Summary of the invention
The present invention aims to provide one type of new dye composition and can address the above problem.This compounds not only should have improved ozone resistance, also has good water-soluble and the permanent stability in jetting ink simultaneously.
The present invention at first provides one type of black tetrazo sulfoacid compound or its salt, and said compound has the structure of general formula I:
Among the formula I, R
1-R
4Be selected from independently of one another H or-(CH
2)
nX, wherein,
X is-H ,-OH ,-CO
2H or-SO
3H;
N is the integer of 1-12.
The present invention's purpose on the other hand is to provide the preparation method of above-mentioned black tetrazo sulfoacid compound or its salt, comprises the steps:
1) compound ii is soluble in water, add concentrated hydrochloric acid, under the cooling conditions, drip sodium nitrite in aqueous solution, get diazotization solution;
Wherein said compound I I is 2-amino-5-(2-sulfonic acid oxygen ethyl sulfuryl) Phenylsulfonic acid; It and said concentrated hydrochloric acid mol ratio are 1:3-6, with the mol ratio of said Sodium Nitrite be 1:1-1.2;
2) with above-mentioned diazotization solution, under cooling conditions, splash in the aqueous solution of compound III, stirred 2-5 hour, regulating pH then is 3-4, continues reaction 2 hours, obtains red solution; Regulating pH is at 8-10, continues reaction 2-5 hour, obtains dark solution;
Described compound III is 4-amino-5-hydroxyl-naphthalene-2,7-disulfonic acid (being commonly called as H-acid), and the mol ratio of compound III and compound ii is 0.49-0.52:1;
Dark solution is removed remaining inorganic salt through high pressure r-o-nf membrane system, behind the membrane-concentrated, gets intermediate product Dye I-0:
3) intermediate product Dye I-0 and NHR
1R
2And/or NHR
3R
41:2-10 reacts in water according to mol ratio, drips the alkali aqueous solution of cation salt, regulates pH at 4-12, at 30-70 ℃, reaction, through purifying, separate out, drying, obtain the compound or its salt of general formula I.
The purpose of further aspect of the present invention is to provide a kind of composition for ink, and said composition for ink contains the invention described above described black tetrazo sulfoacid compound or its salt.
The present invention also aims to provide the application of combination of inks in spray ink Printing of the invention described above.
The present invention has following beneficial effect:
1) introduces two sulfonic groups on the molecular structure of compound of Formula I, increase the dyestuff dissolubility;
2) sulfonic introducing has reduced the cloud density on the dye matrix molecule, improves ozone resistance;
3) group-NR
1R
2Or-NR
3R
4Introducing, dyestuff is flexible to be increased, and is difficult for crystallization, increases with the avidity of organic wetting Agent for Printing Inks in the ink such as terepthaloyl moietie, glycerols additive, helps promoting the stability of ink, increased simultaneously on printing paper diffusion resistance can and water resistance.
4) group-NR
1R
2Or-NR
3R
4Introducing, make the further increase of dye molecule amount, improved the diffusion resistance of dyestuff on printing paper can and the water resistance of image.
Dye composition of the present invention and composition thereof is high to the solvability of water, permanent stability are high, especially is fit to the desired blackness of spray ink Printing, and the image that the jetting ink that is made into by this dye composition prints is fast light, moisture-proof, ozone proof fastness are excellent.Compound of the present invention and corresponding compositions are suitable for makes the tinting material in many materials, the for example toner of printing ink, coating, lacquer, Laser Printing, marker, paper, fabric, glass, pottery or polymer materials or the like.
Embodiment
Black tetrazo sulfoacid compound of the present invention has the structure of general formula I:
Among the formula I, R
1-R
4Be selected from independently of one another H or-(CH
2)
nX, wherein,
X is-H ,-OH ,-CO
2H or-SO
3H;
N is the integer of 1-12.
In the embodiment, described n is the integer of 1-6.
In another concrete embodiment, described R
1-R
4Be selected from independently of one another-H ,-CH
3,-(CH
2)
2OH ,-(CH
2)
3CO
2H ,-(CH
2)
3SO
3H or-(CH
2)
5CO
2H.Preferred R
1=R
3, be selected from-CH
3,-(CH
2)
2OH ,-(CH
2)
3CO
2H ,-(CH
2)
3SO
3H and-(CH
2)
5CO
2H; More preferably R
2=R
4, be selected from-H ,-CH
3With-(CH
2)
2OH.
