JP4840838B2 - Organic colorant having metallic luster and use thereof - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an organic colorant having a metallic luster. More specifically, the present invention relates to an organic colorant which can produce a film from a solution and has a metallic luster in the film state and greatly expands the range of use in the conventional dispersion and its use.
[0002]
[Prior art]
As inks having metallic luster, for example, ballpoint pen ink (Patent Document 1) and marking pen ink (Patent Document 2) are known, all of which are obtained by dispersing metal powder or pigment in an organic solvent or an aqueous solution. Various efforts have been made to impart dispersion stability (for example, Patent Document 3). In addition, when metal powder is used, inventions such as addition of arginine to prevent gas generation due to corrosion over time (Patent Document 4) have been made, but as long as brass or aluminum is used, the alteration is stored. Sometimes it is extremely difficult to completely prevent printed matter after use.
[0003]
[Patent Document 1]
Japanese Patent Publication No. 5-43758 [Patent Document 2]
JP-A-9-132747 [Patent Document 3]
Republished No. 98/26014 [Patent Document 4]
Japanese Patent Laid-Open No. 2000-309740
[Problems to be solved by the invention]
The object of the present invention is to provide an organic colorant having a metallic luster at the time of film formation, and there is no change over time such as sedimentation, aggregation, and discoloration during storage, which has often been a problem with conventional metal powders, and the line breaks during use. To provide colorants that do not have to worry about ink clogging.
[0005]
[Means for Solving the Problems]
The colorant obtained by this invention can be easily prepared from a triphenylamine derivative or a trihalogen-substituted benzene derivative, and is stable to light and heat. The compound of the present invention is represented by the following general formula [3] and general formula [4].
General formula [3]
[0006]
[Chemical 3]
[0007]
[ Wherein , A ₁ represents a phenyl residue which may have a methylanilino group, a biphenyl residue, a carbonyl group or a fluorene residue which may have a dicyanomethylene group, or a spirofluorene residue which may have a diphenylamino group. , A bisphenol residue or a triphenylamine residue, X ₁ represents a phenylene group, and R ₁ represents a phenyl group or an alkyl group. n is an integer of 2 or more, X ₁ is may be the same or different. ]
[0008]
[Formula 4]
[0009]
[Wherein, A ₂ represents a phenyl residue which may have a methylanilino group, a biphenyl residue, a carbonyl group or a fluorene residue which may have a dicyanomethylene group, or a spirofluorene residue which may have a diphenylamino group. Represents a bisphenol residue or a triphenylamine residue, X ₂ represents a phenylene group, and R ₂ represents a phenyl group or an alkyl group. n is an integer of 2 or more, X ₂ may be the same or different. ]
Here, a biphenyl residue refers to a compound in which two or more aromatic ring residues are bonded by a single bond, a fluorene residue refers to a compound containing a fluorene ring as part of its structure, and a triphenylamine residue is A compound containing a triphenylamine structure as part of its structure.
[0011]
This compound is composed of tetracyanoethylene and 0 to 140 ° C. in a solvent alone or in a mixture (for example, dimethylformamide, dimethyl sulfoxide, xylene) that dissolves a compound having a basic skeleton such as triphenylamine. Preferably, after reacting at 10 to 80 ° C., extraction and washing can be easily performed and purified by performing treatments such as extraction, washing, and column separation purification.
[0012]
As the skeleton underlying, lifting one Kaori Kowazan based on the aryl amino group as part of the structure, the double ring residue, condensed polycyclic residue, alicyclic residue, spirocyclic residue, bi phenyl residues, off fluorene residue, such as the said dendrimer structure to core the door triphenylamine skeleton, it preferably is compound is suitable which has an easy substitution positions electrophilic substitution, for adjusting the reaction conditions, etc. There are a wide range of compounds that react with.
[0013]
Typical examples of use as a colorant include the case where this compound is dissolved in an organic solvent such as toluene, methyl ethyl ketone, ethyl acetate, dimethylformamide and applied as it is by a technique such as cast, dip, spin coating, and other binders. In some cases, it may be mixed with ingredients and adhered to the object to be coated. The binder component used here includes alkyd melamine resin, acrylic melamine resin, epoxy resin, polyester resin, benzoguanamine resin, etc. used for general paints, modified phenolic resin used for printing ink, petroleum resin, ballpoint pen, etc. Xanthan gum for ink, petroleum resin, and the like are mentioned, and a solvent-soluble resin can be selected from a single type or a combination of several types depending on the object to be coated and the usage form.
