtained.
An isocyanate having a -QM group (the compound represented by the formula (9) in the above synthesis scheme example) is added to the hydroxy group of the obtained compound represented by the formula (8) at a predetermined temperature (for example, 30 to 140 ° C). ) To obtain a compound represented by the formula (1) of the present invention.

  The above scheme is an example of condensing the compound represented by the formula (5) to the compound represented by the formula (4). First, the compound represented by the formula (4) is represented by the formula (7). May be condensed, and then the compound represented by the formula (5) may be condensed.

  The synthesis scheme exemplified above is represented by the formula (1) of the present invention by the primary condensation step shown in the first step, the secondary condensation step shown in the second step, and the tertiary condensation step shown in the third step. It is a method of synthesizing the represented xanthene compound.

  In the primary condensation step shown in the first step, the compound represented by formula (4) and the amine represented by formula (5) are condensed by heating in the presence of an organic solvent or a condensing agent. Next, in the secondary condensation step shown in the second step, the compound represented by formula (6) obtained in the primary condensation step and the amines represented by formula (7) are combined with an organic solvent or A compound represented by the formula (8) can be obtained by condensation by heating again in the presence of a condensing agent. Next, in the third condensation process shown in the third step, the compound represented by the formula (8) obtained in the second condensation process and the isocyanate represented by the formula (9) are mixed with an organic solvent or necessary. Accordingly, the xanthene compound represented by the formula (1) can be obtained by condensation with ice cooling or heating as necessary in the presence of a base catalyst.

  In the primary condensation step shown in the first step of the synthesis scheme exemplified above and the secondary condensation step shown in the second step, for example, alcohols such as methanol, ethanol, n-propanol, iso-propanol, and n-butanol are used. N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP), N, N-dimethylacetamide, N, N-dimethylformamide (hereinafter abbreviated as DMF), dimethyl sulfoxide, sulfolane, chlorobenzene, dichlorobenzene, trichlorobenzene and nitrobenzene It is preferable to use organic solvents such as singly or in combination. In the third condensation step shown in the third step, for example, organic solvents such as NMP, DMF, dimethyl sulfoxide, sulfolane, chlorobenzene, dichlorobenzene, trichlorobenzene, and nitrobenzene are preferably used alone or in combination.

  The reaction temperature in the primary condensation step is preferably 5 to 90 ° C, and more preferably 30 to 75 ° C. The reaction temperature in the secondary condensation step is preferably 40 to 130 ° C, more preferably 50 to 110 ° C. The reaction temperature in the tertiary condensation step is preferably 30 to 140 ° C, more preferably 40 to 110 ° C.

  When the compound represented by the formula (5) and the compound represented by the formula (7) are the same, one step of the compound represented by the formula (4) and the compound represented by the formula (5) A compound represented by the formula (8) can also be obtained by a condensation reaction. The reaction temperature at that time is preferably 40 to 130 ° C.

  In the primary condensation step and the secondary condensation step, a condensing agent can be used as necessary, and as the condensing agent that can be used, for example, zinc chloride, magnesium chloride, aluminum chloride or the like is preferably used. When using a condensing agent, it is preferable to contain 0.5-2.0 molar equivalent in each of a primary condensation process and a secondary condensation process.

  In the tertiary condensation step, a base catalyst can be used as necessary. Examples of the base catalyst that can be used include triethylamine, pyridine, N, N-dimethyl-4-aminopyridine, and N, N-dimethylpiperazine. Etc. are preferably used. When using a base catalyst, it is preferable to contain 0.1-4.0 molar equivalent.

  Although the specific example of the xanthene compound shown by the said Formula (1) of this invention below is shown, this invention is not limited to these.

  The oily or aqueous dye composition of the present invention contains a xanthene compound represented by the formula (1) of the present invention, an oil-soluble organic solvent in the case of an oily dye composition, and an aqueous medium in the case of an aqueous dye. The content of the xanthene compound represented by the formula (1) in the oily or aqueous dye composition of the present invention is usually 0.1 to 50% by mass, preferably 0.2 to 40% by mass, more preferably 0.5. ˜20 mass%.

  The oil-based dye composition of the present invention can be prepared by dissolving or dispersing the xanthene compound represented by the formula (1) 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, DMF, dimethyl sulfoxide, sulfolane, NMP, 2-pyrrolidone, etc. These organic solvents may be used, and these solvents may be used alone or in combination of two or more.

  The aqueous dye composition of the present invention can be prepared by dissolving or dispersing the xanthene compound represented by the formula (1) of the present invention in an aqueous medium. Examples of the aqueous medium include water or a water-soluble organic solvent. Examples of the water-soluble organic solvent include alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol and benzyl alcohol; ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol Polyhydric alcohols such as polypropylene glycol, glycerin, trimethylolpropane, 1,3-pentanediol and 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 Le and dipropylene glycol monomethyl ether; ethanolamine, diethanolamine, amines such as triethanolamine and morpholine; 2-pyrrolidone, NMP, 1,3-dimethyl - imidazolidinone. These solvents may be used alone or in combination of two or more.