Salt described in black tetrazo sulfoacid compound of the present invention or its salt is lithium salts, sodium salt, sylvite, ammonium salt or the organic ammonium salt of corresponding black tetrazo sulfoacid compound; Wherein said organic ammonium salt positively charged ion has N
+R
5R
6R
7R
8Formula, R wherein
5, R
6, R
7And R
8Be selected from independently of one another-H, C
1-18Alkyl, cyclohexyl ,-CH
2CH
2OH, CH (CH
3) CH
2OH and benzyl.
More preferably, described salt be corresponding black tetrazo sulfoacid compound lithium salts, sodium salt, sylvite, ammonium salt, monoethanolamine salt, diethanolamine salt, triethanolamine salt, monoisopropanolamine salt, diisopropanol amine salt or tri-isopropanolamine salt.Wherein most preferably lithium salts, sodium salt, sylvite or diethanolamine salt.
Black tetrazo sulfoacid compound of the present invention or its salt most preferably comprise following compound (Dye-1 ~ 7):
|
R
1 |
R
2 |
R
3 |
R
4 |
Salt-forming cation |
Dye?I-1 |
-CH
2CH
2OH
|
-H |
-CH
2CH
2OH
|
-H |
Na
+ |
Dye?I-2 |
-CH
2CH
2OH
|
-CH
2CH
2OH
|
-CH
2CH
2OH
|
-CH
2CH
2OH
|
Na
+ |
Dye?I-3 |
-(CH
2)
3CO
2Na
|
-H |
-(CH
2)
3CO
2Na
|
-H |
Na
+ |
Dye?I-4 |
-(CH
2)
5CO
2Na
|
-H |
-(CH
2)
5CO
2Na
|
-H |
Na
+ |
Dye?I-5 |
-CH
3 |
-CH
3 |
-CH
3 |
-CH
3 |
[NH
2(CH
3)
2]
+ |
Dye?I-6 |
-CH
2CH
2OH
|
-CH
2CH
2OH
|
-CH
2CH
2OH
|
-CH
2CH
2OH
|
[NH
2(CH
2CH
2OH)
2]
+ |
Dye?I-7 |
-(CH
2)
3SO
3Na
|
-H |
-(CH
2)
3SO
4Na
|
-H |
Na
+ |
Black tetrazo sulfoacid compound or its salt of the invention described above can be used for preparing composition for ink.Said composition for ink comprises said black tetrazo sulfoacid compound or its salt and water at least, can also comprise water-miscible organic solvent or additive for ink.
In the embodiment, according to mass percent, the usage quantity of said compound or its salt in composition for ink is generally 0.l-20%; Preferred 1-20%; More preferably 1-15%, most preferably 2-10%;
The usage quantity of described water-soluble solvent in composition for ink is generally 0-50%; Preferred 5-50%.
Described water-miscible organic solvent concrete for example but be not limited only to: C such as methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol
1-4Alkanol; N, acid amides such as dinethylformamide or DMAC N,N; Lactan such as 2-Pyrrolidone, N-N-methyl-2-2-pyrrolidone N-; Terepthaloyl moietie, l, 2-Ucar 35,1, ammediol, 1,2-butyleneglycol, 1,4-butyleneglycol, 1,6-pinakon, Diethylene Glycol, triethylene glycol, TEG, dipropylene glycol, sulphur glycol, polyoxyethylene glycol; Glycerine, hexane-l, 2, polyvalent alcohols (trivalent alcohol) such as 6-triol; Ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether; The C of polyvalent alcohols such as triethylene glycol monomethyl ether, Triethylene glycol ethyl ether, triethylene glycol butyl ether
1-4Alkyl oxide; Gamma-butyrolactone or DMSO 99.8MIN., urea, thanomin, diethylolamine, trolamine etc.These water-miscible organic solvents can separately or mix and use.
Wherein preferred 2-Pyrrolidone, N-N-methyl-2-2-pyrrolidone N-, terepthaloyl moietie, Diethylene Glycol, triethylene glycol, dipropylene glycol, ethylene glycol monobutyl ether.Most preferably 2-Pyrrolidone, N-N-methyl-2-2-pyrrolidone N-, Diethylene Glycol, ethylene glycol monobutyl ether.
