JP6161558B2 - Methine compounds - Google Patents

Description

  The present invention relates to a novel methine 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 having poor solubility in a solvent to obtain solubility in the solvent. However, since it is affected by the introduced substituent effect, the physical properties are not necessarily the original compounds. Are not necessarily equal.

Methine compounds are widely used as dyes because of their clear hues, high color development, and robustness to light, heat, etc. For various paints, water-based inks, oil-based inks, and inkjets. It is used in a wide range of applications such as inks and color filters. As such a dye, for example, a methine compound represented by the following formula (100) as described in Non-Patent Document 1 is known.
However, as a result of investigations by the present inventors, the methine compound represented by the following formula (100) has insufficient solubility in a solvent such as cyclopentanone or ethyl lactate used in the colored resin composition for color filters. there were.

Dyes and pigments (2007), 74 (2), 306-312

  An object of this invention is to provide the methine compound excellent in solvent solubility, the dye composition containing this methine compound, and the color filter obtained using this dye composition.

  As a result of intensive studies to solve the above problems, the present inventor has found that a novel methine compound having a specific structure is remarkably superior in solvent solubility compared to a conventionally known methine dye (compound). The invention has been completed.

That is, the present invention
(1) The following formula (1)

(In the formula (1), A represents an alkyl group having 1 to 4 carbon atoms, R ^{1 to} R ³ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. X represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms, and Z represents an alkylene group having 1 to 4 carbon atoms.)
A methine compound represented by
(2) The methine compound according to item (1), wherein A in formula (1) is a methyl group,
(3) The methine compound according to the above item (1), wherein R ^{1 to} R ³ in formula (1) are each independently a hydrogen atom or an alkoxy group having 1 to 4 carbon atoms,
(4) The methine compound according to item (3), wherein R ^{1 to} R ³ in formula (1) are hydrogen atoms,
(5) The methine compound according to item (1), wherein X in formula (1) is a chlorine atom,
(6) The methine compound according to item (1), wherein Z in formula (1) is an n-propylene group,
(7) An oil-based dye composition comprising the methine compound according to any one of (1) to (6) and an oil-soluble organic solvent,
(8) An aqueous dye composition containing the methine compound according to any one of (1) to (6) and an aqueous medium,
(9) Printed matter obtained using the oil-based dye composition according to (7) or the aqueous dye composition according to (8)
(10) A color filter obtained using the oil-based dye composition according to (7) or the aqueous dye composition according to (8) above,
About.

  The methine 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 solvent solubility.

The methine compound of the present invention is represented by the formula (1).
In formula (1), A represents an alkyl group having 1 to 4 carbon atoms, and the alkyl group having 1 to 4 carbon atoms is linear or branched as long as the alkyl group has 1 to 4 carbon atoms. Is not limited. The alkyl group may have a substituent.
Specific examples of the alkyl group having 1 to 4 carbon atoms represented by A in the formula (1) include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec- A butyl group and t-butyl group are mentioned.

Examples of the substituent that the alkyl group represented by A in Formula (1) may have include, for example, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), hydroxy group, 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.), carboxyl group, amide group (for example, acetamide group etc.), sulfonamide Group (for example, methanesulfonamide group, ethanesulfonamide group, propanesulfonamide group, etc.) and sulfo group.
A in Formula (1) is preferably a linear alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and still more preferably a methyl group.

In formula (1), R < ¹ > -R < ³ > represents a hydrogen atom, a halogen atom, a C1-C4 alkyl group, or a C1-C4 alkoxy group each independently.
The alkyl group having 1 to 4 carbon atoms represented by R ^{1 to} R ³ in Formula (1) is the same as that described in the section for the alkyl group having 1 to 4 carbon atoms represented by A in Formula (1).
The alkyl group having 1 to 4 carbon atoms represented by R ^{1 to} R ^{3 in} Formula (1) may have a substituent, and examples of the substituent that may be included include A in Formula (1). This is the same as that described in the section of the substituent that the alkyl group represented may have.
Specific examples of the halogen atom represented by R ^{1 to} R ^{3 in} Formula (1) and the alkoxy group having 1 to 4 carbon atoms are the substituents that the alkyl group represented by A in Formula (1) may have. This is the same as described in the section of halogen atom and alkoxy group.
R ^{1 to} R ³ in Formula (1) are each independently preferably a hydrogen atom or an alkoxy group having 1 to 4 carbon atoms, and all of R ^{1 to} R ³ are hydrogen atoms, or R ¹ and More preferably, R ³ is an alkoxy group having 1 to 4 carbon atoms and the others are hydrogen atoms, and all of R ^{1 to} R ³ are hydrogen atoms, or R ¹ and / or R ³ are carbon atoms. It is more preferable that the alkoxy group has 1 or 2 and the others are hydrogen atoms, and it is particularly preferable that all are hydrogen atoms.