An acid or an alkali may be added to the aqueous dye composition. Examples of the acid that can be added to the aqueous dye composition include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, and organic acids such as oxalic acid and citric acid.
Examples of the alkali that can be added to the aqueous dye composition include alkali metal hydroxides such as sodium hydroxide, lithium hydroxide and potassium hydroxide, and alkali metal carbonates such as sodium carbonate, lithium carbonate and potassium carbonate. The acid or alkali content that can be added to the aqueous dye composition is usually 0.1 to 30% by mass, preferably 0.2 to 20% by mass, and more preferably 0.3 to 15% by mass.

  In the oily or aqueous dye composition of the present invention, a coloring material other than the xanthene compound represented by the formula (1) may be used in combination as necessary for the purpose of adjusting the hue. Examples of color materials that can be used in combination 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. Although it is mentioned, it is not limited to these, It adds in the state melt | dissolved or disperse | distributed to the solvent. The amount of the coloring material that can be used in combination in the oily or aqueous dye composition of the present invention is not particularly limited, and is usually 15% by mass or less, preferably 5 to 10%, based on the xanthene compound represented by the formula (1). Mass is used.

  In the oil-based dye composition and the aqueous dye composition of the present invention, a dispersant can be used together as necessary for the purpose of improving the dispersibility of the xanthene compound represented by the formula (1).

  Dispersants that can be used in the oil-based dye composition include sodium dodecylbenzene sulfonate, 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 inic acid derivatives, itaconic acid, itaconic acid derivatives, fumaric acid, fumaric acid derivatives, etc., or a random copolymer, or a high salt thereof. Examples thereof include molecular dispersants, and one or more of these are usually 500% by mass or less, preferably 10 to 450% by mass with respect to the xanthene compound represented by formula (1) and the colorant used in combination as necessary. More preferably, 100 to 400% by mass is used.

  As a dispersant that can be used in the aqueous dye composition, in addition to a surfactant, a dispersant commonly used for preparing a pigment dispersion, for example, a polymer dispersant can be suitably used. Specific examples of the polymer dispersant include polyvinyl alcohols, polyvinyl pyrrolidones, polyacrylic acid, acrylic acid-acrylonitrile copolymer, acrylate-acrylonitrile copolymer, vinyl acetate-acrylic ester copolymer. , Acrylic resins such as acrylic acid-acrylic acid ester copolymer, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, styrene-methacrylic acid-acrylic acid ester copolymer, styrene-α-methylstyrene -Styrene-acrylic resins such as acrylic acid copolymer, styrene-α-methylstyrene-acrylic acid-acrylic acid ester copolymer, styrene-maleic acid copolymer, styrene-maleic anhydride copolymer, isobutylene-malein Acid resin, rosin-modified maleic acid resin, vinyl naphthalene Acrylic acid copolymer, vinyl naphthalene-maleic acid copolymer, vinyl acetate-ethylene copolymer, vinyl acetate-fatty acid vinyl ethylene copolymer, vinyl acetate-maleic acid ester copolymer, vinyl acetate-crotonic acid copolymer Examples include polymers, vinyl acetate copolymers such as vinyl acetate-acrylic acid copolymers, and salts thereof. It is usually used in an amount of 100% by mass or less, preferably 10 to 70% by mass, based on the xanthene compound represented by the formula (1) and the coloring material used in combination.

  Examples of the method for finely dispersing the xanthene compound represented by the formula (1) include methods 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 addition, when dispersion is performed using a sand mill (bead mill), it is preferable to perform processing under conditions that can improve the grinding efficiency, such as using beads with a small diameter or increasing the filling rate of beads, and further after the grinding treatment. It is also preferable to remove elementary particles by filtration, centrifugation, or the like.

  The dye composition of the present invention may contain a surface adjusting agent, an antifoaming agent, an antiseptic / antifungal agent, a pH adjusting agent and the like as other additives. As the surface conditioner, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, a known nonionic, polysiloxane or polydimethylsiloxane based copolymer of ethylene oxide and propylene oxide, etc. As surfactants and antifoaming agents, silicone-based and acetylene-based known antifoaming agents, and as antiseptic and antifungal agents, sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, zinc pyridinethione Known antiseptic / antifungal agents such as 1-oxide, 1,2-benzisothiazolin-3-one, amine salt of 1-benzisothiazolin-3-one, and pH adjusters include sodium hydroxide, potassium hydroxide, Alkali hydroxide such as lithium hydroxide Li metals, triethanolamine, diethanolamine, dimethylethanolamine, known pH adjusting agent such as tertiary amines such as diethylethanolamine and the like, which can be added as required, respectively.

