JP2016160411A - Azo compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an azo compound having excellent solubility and an oily or aqueous dye composition thereof.SOLUTION: The present invention provides an azo compound represented by formula (1) (Ris H, a halogen atom, an aryl group, a C1-4 alkyl group or the like; Ris a C1-4 alkyl group; Ris H, an amino group or a C1-4 alkyl group; Ris H, a halogen atom, a nitro group, an aryl group or a C1-4 alkyl group; M is Cr or Co; Ris a C1-28 alkyl group; m is an integer of 1-4; x and y are an integer of 1-24; 3≤x+y≤25).SELECTED DRAWING: None

Description

  The present invention relates to a novel azo compound.

  C. I. Acid Yellow 59 is used as a yellow dye in a wide range of applications such as various paints, fiber materials, water-based inks, oil-based inks, and inkjet inks.

  Patent Document 1 discloses C.I. I. Although there is a description of azo compounds such as Acid Yellow 59, C.I. I. Azo compounds such as Acid Yellow 59 have insufficient solubility alone.

Japanese Patent Laid-Open No. 03-056570

  An object of the present invention is to provide a novel azo compound excellent in solubility in a solvent and a dye composition using the compound as a dye.

  As a result of intensive studies to solve the above problems, the present inventors have found that azo compounds having a specific structure have higher solubility in oil-soluble organic solvents and aqueous media than conventionally known azo compounds. The headline and the present invention have been completed.

That is, the present invention
(1) An azo compound represented by the following formula (1)

(In formula (1), each R ¹ independently represents a hydrogen atom, a halogen atom, a nitro group, an aryl group, a sulfonamide group, a carboxyl group, an alkyl group having 1 to 4 carbon atoms, —SO ₂ NHR ² or —COOR ^2. R ² independently represents an alkyl group having 1 to 4 carbon atoms, R ³ independently represents a hydrogen atom, an amino group, or an alkyl group having 1 to 4 carbon atoms, and R ⁴ represents independently hydrogen. Represents an atom, a halogen atom, a nitro group, an aryl group, an alkyl group having 1 to 4 carbon atoms, —SO ₂ NHR ⁵ or —COOR ^5. R ⁵ represents a hydrogen atom, monovalent aliphatic carbonization having 1 to 8 carbon atoms. hydrogen group, a cyclohexyl group, an alkyl cyclohexyl group having a carbon number of 1 to 4 alkyl moiety, an alkoxyalkyl group of 2 to 15 carbon ^{atoms, -R 6 -CO-O-R} 7, -R 6 -O-CO-R ⁷ or an aralkyl group having 7 to 10 carbon atoms, when a plurality of R ⁵ are present, each R ⁵ may be the same as or different from each other, and R ⁶ is 1 to 8 carbon atoms. In the case where a plurality of R ⁶ are present, each R ⁶ may be the same as or different from each other, and R ⁷ is a monovalent aliphatic carbon having 1 to 8 carbon atoms. If .R ⁷ representing a hydrogen group there are multiple, each of R ⁷ may be the same or different from one another .M is .R ⁸ representing the Cr or Co represents an alkyl group having 1 to 28 carbon atoms. m independently represents an integer of 1 to 4. x and y each independently represents an integer of 1 to 24 and satisfies the condition of 3 ≦ x + y ≦ 25.
(2) The azo compound according to item (1), wherein R ¹ in formula (1) is a hydrogen atom,
(3) The azo compound according to the above item (1) or (2), wherein R ² in formula (1) is an alkyl group having 1 to 4 carbon atoms,
(4) The azo compound according to any one of (1) to (3), wherein R ³ and R ⁴ in formula (1) are hydrogen atoms,
(5) The azo compound according to any one of (1) to (4), wherein M in Formula (1) is Cr;
(6) The azo compound according to any one of (1) to (5), wherein R ⁸ in formula (1) is an alkyl group having 8 to 16 carbon atoms,
(7) The azo compound according to any one of (1) to (6), wherein x and y in the formula (1) satisfy a condition of 3 ≦ x + y ≦ 20,
(8) An oil-based dye composition comprising the compound according to any one of (1) to (7) and an oil-soluble organic solvent,
(9) An aqueous dye composition comprising the compound according to any one of (1) to (7) and an aqueous medium,
About.