[0014]
Further, the compound of the present invention is dispersed in a thermoplastic resin insoluble in a solvent such as polyethylene, polypropylene, polystyrene, and polycarbonate with a mixing device such as a Henschel mixer and a dispersing device such as a biaxial extruder, and then pulverized or thermosetting. There is a form in which the resin precursor, UV curable resin precursor or electron beam curable resin precursor is dispersed and dispersed as a whole and then used as colored particles. In this case, the colored particles are used as a solvent alone or the binder described above. Can be mixed and dispersed with ingredients. The resin in this case may be essentially insoluble in the solvent used, and is not limited to the above exemplary resins.
[0015]
Specific examples of the compounds obtained by the present invention are listed below.
[0016]
[Chemical formula 5]
[0017]
【Example】
The present invention will be specifically described below based on examples, but the compounds are not limited thereto.
[0018]
[Example 1]
Synthesis of N, N'-bis (4-tricyanoethenylphenyl) -N, N'-diphenylbenzidine (compound (1))
(Reaction formula)
[0019]
[Chemical 6]
[0020]
(operation)
Under a nitrogen atmosphere, 0.512 mmol of N, N, N ′, N′-tetraphenylbenze and 0.509 mmol of tetracyanoethylene (TCNE) were dissolved in 2.0 mL of dry DMF and stirred at 80 ° C. for 48 hours. Saturated brine (50 mL) was added, and the mixture was extracted with chloroform (50 mL × 3). The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure, and then purified by column chromatography (silica gel, chloroform) to obtain N, N′-bis (4-tricyanoethenylphenyl) -N, N′-diphenyl bench. Gin (0.0799 g, 0.117 mmol, 23%) (compound (1)) was obtained.
[0021]
[Chemical 7]
[0022]
[0023]
[Chemical 8]
[0024]
[Example 2]
Synthesis of 2,7-bis {N-phenyl-N- [p- (tricyanoethenyl) phenyl] amino} fluorene (compound (2)) (reaction formula)
[0025]
[Chemical 9]
[0026]
(operation)
2,7-bis (diphenylamino) fluorene (0.103 g, 0.200 mmol) and tetracyanoethylene (0.061 g, 0.475 mmol) were dissolved in N, N-dimethylformamide (DMF) (1.0 mL) and dissolved at 80 ° C. Stir for hours.
[0027]
Water (50 mL) was added, and the mixture was extracted with chloroform (30 mL × 3). The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. 2,7-bis {N-phenyl-N- [p- (tricyanoethenyl) phenyl] amino} fluorene (0.0488 g) forming a golden glossy thin film by column chromatography (silica gel, chloroform: hexane = 1: 1) 0.0681 mmol, 34%).
[0028]
[Chemical Formula 10]
[0029]
[Example 3]
Synthesis of 9- (dicyanomethylene) -2,7-bis [{N-phenyl-N- (4-tricyanophenyl)} amino] fluorene (compound (3)) (reaction scheme)
[0030]
Embedded image
[0031]
(operation)
9- (Dicyanomethylene) -2,7-bis (diphenylamino) fluorene (0.159 g, 0.280 mmol) and tetracyanoethylene (0.080 g, 0.560 mmol) in N, N-dimethylformamide (DMF) (1.0 mL) Dissolved and stirred at 80 ° C. for 16 hours.
[0032]
Water (30 mL) was added and extracted with toluene (30 mL × 4). The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. 9- (Dicyanomethylene) -2,7-bis {N-phenyl-N- [p- (tricyanoethenyl) phenyl] amino} fluorene (0.110 g, 0.144) forming a golden glossy thin film by column chromatography (chloroform) mmol, 51%).
[0033]
Embedded image
[0034]
[Example 4]
1,3-bis {[4- (tricyanoethenyl) phenyl] phenylamino} -5- (diphenylamino) benzene (compound (5)) and 1,3,5-tris {[4- (tricyanoethenyl) Synthesis of phenyl] phenylamino} benzene (compound (4))
(Reaction formula)
[0035]
Embedded image
[0036]
(operation)
Under a nitrogen atmosphere, 0.500 mmol of 1,3,5-tris (diphenylamino) benzene and 2.00 mmol of tetracyanoethylene (TCNE) were dissolved in 1.5 mL of dry DMF and stirred at 70 ° C. for 73 hours. Saturated brine (100 mL) was added, and the mixture was extracted with chloroform (100 mL × 3). The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. By purification by column chromatography (silica gel, chloroform), 1,3-bis {[4- (tricyanoethenyl) phenyl] phenylamino} -5- (diphenylamino) benzene (compound (5) 0.0940 mmol (19 %), 1,3,5-tris {[4- (tricyanoethenyl) phenyl] phenylamino} benzene (compound (4)) 0.316 mmol (63%) was obtained.