In formula (1), X represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.
Specific examples of the halogen atom represented by X in the formula (1) are the same as those described in the section of the halogen atom as a substituent that the alkyl group represented by A in the formula (1) may have.
The alkyl group having 1 to 4 carbon atoms represented by X in the formula (1) is the same as that described in the section of the alkyl group having 1 to 4 carbon atoms represented by A in the formula (1).
X in the formula (1) is preferably a halogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a halogen atom, still more preferably a chlorine atom or a bromine atom, It is particularly preferred.

  In formula (1), Z represents an alkylene group having 1 to 4 carbon atoms, and if the alkylene group having 1 to 4 carbon atoms is an alkylene group having 1 to 4 carbon atoms, it is linear or has a side chain. Although not limited to any of these, a linear alkylene group having 1 to 4 carbon atoms (methylene group, ethylene group, n-propylene group, and n-butylene group) is preferable, and a straight chain carbon group having 1 to 3 carbon atoms. An alkylene group is more preferable, and an n-propylene group is still more preferable.

As the methine compound represented by the formula (1) of the present invention, a compound in which preferable ones are combined for each of the above A, X, Z, R ¹ , R ² and R ³ is preferable, and a more preferable one is combined. Compounds are more preferred. The same applies to combinations of preferable and more preferable ones.

The methine compound represented by the formula (1) of the present invention is produced by various methods. For example, a standard method is described with reference to the methods described in Dies and pigments (2007), 74 (2), 306-312. It can be obtained by reacting a formyl derivative represented by the following formula (AA), which is also available as a commercial product, with an aniline derivative represented by the following formula (B) in acetic acid. In the following formulas (AA) to (B), A, X, Z, R ¹ , R ² and R ³ each have the same meaning as in the above formula (1).

  Specific examples of the methine compound represented by the above formula (1) are shown below, but the present invention is not limited to these specific examples.

  The oily or aqueous dye composition of the present invention contains a methine 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 methine 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 methine 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, tetrafluoropropanol and diacetone alcohol; ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether , Glycol derivatives such as propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol diacetate; methyl ethyl ketone, cyclo Such as pentanone and cyclohexanone Tons; ethers such as butyl phenyl ether, benzyl ether, hexyl ether; esters such as ethyl acetate, butyl acetate, ethyl benzoate, butyl benzoate, ethyl laurate, butyl laurate; acetonitrile, DMF, dimethyl sulfoxide, Examples include polar organic solvents such as sulfolane, NMP, and 2-pyrrolidone. These solvents may be used alone or in admixture of two or more.

  The aqueous dye composition of the present invention can be prepared by dissolving or dispersing the methine 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 methine 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.

  When using the dye composition of this invention for a color filter use, it is preferable to use an organic pigment together. Specific examples of organic pigments that can be used in combination include C.I. I. Pigment Red 2, 5, 17, 31, 32, 41, 122, 123, 144, 149, 166, 168, 170, 171, 175, 176, 177, 178, 179, 180, 185, 187, 202, 206, Red pigments such as C. 207, 209, 214, 220, 221, 224, 242, 243, 254, 255, 262, 264, 272; I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214, etc., yellow pigments, C.I. I. Orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73. C. I. And green pigments such as CI Pigment Green 7, 36, and 58. Of these, the red color filter is C.I. I. Pigment red 177, C.I. I. Pigment red 242, C.I. I. Pigment red 254, C.I. I. Pigment yellow 138 and C.I. I. Preferably, at least one selected from the group consisting of CI Pigment Yellow 150 is used in combination. Pigment Green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 58, C.I. I. Pigment yellow 138 and C.I. I. It is preferable to use at least one selected from the group consisting of CI Pigment Yellow 150.

  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 methine 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 methine 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, based on the methine 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 methine compound represented by the formula (1) and the coloring material used in combination.

