CN116574393A - Dye, preparation method thereof and black digital ink-jet printing ink - Google Patents
Dye, preparation method thereof and black digital ink-jet printing ink Download PDFInfo
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- CN116574393A CN116574393A CN202310458193.4A CN202310458193A CN116574393A CN 116574393 A CN116574393 A CN 116574393A CN 202310458193 A CN202310458193 A CN 202310458193A CN 116574393 A CN116574393 A CN 116574393A
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- 238000007641 inkjet printing Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229910001413 alkali metal ion Inorganic materials 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 57
- 238000005859 coupling reaction Methods 0.000 claims description 55
- 239000000376 reactant Substances 0.000 claims description 55
- 238000006243 chemical reaction Methods 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000012954 diazonium Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- HBZVNWNSRNTWPS-UHFFFAOYSA-N 6-amino-4-hydroxynaphthalene-2-sulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=C(O)C2=CC(N)=CC=C21 HBZVNWNSRNTWPS-UHFFFAOYSA-N 0.000 claims description 16
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 claims description 15
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 14
- 239000012670 alkaline solution Substances 0.000 claims description 13
- 239000011734 sodium Substances 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 7
- IYYOZQDGQBNUNI-UHFFFAOYSA-N [diazonio(nitro)amino]benzene Chemical class [N+](=O)([O-])N(C1=CC=CC=C1)[N+]#N IYYOZQDGQBNUNI-UHFFFAOYSA-N 0.000 claims description 5
- 230000008878 coupling Effects 0.000 claims description 5
- 238000010168 coupling process Methods 0.000 claims description 5
- VBEGHXKAFSLLGE-UHFFFAOYSA-N n-phenylnitramide Chemical compound [O-][N+](=O)NC1=CC=CC=C1 VBEGHXKAFSLLGE-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 3
- REJHVSOVQBJEBF-UHFFFAOYSA-N 5-azaniumyl-2-[2-(4-azaniumyl-2-sulfonatophenyl)ethenyl]benzenesulfonate Chemical compound OS(=O)(=O)C1=CC(N)=CC=C1C=CC1=CC=C(N)C=C1S(O)(=O)=O REJHVSOVQBJEBF-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000003637 basic solution Substances 0.000 claims 1
- 239000000975 dye Substances 0.000 abstract description 102
- 230000003647 oxidation Effects 0.000 abstract description 15
- 238000007254 oxidation reaction Methods 0.000 abstract description 15
- 239000011203 carbon fibre reinforced carbon Substances 0.000 abstract description 10
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000000982 direct dye Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 28
- 239000000976 ink Substances 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 23
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 18
- 235000010288 sodium nitrite Nutrition 0.000 description 14
- 238000012360 testing method Methods 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- QPILZZVXGUNELN-UHFFFAOYSA-M sodium;4-amino-5-hydroxynaphthalene-2,7-disulfonate;hydron Chemical compound [Na+].OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S([O-])(=O)=O)=CC2=C1 QPILZZVXGUNELN-UHFFFAOYSA-M 0.000 description 12
- 239000002253 acid Substances 0.000 description 11
- MMVDLMPGBRLTSO-UHFFFAOYSA-N 1-(diazonioamino)-4-nitrobenzene Chemical class [O-][N+](=O)C1=CC=C(N[N+]#N)C=C1 MMVDLMPGBRLTSO-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000012266 salt solution Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- 150000001989 diazonium salts Chemical class 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 5
- UZZFFIUHUDOYPS-UHFFFAOYSA-L disodium 4-amino-3,6-bis[[4-[(2,4-diaminophenyl)diazenyl]phenyl]diazenyl]-5-oxido-7-sulfonaphthalene-2-sulfonate Chemical compound [Na+].[Na+].Nc1ccc(N=Nc2ccc(cc2)N=Nc2c(N)c3c(O)c(N=Nc4ccc(cc4)N=Nc4ccc(N)cc4N)c(cc3cc2S([O-])(=O)=O)S([O-])(=O)=O)c(N)c1 UZZFFIUHUDOYPS-UHFFFAOYSA-L 0.000 description 4
- DHQJMKJYFOHOSY-UHFFFAOYSA-L disodium 4-amino-3-[[4-[4-[(2,4-diaminophenyl)diazenyl]-3-methylphenyl]-2-methylphenyl]diazenyl]-5-oxido-6-phenyldiazenyl-7-sulfonaphthalene-2-sulfonate Chemical compound [Na+].[Na+].Cc1cc(ccc1N=Nc1ccc(N)cc1N)-c1ccc(N=Nc2c(N)c3c(O)c(N=Nc4ccccc4)c(cc3cc2S([O-])(=O)=O)S([O-])(=O)=O)c(C)c1 DHQJMKJYFOHOSY-UHFFFAOYSA-L 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- GWAKFAUFNNPZFE-UHFFFAOYSA-K trisodium 2-[4-[(2-amino-4-oxidophenyl)diazenyl]anilino]-5-[(1-amino-8-oxido-7-phenyldiazenyl-3,6-disulfonaphthalen-2-yl)diazenyl]benzenesulfonate Chemical compound NC1=C(C(=CC2=CC(=C(C(=C12)O)N=NC1=CC=CC=C1)S(=O)(=O)[O-])S(=O)(=O)[O-])N=NC1=CC(=C(C=C1)NC1=CC=C(C=C1)N=NC1=C(C=C(C=C1)O)N)S(=O)(=O)[O-].[Na+].[Na+].[Na+] GWAKFAUFNNPZFE-UHFFFAOYSA-K 0.000 description 4