[0037]
Embedded image
[0038]
[0039]
Embedded image
[0040]
[Example 5]
Synthesis of tris << 4- {N- [4- (tricyanoethenyl) phenyl] phenylamino} phenyl >> amine (compound (6))
(Reaction formula)
[0041]
Embedded image
[0042]
(operation)
Under a nitrogen atmosphere, 1.00 mmol of tris [4- (diphenylamino) phenyl] amine and 3.00 mmol of tetracyanoethylene (TCNE) were dissolved in 4.0 mL of dry DMF and stirred at 80 ° C. for 48 hours.
After completion of the reaction, saturated brine (150 mL) was added, and the mixture was extracted with toluene (100 mL × 3) and chloroform (100 mL × 3). The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. By purification by column chromatography (silica gel, chloroform), tris << 4- {N- [4- (tricyanoethenyl) phenyl] phenylamino} phenyl >> amine [compound (6)] 0.585 mmol (59%), Got.
[0043]
Embedded image
[0044]
[Example 6]
2,2 ', 7,7'-tetrakis {N-phenyl [4- (tricyanoethenyl) phenyl] amino} -9,9'-spirofluorene (compound (7)) and 2- (diphenylamino) -2 Synthesis of ', 7,7'-tris {N-phenyl [4- (tricyanoethenyl) phenyl] amino} -9,9'-spirofluorene (compound (8))
(Reaction formula)
[0045]
Embedded image
[0046]
(operation)
2,2 ', 7,7'-Tetrabromo-9,9'-spirofluorene (0.635 mmol), diphenylamine (2.54 mmol), sodium tert-butoxide (293 mg, 3.05 mmol) in o-xylene (1.0 mL) Suspended and stirred. A solution prepared by dissolving palladium acetate (1.22x10 ^-3 mmol) and tri- (tert-butoxy) phosphine (2.54x10 ^-3 mmol) in o-xylene (1.0 mL) was slowly added dropwise at 120 ° C. For 5 hours. Saturated brine (30 mL) was added, and the mixture was extracted with chloroform (30 mLx3). The organic layer was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, separated by column chromatography (silica gel, chloroform: hexane = 5: 6), and the obtained main product was used as it was in the next reaction.
This product (0.454 mmol) and tetracyanoethylene (1.82 mmol) were dissolved in N, N-dimethylformamide (DMF) (3.0 mL) and stirred at 80 ° C. for 24 hours. Saturated brine (100 mL) was added, and the mixture was extracted with toluene (100 mL × 3). The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was separated by ram chromatography (silica gel, chloroform) to give 2- (diphenylamino) -2 ', 7,7'-tris {N-phenyl [4- (tricyanoethenyl) phenyl] amino} -9 , 9'-Spirofluorene (Compound (8)) (0.154 mmol, 24%) and 2 ', 7,7'-tetrakis {N-phenyl [4- (tricyanoethenyl) phenyl] amino} -9,9' -Spirofluorene (0.174 mmol, 24%) (compound (7)) was obtained.
[0047]
Embedded image
[0048]
[0049]
Embedded image
[0050]
[Example 7]
Synthesis of 2,2-bis- {4- {N-phenyl-N- [p- (tricyanoethenyl) phenyl] amino} phenyl} propane (compound (30)) (reaction scheme)
[0051]
Embedded image
[0052]
(operation)
Dissolve 2,2-bis [4- (diphenylamino) phenyl] propane (0.159 g, 0.280 mmol) and tetracyanoethylene (0.530 g, 0.999 mmol) in N, N-dimethylformamide (DMF) (1.5 mL). The mixture was stirred at 80 ° C. for 20 hours.
[0053]
Water (50 mL) was added and the mixture was extracted with toluene (50 mL × 8). The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. 2,2-bis- {4- {N-phenyl-N- [p- (tricyanoethenyl) phenyl] amino} phenyl} propane (0.612 g, 0.835 mmol) forming a golden glossy thin film by column chromatography (chloroform) , 83%).
[0054]
Embedded image
[0055]
[Example 8]
1,3-bis [N-methyl-p- (tricyanoethenyl) anilino] -5- (N-methylanilino) benzene (32) and 1,3,5, -tris [N-methyl-p- (tricyanoeth Tenyl) anilino] benzene (31)
(Reaction formula)
[0056]
Embedded image
[0057]
(operation)
Under nitrogen atmosphere, 1,3,5-tribromobenzene (5.00 mmol), N-methylaniline (15.5 mmol) and sodium tert-butoxide (18.0 mmol) were suspended in o-xylene (7.0 mL) under anhydrous conditions. , Stirred. A solution prepared by dissolving palladium acetate (4.33x10 ^-3 mmol) and tri- (tert-butoxy) phosphine (1.50x10 ^-2 mmol) in o-xyle (2.0 mL) was slowly added dropwise to the solution at 120 ° C. For 21 hours.