  The azo compound of the present invention exhibits characteristics excellent in solubility in oil-soluble organic solvents and aqueous media as compared with conventionally known azo compounds, and also has characteristics excellent in heat resistance. That is, by using the azo compound of the present invention, an oil-based dye composition and an aqueous dye composition having a higher dye concentration can be prepared, and can be used for a wide range of applications such as inkjet inks.

The azo compound of the present invention is represented by the formula (1).
In formula (1), each R ¹ independently represents a hydrogen atom, a halogen atom, a nitro group, an aryl group, a sulfonamide group, a carboxyl group, an alkyl group having 1 to 4 carbon atoms, —SO ₂ NHR ² or —COOR ² . Represent. R ² independently represents an alkyl group having 1 to 4 carbon atoms.
Examples of the halogen atom represented by R ^{1 in the} formula (1) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the aryl group represented by R ^{1 in the} formula (1) include a phenyl group and a naphthyl group, and the aryl group may have a substituent. Examples of the substituent which may have include, for example, a halogen atom (fluorine atom, chlorine atom, bromine atom and iodine atom), an alkoxy group (for example, methoxy group, ethoxy group, iso-butoxy group, etc.) 4 alkoxy groups), cyano groups and nitro groups.

The alkyl group having 1 to 4 carbon atoms represented by R ^{1 in the} formula (1) is not limited to a straight chain or branched chain as long as it has 1 to 4 carbon atoms. The alkyl group may have a substituent.
Specific examples of the alkyl group having 1 to 4 carbon atoms represented by R ^{1 in the} formula (1) include methyl group, ethyl group, n-propyl group, n-butyl group, iso-propyl group, iso-butyl group, sec -A butyl group and a tert- butyl group are mentioned.
Examples of the substituent that the alkyl group having 1 to 4 carbon atoms represented by R ^{1 in} Formula (1) may have include the substituent that the aryl group represented by R ^{1 in} Formula (1) may have. The same thing is mentioned.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ² in the formula (1) include the same as the alkyl group having 1 to 4 carbon atoms represented by R ^{1 in} the formula (1). In addition, the alkyl group may have a substituent, and the substituent that may be included is the same as the substituent that the aryl group represented by R ^{1 in} Formula (1) may have. Can be mentioned.
R ² in formula (1) is preferably a methyl group, an ethyl group, an n-propyl group or an n-butyl group, more preferably a methyl group, an ethyl group or an n-butyl group, and a methyl group Alternatively, an ethyl group is more preferable, and a methyl group is particularly preferable.

R ¹ in Formula (1) is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or —SO ₂ NHR ² , and is a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or n-butyl. Or —SO ₂ NHR ² , wherein R ² is more preferably a methyl group, an ethyl group, an n-propyl group or an n-butyl group, and a hydrogen atom, a methyl group, an ethyl group, an n-butyl group or —SO ₂ NHR ² , wherein R ² is preferably a methyl group, an ethyl group or an n-butyl group, is a hydrogen atom, a methyl group, an ethyl group or —SO ₂ NHR ² , wherein R ² is A methyl group or an ethyl group is particularly preferable, and a hydrogen atom is most preferable.

In formula (1), each R ³ independently represents a hydrogen atom, an amino group or an alkyl group having 1 to 4 carbon atoms.
Examples of the amino group represented by R ^{3 in the} formula (1) include an amino group, a mono- or dialkyl-substituted amino group, a mono- or diaryl-substituted amino group, and a monoalkylmonoaryl-substituted amino group. Examples of the alkyl group in these substituted amino groups include those similar to the alkyl group having 1 to 4 carbon atoms represented by R ¹ , and examples of the aryl group in these substituted amino groups are the same as those of the aryl group represented by R ¹ . Things. The alkyl group or aryl group in the substituted amino group may have a substituent, and the substituent that may have may be the aryl group represented by R ^{1 in} Formula (1). The thing similar to a good substituent is mentioned.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ^{3 in the} formula (1) include the same as the alkyl group having 1 to 4 carbon atoms represented by R ¹ . In addition, the alkyl group may have a substituent, and the substituent that may be included is the same as the substituent that the aryl group represented by R ^{1 in} Formula (1) may have. Can be mentioned.
R ³ in Formula (1) is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an n-butyl group. A hydrogen atom, a methyl group, an ethyl group or an n-butyl group is more preferable, a hydrogen atom, a methyl group or an ethyl group is particularly preferable, and a hydrogen atom is most preferable.