  In addition, the oil-based or aqueous dye composition of the present invention has a polyamide-based, polyurethane-based, polyester-based, epoxy-based, or polyacrylic resin that is compatible with the medium in the composition for the purpose of improving the fixability of the dye to the object to be colored. It is preferable to contain a binder resin such as a monomer or an oligomer having an ethylenic unsaturated group and an ethylenically unsaturated group. The binder resin is usually used in an amount of 10000% by mass or less based on the xanthene compound represented by the formula (1) in the dye composition and the color material used in combination as necessary. In addition, what is necessary is just to use an appropriate quantity for a polymerization initiator, a hardening | curing agent, etc. according to the usage-amount of binder resin. 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 xanthene compound represented by the formula (1) of the present invention is an oil-based dye composition or a water-based dye composition, such as various paints, water-based inks, oil-based inks, ink-jet inks, ink-jet UV inks and other printing inks, thermal recording. Examples thereof include ink sheets in materials, color toners for electrophotography, dyeing solutions for dyeing various fibers, and various coloring compositions for resin coloring. The oil dye composition and the aqueous dye composition are used for materials to be colored such as plain paper, coated paper, plastic film, fiber and cloth (cellulose, nylon, wool, etc.), leather, and plastic substrate. The dye composition of the present invention can be applied to the material to be colored by various dyeing methods such as dyeing and printing; various recording methods such as thermal recording and electrophotographic recording; screen printing, offset printing, letterpress printing, flexographic printing Various printing methods such as printing and ink jet printing; or 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 was measured with a spectrophotometer “trade name UV-3150, manufactured by Shimadzu Corporation”. In the examples, “part” is based on mass unless otherwise specified.

Example 1 (Synthesis of xanthene compound represented by Compound No. 1)
(Step 1-1)
A 200 ml four-necked flask is charged with 20.3 parts of the compound represented by the above formula (4), 120 parts of sulfolane and 6.7 parts of 2- (ethylamino) ethanol (Tokyo Chemical Industry Co., Ltd.), and 70 ° C. For 1 hour. When the temperature of the reaction solution falls to 50 ° C., the reaction solution is poured into 2N hydrochloric acid water, and the precipitated crystals are collected by filtration, washed and dried, whereby a dye intermediate 10.5 represented by the following formula (101) is obtained. Got a part.

(Step 1-2)
In a 200 ml four-necked flask, 10.5 parts of the dye intermediate represented by the formula (101) obtained in Step 1-1, 50 parts of sulfolane, 20 parts of NMP and diethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) 8.4 A portion was added and stirred at 65 ° C. for 3 hours. When the temperature of the reaction solution dropped to 50 ° C., the reaction solution was poured into 10% brine, and 35% aqueous hydrochloric acid was added to adjust the pH to 3. The precipitated crystals were collected by filtration, washed, and dried to obtain 9.2 parts of a dye intermediate represented by the following formula (102).

(Step 1-3)
In a 200 ml four-necked flask, 8.9 parts of the dye intermediate represented by the formula (102) obtained in Step 1-2, 80 parts of NMP, 4.3 parts of pyridine, and Karenz MOI (manufactured by Showa Denko) 18 2 parts were added and stirred at 100 ° C. for 6 hours. The reaction solution was poured into 2700 parts of ethyl acetate, and the precipitated crystals were collected by filtration, washed and dried. 0.5 part of 1 was obtained. The maximum absorption wavelength of the xanthene compound was 553 nm (methanol).

Example 2 (Synthesis of xanthene compound represented by Compound No. 8)
The xanthene compound No. 1 was similarly changed except that the Karenz MOI in Step 1-3 of Example 1 was changed to Karenz AOI (manufactured by Showa Denko). 0.4 part of 8 was obtained. The maximum absorption wavelength of the xanthene compound was 553 nm (methanol).

Example 3 (Preparation of oil-based dye composition of Compound No. 1)
After mixing 100 mg of the xanthene compound obtained in Example 1 and 1900 mg of diacetone alcohol in a 20 ml sample tube, the mixture was stirred at 25 ° C. for 1 hour to prepare an oil dye composition having a xanthene compound concentration of 5%. In the obtained oil-based dye composition, no visual residue was confirmed. Moreover, the residue by visual observation was not confirmed also about the oil-based dye composition with the xanthene compound density | concentration adjusted by the method similar to the above using 100 mg of xanthene compounds and 900 mg of diacetone alcohols. Moreover, the residue by visual observation was not confirmed also about the oil-based dye composition which changed the said diacetone alcohol into methyl lactate and adjusted the xanthene compound density | concentration by the same method with 5% and 10%, respectively.