Water (50 mL) was added, and the mixture was extracted with chloroform (50 mLx3). The organic layer was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and washed with methanol. The product obtained here was used for the next reaction as it was.
This product (1.00 mmol) and tetracyanoethylene (3.10 mmol) were dissolved in N, N-dimethylformamide (DMF) (2.0 mL) and stirred at 80 ° C. for 2 hours.
Water (30 mL) was added, followed by extraction with chloroform (30 mL × 3). The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. By separating the residue by column chromatography, 1,3-bis [N-methyl-p- (tricyanoethenyl) anilino] -5- (N-methylanilino) benzene (compound (32) (0.224 mmol), 1,3,5, -Tris [N-methyl-p- (tricyanoethenyl) anilino] benzene (compound (31) (0.0861 mmol) was obtained.
[0058]
Embedded image
[0059]
[0060]
Embedded image
[0061]
The compounds (1) to (8) and (30) to (32) obtained in Examples 1 to 8 were cast from a solution of a solvent capable of dissolving each compound, and had a metallic luster.
[0062]
[Example 9]
The ink obtained by dissolving the compound (1) obtained in Example 1 in a petroleum solvent together with a rosin-modified phenolic resin had adhesion to paper and metal and had a metallic luster. In addition, the paint dissolved in the xylene solution of the alkyd-modified acrylic resin had a sufficient color and color design with adhesion to a plastic film and metal and a metallic luster.
[0063]
[Example 10]
When the compound (2) obtained in Example 2 was dissolved in an alicyclic compound solvent solution of a petroleum-based resin and used as an ink for writing instruments, it was excellent in stability during storage and line drawing stability during writing, and there was no blur. It was.
[0064]
Example 11
When the compound (3) obtained in Example 3 was dissolved in a propylene glycol solution containing xanthan gum and used as an aqueous ballpoint pen ink, it was excellent in storage stability, the drawn line color was gold, and the line blur was There was no.
[0065]
Example 12
Excellent storage stability and printability when the inks used in the applications of Examples 9 to 11 were prepared for the compounds (4) to (8) and (30) to (32) obtained in Examples 4 to 8. Had.
[0066]
Example 13
30% by weight of propylene homopolymer "Hipol J800P"
(MFR: 22, manufactured by Mitsui Petrochemical Industries, Ltd.)
Polypropylene wax “Biscol 330P” 30% by weight
(Number average molecular weight: 15000, manufactured by Sanyo Chemical Industries)
Compound (1) 50% by weight
The above three components were premixed with a Henschel mixer and kneaded using a twin screw extruder PCM-30 (Ikegai Co., Ltd.) at a temperature of 200 ° C. and a rotation speed of 350 rpm to obtain a master batch. This was further put into a resin grinder and pulverized into a powder to obtain a colored powder. This powder became a printing ink having a metallic luster by dispersing three rolls in a resin-type varnish of rosin-modified phenol / petroleum solvent system.
[0067]
【The invention's effect】
According to the present invention, it is possible to easily obtain an ink / paint having a metallic luster that can be used stably over a long period of time without causing a change with time during storage or a problem during use, which would be a problem with a metal powder dispersion. Moreover, this coloring agent can also be used as a dispersion. Accordingly, it is possible to expand the application range of the colorant having a metallic luster that has been limited in the conventional use range.

Claims (5)

A colorant having a metallic luster represented by the following general formula [1].
General formula [1]
[Wherein, A ₁ represents a phenyl residue which may have a methylanilino group, a biphenyl residue, a fluorene residue which may have a carbonyl group or a dicyanomethylene group, and a spirofluorene residue which may have a diphenylamino group. , A bisphenol residue or a triphenylamine residue, X ₁ represents a phenylene group, and R ₁ represents a phenyl group or an alkyl group. n is an integer of 2 or more, X ₁ is may be the same or different. ]   A film-forming material using the substance according to claim 1 as a colorant.   The film-forming material according to claim 2, further comprising a binder component. The film-forming material according to claim 2 or 3, comprising colored particles comprising a colorant and a solvent-insoluble resin. A compound represented by the following general formula [2].
General formula [2]
[Wherein, A ₂ represents a phenyl residue which may have a methylanilino group, a biphenyl residue, a carbonyl group or a fluorene residue which may have a dicyanomethylene group, or a spirofluorene residue which may have a diphenylamino group. Represents a bisphenol residue or a triphenylamine residue, X ₂ represents a phenylene group, and R ₂ represents a phenyl group or an alkyl group. n is an integer of 2 or more, X ₂ may be the same or different. ]