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 3
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 3
- 238000006193 diazotization reaction Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 3
- LQNUZADURLCDLV-IDEBNGHGSA-N nitrobenzene Chemical group [O-][N+](=O)[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 LQNUZADURLCDLV-IDEBNGHGSA-N 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- AZFNGPAYDKGCRB-XCPIVNJJSA-M [(1s,2s)-2-amino-1,2-diphenylethyl]-(4-methylphenyl)sulfonylazanide;chlororuthenium(1+);1-methyl-4-propan-2-ylbenzene Chemical compound [Ru+]Cl.CC(C)C1=CC=C(C)C=C1.C1=CC(C)=CC=C1S(=O)(=O)[N-][C@@H](C=1C=CC=CC=1)[C@@H](N)C1=CC=CC=C1 AZFNGPAYDKGCRB-XCPIVNJJSA-M 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- IDNHOWMYUQKKTI-UHFFFAOYSA-M lithium nitrite Chemical compound [Li+].[O-]N=O IDNHOWMYUQKKTI-UHFFFAOYSA-M 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 235000010289 potassium nitrite Nutrition 0.000 description 2
- 239000004304 potassium nitrite Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 2
- ZTGKHKPZSMMHNM-UHFFFAOYSA-N 3-(2-phenylethenyl)benzene-1,2-disulfonic acid Chemical group OS(=O)(=O)C1=CC=CC(C=CC=2C=CC=CC=2)=C1S(O)(=O)=O ZTGKHKPZSMMHNM-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000001042 pigment based ink Substances 0.000 description 1
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011158 quantitative evaluation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B43/00—Preparation of azo dyes from other azo compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/32—Inkjet printing inks characterised by colouring agents
- C09D11/328—Inkjet printing inks characterised by colouring agents characterised by dyes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The application relates to the technical field of dye synthesis, and provides a dye, a preparation method thereof and black digital ink-jet printing ink, wherein the molecular structural general formula I of the dye is as follows:wherein R in the general molecular structural formula 1 、R 2 、R 3 、R 4 、R 5 Respectively and independently select alkali metal ion and NH [ (CH) 2 ) n OH] 3 + Any one of n is 1 to 5. The molecular structural general formula of the dye provided by the application is shown as formula I, so that the dye is a black direct dye, and contains a carbon-carbon double bond (C=C) and nitro (NO 2 ) The carbon-carbon double bond can absorb ultraviolet light to endow the dye with good light resistance, and the nitro group can endow the dye with good oxidation resistance, so that the dye of the application has excellent light resistance and oxidation resistance simultaneouslyThe weather resistance is good.
Description
Technical Field
The application belongs to the technical field of dye synthesis, and particularly relates to a dye, a preparation method thereof and black digital inkjet printing ink.
Background
Digital ink-jet ink is divided into pigment ink-jet ink and dye ink-jet ink, wherein images sprayed by the pigment ink-jet ink have the advantages of light resistance, ozone resistance, good water fastness and the like, but the defects of difficult processing, easy blockage of an ink-jet head, insufficient bright color, high cost and the like limit the application of the digital ink-jet ink. Compared with pigment type ink-jet ink, the dye type ink-jet ink has the advantages of good permeability, wear resistance and stability, difficult blockage of a printing head, bright color, complete color spectrum of the used dye, wide selection range and the like, and more than 60 percent of the components are water, so that the cost is relatively low, and the environment-friendly requirement is met. Dye-type inkjet inks have thus been the dominant product in the market place. However, dye-based inkjet inks have disadvantages such as poor weather resistance, poor light resistance and oxidation resistance, and poor water fastness, which are inferior to pigment-based inks, due to the structural problems of the dyes themselves, and it is difficult to satisfy the market demand for high quality images and characters.