Below be ink group of the present invention one of embodiment, according to mass percent, said compsn is made up of following component:
Component i 1-20%
Water-miscible organic solvent 5-50%
Water surplus
Wherein, described component i is one or more mixtures according to arbitrary proportion in black tetrazo sulfoacid compound of the present invention or its salt.
Again in the concrete embodiment, also contain the additive for ink of 0-5% in the said composition for ink according to weight percent.Comprise: Antisepticize and mildew preventive, pH adjustment agent, chelating reagent, rust-preventive agent, water-soluble UV light absorber, water-soluble high-molecular compound, dyestuff solvating agent, tensio-active agent etc.
The preparation of composition for ink of the present invention is with black tetrazo sulfoacid compound of the present invention or its salt, or its mixture, in the water-soluble or described water-miscible organic solvent, and can dissolve and process with above-mentioned additive for ink etc. according to need making it.
In above-mentioned method of manufacture, the dissolving of each composition is not had special restriction in proper order.Dyestuff is dissolved in water or the described water-miscible organic solvent, adds the ink control agent and make its dissolving, also can after dyestuff is dissolved in water, add aqueous solvent, the ink modulator makes it dissolving.Order that also can be therewith is different.More can carry out in the solution of desalting treatment, add water-miscible organic solvent, additive for ink is made composition for ink at reaction solution that will contain this dyestuff or the lysate reverse osmosis membrane that contains this pigment.When the modulation composition for ink, employed water is preferably the less deionized waters of impurity such as ion exchanged water or zero(ppm) water.Use membrane filter etc. to carry out secondary filter and remove inclusion then.The filter membrane aperture of carrying out secondary filter is generally 1 micron to 0.01 micron, preferred 0.8 micron to 0.2 micron.
With the black ink composition of The compounds of this invention or its mixture preparation, be applicable to and impress, duplicating, mark, notes, chart, affix one's seal or print, especially for spray ink Printing.Its advantage is that the gained image has good patience for water, daylight, ozone and friction, also can be used to colorant match, particularly forms the black dyes of different color light.
The example by record base material (media) of applicable inkjet printing methods of the present invention can be enumerated like paper, copy paper, printer paper, film, fiber and leather etc.Usually need on the medium ink absorption layer to be set in these base material through surface treatment.For example the ink absorption layer is through dipping or coat above-mentioned base material with polymkeric substance such as positively charged ions; Also contain porous silica, alumina sol or special ceramics etc. in the coating, these white inorganicss and hydrophilic polymers such as Z 150PH or Vinylpyrrolidone polymer are jointly via coating above-mentioned substrate surface.The thin slice that scribbles these ink adsorption layers is commonly referred to as ink-jet dedicated paper (film) or glossy paper (film) etc.In addition, common paper also capable of using certainly.
Usually; Scribble print image on the matrix of porousness white inorganics on above-mentioned surface; Big by the caused electrochromic variable that moves back of ozone, but, therefore can bring into play special effect to the printing of this type of base material because the anti-gaseousness of water-based magenta ink composition of the present invention is excellent.
The example of porousness white inorganics is like lime carbonate, kaolin, talcum, clay, zeyssatite, synthetic amorphous silica, pure aluminium silicate, Magnesium Silicate q-agent, Calucium Silicate powder.White lake, aluminum oxide, zinc barium stone, zeolite, permanent white, calcium sulfate, titanium oxide, zinc sulphide, zinc carbonate etc.
The example of ink-jet printer can enumerate as: utilize the stamping machine of piezoelectricity mode or utilize through the stamping machine of the foaming mode that adds the thermogenesis bubble etc.
Water-based magenta ink composition of the present invention is a black, especially in the ink-jet glossy paper, has high distinct tone, and the fastness of document image is also high, also safe to human body.
Deposition can not take place or separate in composition for ink of the present invention in storage.And, when in spray ink Printing, using ink of the present invention, also can not block shower nozzle.Even ink of the present invention by continuous inkjet printer in fixing long period or by spells under the working conditions, the variation of neither generation physical properties.
Below be embodiment, specify the present invention.In addition, " part " among this paper and " % " refer to weight basis respectively if no special instructions.