In formula (1), R ⁴ each independently represents a hydrogen atom, a halogen atom, a nitro group, an aryl group, an alkyl group having 1 to 4 carbon atoms, —SO ₂ NHR ⁵ or —COOR ⁵ . R ⁵ is a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a cyclohexyl group, an alkylcyclohexyl group having 1 to 4 carbon atoms in the alkyl portion, an alkoxyalkyl group having 2 to 15 carbon atoms, -R ^6- CO—O—R ⁷ , —R ⁶ —O—CO—R ⁷ or an aralkyl group having 7 to 10 carbon atoms is represented. When a plurality of R ⁵ are present, each R ⁵ may be the same as or different from each other. R ⁶ represents a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms. When a plurality of R ⁶ are present, each R ⁶ may be the same as or different from each other. R ⁷ represents a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms. When a plurality of R ⁷ are present, each R ⁷ may be the same as or different from each other.
Examples of the halogen atom represented by R ^{4 in} Formula (1) include the same halogen atoms as those represented by R ¹ .

Examples of the aryl group represented by R ^{4 in} Formula (1) include the same aryl groups as represented by R ¹ . The aryl group may have a substituent, and the substituent that may be included is the same as the substituent that the aryl group represented by R ^{1 in} Formula (1) may have. Is mentioned.
Examples of the alkyl group having 1 to 4 carbon atoms represented by R ^{4 in the} formula (1) include the same alkyl groups as represented by R ¹ . In addition, the alkyl group may have a substituent, and the substituent that may be included is the same as the substituent that the aryl group represented by R ^{1 in} Formula (1) may have. Can be mentioned.

The monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms represented by R ^{5 in the} formula (1) is not limited to a straight chain or branched chain as long as it has 1 to 8 carbon atoms. Further, the aliphatic hydrocarbon group may have a substituent.
Specific examples of the monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms represented by R ^{5 in the} formula (1) include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, Examples include n-hexyl group, n-heptyl group, n-octyl group, iso-propyl group, iso-butyl group, sec-butyl group and tert-butyl group.
As the substituent that the monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms represented by R ⁵ in Formula (1) may have, the aryl group represented by R ^{1 in} Formula (1) has The thing similar to the substituent which may be mentioned is mentioned.

The monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms represented by R ^{5 in the} formula (1) is preferably an alkyl group having 1 to 6 carbon atoms, and is an alkyl group having 1 to 4 carbon atoms. It is more preferable. In addition, the monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms represented by R ⁵ is preferably a straight-chain group. That is, the monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms represented by R ⁵ is particularly preferably a methyl group, an ethyl group, an n-propyl group, or n-butyl.

Specific examples of the alkyl cyclohexyl group having 1 to 4 carbon atoms in the alkyl moiety represented by R ⁵ of formula (1), 2-methylcyclohexyl group, 2-ethyl-cyclohexyl group, 2-n-propyl cyclohexyl group, 2-isopropyl Examples include cyclohexyl group, 2-n-butylcyclohexyl group, 4-methylcyclohexyl group, 4-ethylcyclohexyl group, 4-n-propylcyclohexyl group, 4-isopropylcyclohexyl group and 4-n-butylcyclohexyl group.

Specific examples of the alkoxyalkyl group having 2 to 15 carbon atoms represented by R ^{5 in the} formula (1) include methoxymethyl group, methoxyethyl group, methoxy-n-propyl group, methoxy-n-butyl group, methoxy-n- Pentyl group, 1-ethoxy-n-propyl group, 2-ethoxy-n-propyl group, 1-ethoxy-isopropyl group, 2-ethoxy-isopropyl group, 1-isopropoxy-n-propyl group, 2-isopropoxy- n-propyl group, 1-isopropoxy-isopropyl group, 2-isopropoxy-isopropyl group, octyloxy-n-propyl group, 3-ethoxy-n-propyl group, 3- (2-ethylhexyloxy) propyl group, etc. 1-ethoxy-n-propyl group, octyloxy-n-propyl group, 3-ethoxy-n-propyl group or A 3- (2-ethylhexyloxy) propyl group or the like is preferable.

The divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms represented by R ^{6 in the} formula (1) is not limited to a straight chain or branched chain as long as it has 1 to 8 carbon atoms. Further, the aliphatic hydrocarbon group may have a substituent.
Specific examples of the divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms represented by R ^{6 in the} formula (1) include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, Examples include n-hexylene group, n-heptylene group, n-octylene group, iso-propylene group, iso-butylene group, sec-butylene group and tert-butylene group.
As the substituent that the divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms represented by R ⁶ in Formula (1) may have, the aryl group represented by R ^{1 in} Formula (1) has The thing similar to the substituent which may be mentioned is mentioned.

The divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms represented by R ^{6 in the} formula (1) is preferably an alkylene group having 1 to 6 carbon atoms, and an alkylene group having 1 to 4 carbon atoms. It is more preferable. The divalent aliphatic hydrocarbon group having a carbon number of 1 to 8 R ⁶ represents a straight chain. That is, the divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms represented by R ⁶ is particularly preferably a methylene group, an ethylene group, an n-propylene group or an n-butylene, and a methylene group or an ethylene group. Most preferably it is.

Examples of the monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms represented by R ^{7 in the} formula (1) include the same monovalent aliphatic hydrocarbon groups having 1 to 8 carbon atoms represented by R ^5. It is done.
The monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms represented by R ⁷ is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. In addition, the monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms represented by R ⁷ is preferably a straight chain.

R ⁴ in formula (1) is preferably each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and each independently represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or n-butyl. It is more preferably a group and even more preferably a hydrogen atom.

  In formula (1), M represents Cr (chromium) or Co (cobalt), and is preferably Cr.

In formula (1), R ⁸ represents an alkyl group having 1 to 28 carbon atoms. The alkyl group having 1 to 28 carbon atoms represented by R ⁸ is not limited to a straight chain or branched chain as long as it has 1 to 28 carbon atoms. The alkyl group may have a substituent. Examples of the alkyl group having 1 to 28 carbon atoms represented by R ⁸ include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, and an n-octyl group. N-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-heptadecyl group, n-icosyl group, iso-propyl group, iso-butyl group , Sec-butyl group, tert-butyl group and the like. Examples of the substituent that the alkyl group having 1 to 28 carbon atoms represented by R ^{8 in} Formula (1) may have include the substituent that the aryl group represented by R ^{1 in} Formula (1) may have. The same thing is mentioned.

R ⁸ in the formula (1) is a linear alkyl group having 8 to 16 carbon atoms (n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group). Group, n-tetradecyl group, n-pentadecyl group or n-hexadecyl group), more preferably a linear alkyl group having 10 to 14 carbon atoms, and a linear alkyl group having 12 carbon atoms. More preferably, it is (n-dodecyl group).

  In the formula (1), each m independently represents an integer of 1 to 4, preferably both are the same integer of 1 to 4, and more preferably both are the same integer of 2 to 4.

In formula (1), x and y each independently represent an integer of 1 to 24 and satisfy the condition of 3 ≦ x + y ≦ 25.
In the formula (1), x and y are preferably each independently an integer of 1 to 14. Further, the total of x + y is preferably 3 to 20, and more preferably 5 to 15.

The azo compound of the present invention can be synthesized, for example, by the following method. In the following formulas (2) to (5), R ^{1 to} R ⁵ represent the same meaning as in the above formula (1).
First, a compound represented by the following formula (2) is diazotized by a conventional method, and the obtained diazo compound and a compound represented by the following formula (3) are subjected to a coupling reaction by a conventional method to obtain the following formula (4) To obtain a compound represented by: Next, a compound represented by the following formula (5) can be synthesized by subjecting the obtained compound of the following formula (4) to a condensation reaction with a corresponding chromium compound. Finally, the azo compound of the present invention represented by the above formula (1) can be obtained by reacting the compound represented by the following formula (5) with a desired alkylene oxide-added monoalkylamine compound.

  Specific examples of the azo compound represented by the above formula (1) are shown below, but the present invention is not limited thereto.

  The oily or aqueous dye composition of the present invention contains an azo 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 azo 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. It is -30 mass%, More preferably, it is 2.0-20 mass%.