Example 4 (Preparation of oil-based dye composition of Compound No. 8)
In the same manner as in Example 3 except that the xanthene compound obtained in Example 1 was changed to the xanthene compound obtained in Example 2, xanthene compound No. 1 was obtained. 8 oily dye compositions were prepared respectively. Visual residue was not confirmed in all the prepared oily dye compositions.

Example 5 (Synthesis of xanthene compound represented by Compound No. 2)
(Step 5-1)
In a 1000 ml four-necked flask, 67.3 parts of the compound represented by the above formula (4), 419 parts of NMP and 26.0 parts of dipropylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) were placed, and stirred at 75 ° C. for 3 hours. . The reaction solution was cooled to 10 ° C., and the reaction solution was poured into 2N hydrochloric acid and stirred for 1 hour. The precipitated crystals were collected by filtration, washed, and dried to obtain 36.1 parts of a dye intermediate represented by the following formula (103).

(Step 5-2)
In a 300 ml four-necked flask, 34.3 parts of the formula dye intermediate obtained in Step 5-1, 146 parts of NMP and 16.3 parts of 2- (ethylamino) ethanol were placed, and stirred at 90 ° C. for 1.5 hours. . The reaction solution was poured into 2N aqueous hydrochloric acid, and the precipitated crystals were collected by filtration, washed and dried to obtain 34.9 parts of a dye intermediate represented by the following formula (104).

(Step 5-3)
In a 100 ml four-necked flask, 4.4 parts of the dye intermediate obtained in Step 5-2, 23 parts of NMP, 6.7 parts of Karenz MOI, and 2.0 parts of pyridine were added and stirred at 105 ° C. for 3 hours. After completion of the reaction, this was poured into 150 parts of diisopropyl ether, and the precipitated solid decanted. This solid was dissolved in 53 parts of tetrahydrofuran and poured into 150 parts of diisopropyl ether. By filtering, washing and drying the precipitated solid, the xanthene compound No. 1 of the present invention was obtained. 1.7 parts of 2 were obtained. The maximum absorption wavelength of the xanthene compound was 555 nm (methanol).

Example 6 (Preparation of oil-based dye composition of Compound No. 2)
In the same manner as in Example 3 except that the xanthene compound obtained in Example 1 was changed to the xanthene compound obtained in Example 5, xanthene compound No. 1 was obtained. Two oily dye compositions were prepared respectively. Visual residue was not confirmed in all the prepared oily dye compositions.

Comparative Example 1
A comparative oil dye composition was prepared in the same manner as in Example 3 except that the xanthene compound obtained in Example 1 was changed to the xanthene compound represented by the above formula (100). A visual residual was confirmed in all the comparative oil-based dye compositions obtained.

  From the examples and comparative examples, it is clear that the xanthene compound represented by the formula (1) of the present invention is excellent in solubility in an oily medium.

The xanthene compound of the present invention is excellent in sharpness and color developability, and the xanthene compound has high solubility in an organic medium and is easy to handle. Therefore, the xanthene compound of the present invention can be used in dye-colored bodies, and can be used for various paints, water-based inks, oil-based inks, ink-jet inks, ink-jet UV inks, heat-sensitive recording materials, electrophotographic color toner materials, and various fibers. It can be used for a wide range of applications such as dyeing solution for dyeing and resin coloring.

Claims (6)

Xanthene compound represented by the following formula (1)

(In Formula (1), R < ¹ > -R < ³ > is respectively independently C1-C6 which has a substituent chosen from the group which consists of a hydrogen atom; a halogen atom, an alkoxy group, a cyano group, an amide group, and a phenyl group. Represents an alkyl group or an unsubstituted alkyl group having 1 to 6 carbon atoms, J and Q each independently represents an unsubstituted alkylene group having 2 to 4 carbon atoms, and M represents an ethylenically unsaturated photopolymerizable group. .) The xanthene compound according to claim 1, wherein M is an ethylenically unsaturated photopolymerizable group represented by the following formula (2).

(In Formula (2), R ⁴ represents a hydrogen atom or an unsubstituted alkyl group having 1 to 4 carbon atoms. R ⁵ represents a hydrogen atom, an unsubstituted alkyl group having 1 to 4 carbon atoms, or an unsubstituted phenyl group. Represents.) The xanthene compound according to claim 2, wherein R ⁵ in formula (2) is a hydrogen atom or an unsubstituted alkyl group having 1 to 4 carbon atoms. The xanthene compound according to any one of claims 1 to 3, wherein R ^{1 to} R ³ in Formula (1) are each independently an unsubstituted alkyl group having 1 to 6 carbon atoms. The oil-based dye composition containing the xanthene compound as described in any one of Claims 1 thru | or 4, and an oil-soluble organic solvent. An aqueous dye composition comprising the xanthene compound according to any one of claims 1 to 4 and an aqueous medium.