Embodiment 1
36.5 part 2-amino-5-(2-sulfonic acid oxygen ethyl sulfuryl) Phenylsulfonic acid (being commonly called as sulfonation para-ester) is dissolved under stirring in the 200 gram water, adds 37.5 parts of 30% hydrochloric acid; Add 50 parts of ice, be cooled to 0--5 ℃, stir and drip 50 parts of aqueous solution that contain 7 parts of Sodium Nitrites down; Keep temperature of reaction about 0-5 ℃, stirred 1 hour, add 3 parts in urea; Stir 0.5 hour after-filtration, get limpid diazotization solution.
18 parts of 4-amino-5-hydroxyl-naphthalenes-2,7-disulfonic acid (being commonly called as H-acid) is dissolved in 100 parts of water, adds 50 parts of ice cubes; Stir down, splash into the diazotization solution about 60%, holding temperature is at 5-10 ℃; Stirred 2-3 hour; Using 10% aqueous sodium hydroxide solution adjustment pH is 3, continues reaction 2 hours, obtains red solution.10% aqueous sodium hydroxide solution adjustment pH is 9-10 then, under same temperature, splashes into remaining diazonium solution, keeps pH at 8-8.5, stirring reaction 2-3 hour, obtains dark solution.
Dark solution is removed remaining inorganic salt through high pressure r-o-nf membrane system, behind the membrane-concentrated, adds methyl alcohol, and black solid is separated out, and filters, and drying gets 50 parts of intermediate product Dye I-0:
The mass spectrum of Dye I-0 (EI-MS) m/z (-): 364.6 ([
M-3Na]
3-/ 3), 357.3 ([
M-4Na+H]
3-/ 3), 359.9 ([
M-5Na+2H]
3-/ 3); 574.4 ([
M-2Na]
2-/ 2), 563.4 ([
M-3Na+H]
2-/ 2), 522.4 ([
M-4Na+2H]
2-/ 2), 541.4 ([
M-5Na+3H]
2-/ 2).The richest accurate molecular mass number of dyestuff Dye I-0
MBe 1162.8.
Embodiment 2
Take by weighing 11.6 parts of dyestuff Dye I-0 that obtained by embodiment 1, be dissolved in 100 parts of water, add 1.5 parts of thanomins, regulate pH at 9.5-10.5 with 20% sodium hydroxide, stir and be warming up to 50-60 ℃, continuous dropping sodium is kept pH between the reaction period, and is constant until pH.Reaction solution is cooled off.Remove the inorganic salt in the system with the high pressure reverse osmosis membrane system, after concentrating, add the methyl alcohol with volume, black precipitate is separated out, and filters, and drying obtains 10 parts of black dyes Dye I-1, and its mass spectrum (EI-MS) m/z (-) is: 246.3 ([
M-4Na]
4-/ 4); 336.0 ([
M-3Na]
3-/ 3), 328.7 ([
M-4Na+H]
3-/ 3); 515.5 ([
M-2Na]
2-/ 2), 504.5 ([
M-3Na+H]
2-/ 2), 493.5 ([
M-4Na+2H]
2-/ 2).The richest accurate molecular mass number of dyestuff Dye I-1
MBe 1077.0.
Embodiment 3
By method and the step identical, just, obtain 11 parts of black dyes Dye I-2 with the alternative 1.5 parts of thanomins of 2.5 parts of diethylolamine with embodiment 2.Its mass spectrum (EI-MS) m/z (-) is characterized by: 268.3 ([
M-4Na]
4-/ 4); 365.3 ([
M-3Na]
3-/ 3), 358.0 ([
M-4Na+H]
3-/ 3); 559.5 ([
M-2Na]
2-/ 2), 548.5 ([
M-3Na+H]
2-/ 2), 537.5 ([
M-4Na+2H]
2-/ 2).The richest accurate molecular mass number of dyestuff Dye I-2
MBe 1165.0.
Embodiment 4
By method and the step identical, just, obtain 11 parts of black dyes Dye I-3 with the alternative 1.5 parts of thanomins of 3 parts of 4-propalanine sodium with embodiment 2.Its mass spectrum (EI-MS) m/z (-) is characterized by: 378.7 ([
M-3Na]
3-/ 3), 371.3 ([
M-4Na+H]
3-/ 3), 364.0 ([
M-5Na+2H]
3-/ 3); 579.5 ([
M-2Na]
2-/ 2), 568.5 ([
M-3Na+H]
2-/ 2), 557.5 ([
M-4Na+2H]
2-/ 2), 546.5 ([
M-5Na+3H]
2-/ 2).The richest accurate molecular mass number of dyestuff Dye I-3
MBe 1204.9.