  The oil-based dye composition of the present invention can be prepared by dissolving or dispersing the azo 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 and propylene glycol diacetate; methyl ethyl ketone, cyclopentanone and cyclohexanone Ketones such as butyl Ethers such as phenyl ether, benzyl ether and hexyl ether; ethyl acetate, butyl acetate, isobutyl acetate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, butyl pyruvate, ethyl benzoate, butyl benzoate, methyl lactate And esters such as ethyl lactate, ethyl laurate and butyl laurate; polar organic solvents such as acetonitrile, N, N-dimethylformamide, dimethyl sulfoxide, sulfolane, N-methyl-2-pyrrolidone and 2-pyrrolidone . 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 azo compound represented by the formula (1) of the present invention in an aqueous medium. Examples of the aqueous medium used include water and water-soluble organic solvents. Examples of the water-soluble organic solvent include alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol, diacetone alcohol, and benzyl alcohol; ethylene glycol, diethylene glycol, triethylene glycol, propylene Polyhydric alcohols such as glycol, polyethylene glycol, 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, triethylene glycol monoethyl ether, triethylene group Glycol derivatives such as coal monobutyl ether and dipropylene glycol monomethyl ether; amines such as ethanolamine, diethanolamine, triethanolamine and morpholine; 2-pyrrolidone, N-methyl-2-pyrrolidone and 1,3-dimethyl-imidazolidinone Etc. These solvents may be used alone or in combination of two or more.

  In the oily or aqueous dye composition of the present invention, a coloring material other than the azo 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 as long as the solubility or dispersibility in the oil-soluble organic solvent and the aqueous medium is not impaired, and is represented by the formula (1). The amount of azo compound is usually 15% by mass or less, preferably 5 to 10% by mass.

  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 compound represented by the formula (1).

  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 Known anionic surfactants such as ammonium salts of oxyethylene alkyl ether sulfates, ammonium salts of polyoxyethylene alkyl phenyl ether sulfates and polyoxyalkyl ether phosphates, vinyl naphthalene derivatives, α, β-ethylenically unsaturated carboxylic acids Aliphatic alcohol esters such as styrene, styrene derivatives, acrylic acid, acrylic acid derivatives, methacrylic acid, methacrylic acid derivatives, maleic acid, maleic acid derivatives, maleic anhydride, none Block copolymers consisting of at least two monomers selected from hydromaleic acid derivatives, itaconic acid, itaconic acid derivatives, fumaric acid and fumaric acid derivatives, or random copolymers, or salts thereof Polymer dispersants and the like, and one or more of these are usually 500% by mass or less, preferably 10 to 450% by mass, based on the compound represented by the formula (1) and the color material used in combination as necessary. More preferably 100 to 400% by mass is used.

  As the dispersant used in the aqueous dye composition, in addition to the surfactant, a dispersant conventionally 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 copolymer, styrene-methacrylic acid-acrylic acid ester copolymer Styrene-acrylic resins such as styrene-α-methylstyrene-acrylic acid copolymer, styrene-α-methylstyrene-acrylic acid-acrylic acid ester copolymer, styrene-maleic acid copolymer, styrene-maleic anhydride Acid copolymer, isobutylene-maleic acid resin, rosin modification 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 copolymers such as vinyl acetate-crotonic acid copolymer, vinyl acetate-acrylic acid copolymer, and salts thereof. A dispersing agent is 500 mass% or less normally with respect to the compound represented by Formula (1), and the coloring material used together as needed, Preferably it is 10-450 mass%, More preferably, 100-400 mass% is used.

  Examples of the method for dispersing the azo compound represented by the formula (1) in the form of fine particles include a method using a sand mill (bead mill), a roll mill, a ball mill, a paint shaker, an ultrasonic disperser, or a microfluidizer. 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 use beads having a small diameter or to increase the filling efficiency of the beads such as increasing the filling rate of the 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. Further, when the binder resin has polymerizability, it is more preferable to further use a polymerization initiator, a curing agent and the like. The binder resin is usually used in an amount of 10,000% by mass or less based on the azo 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 azo compound represented by the formula (1) of the present invention is used in various paints, water-based inks, oil-based inks, ink-jet inks and the like as oil-based dye compositions or water-based dye 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 of the alkylene oxide-added monoalkylamine compound to be reacted with the azo compound represented by the formula (1) of the present invention include Esomine C / 15 (manufactured by Lion Corporation), Esomine C / 25 (manufactured by Lion Corporation), Amit 102 (manufactured by Kao Corporation), Amit 105 (manufactured by Kao Corporation), Amit 302 (manufactured by Kao Corporation), Amit 320 (manufactured by Kao Corporation), Nymene L207 (manufactured by NOF Corporation), Naimene F202 (manufactured by NOF Corporation), Naimine F215 (manufactured by NOF Corporation), Genamine C200 (manufactured by Clariant), Genamine C050 (manufactured by Clariant), MazeenC-15 (manufactured by BASF), 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 of the compound obtained by synthesis was measured with a spectrophotometer “UV-3150 manufactured by Shimadzu Corporation”.