  Examples of the method for finely dispersing the methine 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 and an oligomer having an ethylenic unsaturated group, and when the binder resin is polymerizable, a polymerization initiator or a curing agent may be used in combination. More preferred. When the dye composition of the present invention is used for a color filter, it is common to use a compound (resin component) that is usually cured by heat and / or light, and after applying a photolithography technique, if necessary, A cured product cured by light and / or heat is used as a color filter. The binder resin is usually used in an amount of 10000% by mass or less based on the methine 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 methine compound represented by the formula (1) 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 The present invention will be described more specifically with reference to examples. However, the present invention is not limited to the examples. Unless otherwise specified, “part” and “%” in the text are based on mass, and the reaction temperature is the internal temperature. Among the synthesized compounds, those measured for λmax (maximum absorption wavelength) were measured by a diode array detector of Agilent 1100 Series HPLC System, manufactured by Agilent Technology. As a mobile phase for measurement, a 5 mM ammonium acetate aqueous solution / acetonitrile solvent system was used.

Example 1
2. 2.0 parts of a formyl derivative represented by the following formula (2) in 20 parts of acetic acid, 3- (2-amino-4-chlorophenoxy) propane-1-sulfonic acid represented by the following formula (3) The liquid obtained by adding 0 part and stirring at 40 degreeC for 6 hours is cooled to room temperature, Then, it pours into 50 parts of water, and after stirring for 30 minutes, the precipitated solid is separated by filtration, dried after washing with water. As a result, No. of the above specific example. As a result, 1.9 parts of a methine compound (λmax: 435 nm) represented by 1 was obtained.

Synthesis example 1
In the same manner as in Example 1 except that 3.0 parts of the compound represented by the formula (3) were changed to 1.9 parts of the compound represented by the following formula (4), the compound represented by the above formula (100) was used. 1.4 parts of a comparative methine compound (λmax: 422 nm) was obtained.

Example 2 (Preparation of oil-based dye composition)
After mixing 20 mg of the methine compound obtained in Example 1 and 980 mg of cyclopentanone in a 20 mL sample tube, the mixture was shaken with an ultrasonic shaker at room temperature for 5 minutes, and the concentration of the methine compound of 2% according to the present invention. Oil-based dye composition 1 was prepared. In the obtained oil dye composition 1, no visual residual was confirmed.

Example 3
An oily dye composition 2 of the present invention was prepared according to Example 2 except that cyclopentanone was changed to ethyl lactate. In the obtained oily dye composition 2, no visual residual was confirmed.

Comparative Example 1
A comparative oil-based dye composition 1 was prepared according to Example 2 except that the methine compound obtained in Example 1 was changed to the comparative methine compound obtained in Synthesis Example 1. The obtained oil dye composition 1 was confirmed to have a visual residual.

Comparative Example 2
A comparative oil dye composition 2 was prepared according to Example 3 except that the methine compound obtained in Example 1 was changed to the comparative methine compound obtained in Synthesis Example 1. The obtained oil dye composition 2 was confirmed to have a visual difference.

  From the examples and comparative examples, it is clear that the methine compound represented by the formula (1) of the present invention is excellent in solubility in an oil-soluble organic solvent.

The methine compound of the present invention has high solubility in an oil-soluble organic solvent and is easy to handle. Therefore, the methine compound of the present invention can be used for dye-colored bodies and can be used for a wide range of applications such as color filter inks and inkjet inks.

Claims (10)

Following formula (1)

(In the formula (1), A represents an alkyl group having 1 to 4 carbon atoms, R ^{1 to} R ³ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. X represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms, and Z represents an alkylene group having 1 to 4 carbon atoms.)
A methine compound represented by: The methine compound according to claim 1, wherein A in the formula (1) is a methyl group. The methine compound according to claim 1, wherein R ^{1 to} R ³ in formula (1) are each independently a hydrogen atom or an alkoxy group having 1 to 4 carbon atoms. The methine compound according to claim 3, wherein R ^{1 to} R ³ in the formula (1) are hydrogen atoms. The methine compound according to claim 1, wherein X in the formula (1) is a chlorine atom. The methine compound according to claim 1, wherein Z in the formula (1) is an n-propylene group. The oil-based dye composition containing the methine compound as described in any one of Claims 1 thru | or 6, and an oil-soluble organic solvent. An aqueous dye composition comprising the methine compound according to any one of claims 1 to 6 and an aqueous medium. A printed matter obtained using the oil-based dye composition according to claim 7 or the aqueous dye composition according to claim 8. A color filter obtained by using the oil-based dye composition according to claim 7 or the aqueous dye composition according to claim 8.