Embodiment 5
By method and the step identical, just, obtain 11.3 parts of black dyes Dye I-4 with the alternative 1.5 parts of thanomins of 3.5 parts of 4-hexosamine sodium with embodiment 2.Its mass spectrum (EI-MS) m/z (-) is characterized by: 397.3 ([
M-3Na]
3-/ 3), 390.0 ([
M-4Na+H]
3-/ 3), 382.7 ([
M-5Na+2H]
3-/ 3); 607.5 ([
M-2Na]
2-/ 2), 596.5 ([
M-3Na+H]
2-/ 2), 585.5 ([
M-4Na+2H]
2-/ 2), 570.5 ([
M-5Na+3H]
2-/ 2).The richest accurate molecular mass number of dyestuff Dye I-4
MBe 1261.0.
Embodiment 6
By method and the step identical with embodiment 2, just substitute 1.5 parts of thanomins with 3 parts of n n dimetylaniline (being dissolved in the ethanol), with decil alcoholic solution replace sodium hydroxide adjusting pH, obtain 8 parts of black dyes Dye I-5 simultaneously.Its mass spectrum (EI-MS) m/z (-) is characterized by: 238.3 ([
M-4NH
2(CH
3)
2]
4-/ 4); 333.1 ([
M-3NH
2(CH
3)
2]
3-/ 3), 318.1 ([
M-4NH
2(CH
3)
2+ H]
3-/ 3); 524.7 ([
M-2NH
2(CH
3)
2]
2-/ 2), 502.2 ([
M-3NH
2(CH
3)
2+ H]
2-/ 2), 479.7 ([
M-4NH
2(CH
3)
2+ 2H]
2-/ 2).The richest accurate molecular mass number of dyestuff Dye I-5
MBe 1137.3.
Embodiment 7
By method and the step identical with embodiment 2, the ratio identical with embodiment 3 substitute 1.5 parts of thanomins with 2.5 parts of diethylolamine, but adjusting pH is not to use sodium hydroxide, but diethylolamine kept pH, obtains 12 parts of black dyes Dye I-6 at last.Its mass spectrum (EI-MS) m/z (-) is characterized by: 268.3 ([
M-4NH
2(CH
2CH
2OH)
2]
4-/ 4); 393.0 ([
M-3NH
2(CH
2CH
2OH)
2]
3-/ 3), 358.0 ([
M-4NH
2(CH
2CH
2OH)
2+ H]
3-/ 3); 537.5 ([
M-4NH
2(CH
2CH
2OH)
2+ 2H]
2-/ 2).The richest accurate molecular mass number of dyestuff Dye I-6
MBe 1497.0.
Embodiment 8
By method and the step identical, just, obtain 11 parts of black dyes Dye I-7 with the alternative 1.5 parts of thanomins of 5 parts of 3-aminopropanesulfonic acid sodium with embodiment 2.Its mass spectrum (EI-MS) m/z (-) is characterized by: 402.7 ([
M-3Na]
3-/ 3), 395.3 ([
M-4Na+H]
3-/ 3), 388.0 ([
M-5Na+2H]
3-/ 3); 615.5 ([
M-2Na]
2-/ 2), 604.5 ([
M-3Na+H]
2-/ 2), 593.5 ([
M-4Na+2H]
2-/ 2), 582.5 ([
M-5Na+3H]
2-/ 2).The richest accurate molecular mass number of dyestuff Dye I-7
MBe 1276.9.