Example 1 (Synthesis of the azo compound of the above specific example compound No. 1)
(Process 1)
After adding 20 parts of anthranilic acid to 140 parts of water, a 25% aqueous sodium hydroxide solution was added to obtain an aqueous solution having a pH of 7.5 to 8.0. After adding 38 parts of 35% hydrochloric acid to this aqueous solution, the temperature was adjusted to 5 to 10 ° C. with an ice bath, and 26.4 parts of 40% sodium nitrite aqueous solution was added and reacted at the same temperature for about 30 minutes. Thereafter, 2.1 parts of sulfamic acid was further added and stirred for 5 minutes to obtain a diazo reaction solution.
On the other hand, after adding 21.2 parts of 3-methyl-1-phenylpyrazolone to 120 parts of water, a 25% aqueous sodium hydroxide solution was added to obtain an aqueous solution having a pH of 8.5 to 9.0. The aqueous solution was adjusted to 5-10 ° C. in an ice bath, and 25% aqueous sodium hydroxide solution was added as needed to maintain the pH at 8.5-9.0 and the temperature at 5-10 ° C. as described above. The diazo reaction liquid was added dropwise over 15 minutes, and the reaction was further continued for 3 hours while maintaining the pH at 8.5 to 9.0 and the temperature at 5 to 10 ° C. After completion of the reaction, the precipitated solid was collected by filtration and dried to obtain 39 parts of a compound represented by the following formula (7) as a powder.

(Process 2)
To 380 parts of N-methyl-2-pyrrolidone, add 36.1 parts of chromium potassium sulfate dodecahydrate and 11.8 parts of sodium acetate and add about 4 at 110 to 120 ° C. After reacting for a period of time, the mixture was cooled to 20 to 30 ° C., and insoluble matters were removed by filtration to obtain a filtrate. To the obtained filtrate, 960 parts of water and 96.3 parts of 25% aqueous sodium hydroxide solution were added and stirred for 1 hour. Thereafter, 1.4 parts of 25% saline was added, and the precipitated solid was filtered to obtain 25.8 parts of a compound represented by the following formula (8) as a wet cake.

(Process 3)
The entire amount of the wet cake obtained in Step 2 was dissolved in 81 parts of N-methyl-2-pyrrolidone, and the insoluble material was removed by filtration. To the obtained filtrate, 144 parts of water and 9.2 parts of 35% hydrochloric acid were added to adjust the pH to 1-2, followed by stirring for 1 hour. The total amount of the wet cake obtained by filtering the precipitated solid is suspended again in 83 parts of water and stirred for 1 hour, and then the filtration fractionation is repeated twice and dried to be expressed by the following formula (9). 14.6 parts of an azo compound were obtained.

(Process 4)
By mixing 6.9 parts of the azo compound obtained in Step 3 and 4.3 parts of Esomine C15 (manufactured by Lion Corporation) with 100.7 parts of propylene glycol monomethyl ether acetate (PGMEA), the above compound No. 1 was prepared. 11.9 parts of 1 PGMEA solution was obtained. The maximum absorption wavelength of the azo compound was 428 nm (ethanol).

Example 2 (Synthesis of Compound No. 2 above)
By mixing 6.9 parts of the azo compound obtained in Step 3 and 8.7 parts of Esomine C25 (manufactured by Lion Corporation) with 140.9 parts of propylene glycol monomethyl ether acetate (PGMEA), PGMEA of the above compound 2 was mixed. 156.5 parts of solution were obtained. The maximum absorption wavelength of the azo compound was 428 nm (ethanol).

Example 3 (Preparation of dye composition and evaluation of compound solubility)
The azo compound represented by the formula (9) obtained in Step 3 of Example 1 and esomine C15 or esomine C25 are dissolved in methanol, propylene glycol monomethyl ether (PGME) or propylene glycol monomethyl ether acetate (PGMEA), respectively. As a result, the above-mentioned specific compound No. 1 and the above specific compound No. 1 2 dye compositions were obtained respectively. At that time, the solubility in methanol, PGMEA and PGMEA was evaluated as follows.
In a 50 ml sample tube, the azo compound represented by the formula (9), the amines and the solvent were mixed, and after sealing the sample tube, the sample tube was vibrated at 25 ° C. for 15 minutes using an ultrasonic vibrator. Next, after standing at room temperature for 30 minutes, suction filtration was performed, and insoluble matters were visually observed. The case where the insoluble matter could not be confirmed was marked with ◯, and the case where the insoluble matter was confirmed was marked with ×. The results are shown in Table 1.

Comparative Example 1
In place of the azo compound represented by formula (9) and amines, C.I. I. According to the description in Example 3, except that Acid Yellow 59 (AY59) was used, C.I. I. The solubility of Acid Yellow 59 (AY59) in methanol, PGME and PGMEA was evaluated. The results are shown in Table 1.

From the above results, the azo compound represented by the formula (1) of the present invention is a known acid dye, C.I. I. It is clear that the solubility is superior to that of Acid Yellow 59.
As described above, it has been clarified that the azo compound represented by the formula (1) of the present invention is excellent in solubility and can be used in applications such as inkjet inks.

The azo compound of the present invention exhibits a property superior in solubility to a conventionally known azo compound. Therefore, the azo compound of the present invention can be used for a wide range of applications such as inkjet inks.

Claims (9)

An azo compound represented by the following formula (1)

(In formula (1), each R ¹ independently represents a hydrogen atom, a halogen atom, a nitro group, an aryl group, a sulfonamide group, a carboxyl group, an alkyl group having 1 to 4 carbon atoms, —SO ₂ NHR ² or —COOR ^2. R ² independently represents an alkyl group having 1 to 4 carbon atoms, R ³ independently represents a hydrogen atom, an amino group, or an alkyl group having 1 to 4 carbon atoms, and R ⁴ represents independently hydrogen. Represents an atom, a halogen atom, a nitro group, an aryl group, an alkyl group having 1 to 4 carbon atoms, —SO ₂ NHR ⁵ or —COOR ^5. R ⁵ represents a hydrogen atom, monovalent aliphatic carbonization having 1 to 8 carbon atoms. hydrogen group, a cyclohexyl group, an alkyl cyclohexyl group having a carbon number of 1 to 4 alkyl moiety, an alkoxyalkyl group of 2 to 15 carbon ^{atoms, -R 6 -CO-O-R} 7, -R 6 -O-CO-R ⁷ or an aralkyl group having 7 to 10 carbon atoms, when a plurality of R ⁵ are present, each R ⁵ may be the same as or different from each other, and R ⁶ is 1 to 8 carbon atoms. In the case where a plurality of R ⁶ are present, each R ⁶ may be the same as or different from each other, and R ⁷ is a monovalent aliphatic carbon having 1 to 8 carbon atoms. If .R ⁷ representing a hydrogen group there are multiple, each of R ⁷ may be the same or different from one another .M is .R ⁸ representing the Cr or Co represents an alkyl group having 1 to 28 carbon atoms. m independently represents an integer of 1 to 4. x and y each independently represents an integer of 1 to 24 and satisfies the condition of 3 ≦ x + y ≦ 25. The azo compound according to claim 1, wherein R ¹ in formula (1) is a hydrogen atom. (3) The azo compound according to claim 1 or 2, wherein R ² in formula (1) is an alkyl group having 1 to 4 carbon atoms. The azo compound according to any one of claims 1 to 3, wherein R ³ and R ⁴ in the formula (1) are hydrogen atoms. The azo compound according to any one of claims 1 to 4, wherein M in the formula (1) is Cr. The azo compound according to any one of claims 1 to 5, wherein R ⁸ in the formula (1) is an alkyl group having 8 to 16 carbon atoms. The azo compound according to any one of claims 1 to 6, wherein x and y in the formula (1) satisfy a condition of 3 ≦ x + y ≦ 20. The oil-based dye composition containing the compound and oil-soluble organic solvent as described in any one of Claims 1 thru | or 7. An aqueous dye composition comprising the compound according to any one of claims 1 to 7 and an aqueous medium.