Embodiment 9 (contrast dye is synthetic)
Take by weighing 10 parts of (converted is 100%) commercial dyes C.I. REACTIVE BLACK 5 100s (Taixing City, Jiangsu golden pheasant dye chemical industry ltd); Add 100 parts of entry, stirring and dissolving splashes into 45 parts of 20% aqueous sodium hydroxide solutions under the room temperature; Be warming up to 30-40 ° of C under stirring, stirred 2 hours.Add 30 parts of stirrings of salt and saltout, get 8 parts of black dyes Dye II-1 head products.After the filtration, dissolve in 100 parts of water, use high pressure r-o-nf membrane to go out remaining sodium-chlor, steam most of water, adds 20 parts of methyl alcohol, black precipitate is separated out, and filters, and drying must 6 parts of pure dye Dye II-1.Mass spectrum (EI-MS) m/z (-): 352.5 ([
M-2Na]
2-/ 2), 728.0 ([
M-2Na+H]
-), 750.0 ([
M-Na]
-).It is 751.0 that the richest accurate molecular mass of dyestuff Dye II-1 is counted M.
Embodiment 8
(A) preparation of ink
Use the dyestuff of the foregoing description 1-7 gained, according to prescription shown in the following table 1, the preparation composition for ink filters through 0.45 μ m membranous filter, obtains property composition for ink in Heisui River of the present invention.Wherein, add trolamine and regulate that the pH value of composition for ink becomes 8 to 10, the adding deionized water makes total amount reach 100 weight parts.
Simultaneously, in the same way, adopt black 2, the directly black 154 composition control inks of commercial dye C.I. of commercial dye C.I. food.
The experiment of table 1 ink is formed
Component |
Weight part |
Dyestuff |
6 |
Glycerine |
5 |
Urea |
5 |
2-Pyrrolidone |
4 |
Ethylene glycol monobutyl ether |
2 |
Virahol |
3 |
Nonionogenic tenside OP-10 |
0.2 |
Trolamine (regulating pH) |
0.2 |
EDTA |
0.1 |
Sterilant |
0.01 |
Deionized water |
Mend full to 100 weight parts |
(B) spray ink Printing:
Use ink-jet printer (Epson makes Epson270 type stamping machine), on high light printing paper (Epson's manufacturing), carry out spray ink Printing with the composition for ink of above-mentioned preparation.
(C) evaluation of ink jet print image:
(1) the anti-ozone gas property test of print image
Will be through the picture of printing, use the weather-proof appearance of ozone (Chinese Su Rui manufactured) the environment held of 24 ℃ of ozone concn 40ppm, humidity 60%RH, temperature 6 hours.Aberration (Δ E) before and after the determination test.Aberration (Δ E) be with above-mentioned chromatic measuring system (Unterlab) carry out each L*, a*, b* before and after the determination test value, obtain by following formula by the difference of the test front and back of L*, a*, each value of b*:
Δ E=((L*'s is poor)
2+ (a*'s is poor)
2+ (b*'s is poor)
2)
1/2
According to following benchmark, divide 3 ranks to estimate:
ΔE<10 ○
ΔE<20 △
ΔE>20 ×
(2) anti-moisture test of print image
Will be in controlled thermohygrostat (Chinese Su Rui manufactured) through the test picture printed, 50 ℃, the condition held of 90%RH 168 hours, exudative with before and after the visual judgement test of bore hole according to following benchmark, divided 3 ranks to estimate.
Have no to ooze out zero
A little oozes out △
Ooze out many *
(3) solubleness (g/100g water) of dyestuff in water is estimated
Dyestuff is solubleness in water>30 0
Dyestuff is solubleness in water>15-20 △
Dyestuff in water solubleness 15 *
(4) the permanent stability evaluation of dyestuff in aqueous solvent system:
With 20 parts of dyestuffs, 70 parts of system's heating for dissolving of forming with 10 parts of terepthaloyl moietie of water, after the cooling, storage was cooled to 0 ℃ after 7 days in 50 ℃ of homothermic enclosed environments, placed 7 days at 0 ℃ then, filtered, and by following benchmark, divided three ranks to estimate:
Have no to precipitate zero
A little precipitates △
Many depositions *
All test results are shown in table 2:
Result by table 2 is relatively more visible, and sulfonation para-ester dyestuff of the present invention has very excellent ozone resistance, water resistance as the black dyes in the jetted ink in spray ink Printing, and dyestuff has good water-soluble, and dye ink has permanent stability.
Table 2
Industrial applicibility
The solvability of sulfonation para-ester dye composition shown in the general formula I of the present invention in water is high; Good stability; The black ink excellent storage stability that contains this compounds; And use the fastness such as anti-ozone, moisture-proof of the print image of this ink excellent, so this compounds is to be suitable for the black dyes that spray ink Printing is used.