Therefore, there is an urgent need to develop a direct black dye having good light resistance and oxidation resistance.
Disclosure of Invention
The application aims to provide a dye, a preparation method thereof and black digital ink-jet printing ink, and aims to solve the technical problems of poor light resistance and poor oxidation resistance of the existing black dye.
In order to achieve the purposes of the application, the technical scheme adopted by the application is as follows:
in a first aspect, the present application provides a dye having the general molecular structure of formula I:
wherein R in the general molecular structural formula 1 、R 2 、R 3 、R 4 、R 5 Are respectively and independently selected from alkali metal ions and NH [ (CH) 2 ) n OH] 3 + Any one of n is 1 to 5.
In a second aspect, the present application provides a method for preparing a dye, comprising the steps of:
carrying out coupling reaction on a first reactant shown in a formula V, a second reactant shown in a formula VI and 2-amino-8-naphthol-6-sulfonic acid in an alkaline solution to obtain the dye;
in a third aspect, the present application provides a dye provided by the present application and/or an application of the dye prepared by the preparation method of the dye provided by the present application in black digital inkjet printing ink.
In a fourth aspect, the present application provides a black digital inkjet printing ink, comprising the following components in percentage by weight, based on 100% of the total weight of the black digital inkjet printing ink:
1 to 15 percent of dye,
5-40% of organic solvent,
40-70% of water;
wherein the dye is the dye provided by the application and/or the dye prepared by the preparation method of the dye provided by the application.
Compared with the prior art, the application has the following beneficial effects:
the dye provided by the first aspect of the application has a molecular structural formula shown as formula I, so that the dye is a black direct dye, and contains a carbon-carbon double bond (C=C) and a nitro group (NO 2 ) The carbon-carbon double bond can absorb ultraviolet light to endow the dye with good light resistance, and the nitro can endow the dye with good oxidation resistance, so that the dye disclosed by the application has excellent light resistance and oxidation resistance and good weather resistance.
According to the preparation method of the dye, the dye with the molecular structural general formula I can be obtained by carrying out coupling reaction on the first reactant shown in the formula V, the second reactant shown in the formula VI and the 2-amino-8-naphthol-6-sulfonic acid in an alkaline solution, and the dye with the molecular structural general formula I has excellent light resistance and oxidation resistance due to the fact that the molecular structural general formula contains carbon-carbon double bonds and nitro groups.
The dye provided by the third aspect of the application is applied to black digital ink-jet printing ink, and the dye has the molecular structural general formula I which simultaneously contains a carbon-carbon double bond (C=C) and a nitro (NO 2 ) The dye has excellent light resistance and oxidation resistance at the same time, due toThe black digital ink-jet printing ink has good weather resistance.
According to the fourth aspect of the application, a black digital ink-jet printing ink is provided, and 1-15% of the dye is the dye provided by the application and/or the dye prepared by the preparation method provided by the application, so that the black digital ink-jet printing ink has excellent light resistance, oxidation resistance and weather resistance.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear, the application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the application.
In the present application, the term "and/or" describes an association relationship of an association object, which means that three relationships may exist, for example, a and/or B may mean: a alone, a and B together, and B alone. Wherein A, B may be singular or plural. The character "/" generally indicates that the context-dependent object is an "or" relationship.
In the present application, "at least one" means one or more, and "a plurality" means two or more. "at least one of" or the like means any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (individual) of a, b, or c," or "at least one (individual) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, c may be single or multiple, respectively.
It should be understood that, in various embodiments of the present application, the sequence number of each process described above does not mean that the execution sequence of some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its functions and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in this application and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weights of the relevant components mentioned in the description of the embodiments of the present application may refer not only to the specific contents of the components, but also to the proportional relationship between the weights of the components, so long as the contents of the relevant components in the description of the embodiments of the present application are scaled up or down within the scope of the disclosure of the embodiments of the present application. Specifically, the mass described in the specification of the embodiment of the application can be mass units known in the chemical industry field such as mu g, mg, g, kg.
The terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated for distinguishing between objects such as substances from each other. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the application. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature.
The first aspect of the embodiment of the application provides a dye, and the molecular structural general formula I of the dye is as follows:
wherein R in the general molecular structural formula 1 、R 2 、R 3 、R 4 、R 5 Are respectively and independently selected from alkali metal ions and NH [ (CH) 2 ) n OH] 3 + Any one of n is 1 to 5.
The dye provided by the embodiment of the application has a molecular structural general formula shown as formula I, so that the dye is a black direct dye, and contains a carbon-carbon double bond (C=C) and a nitro (NO 2 ) The carbon-carbon double bond can absorb ultraviolet light to endow the dye with good light resistance, and the nitro groupThe dye can be endowed with good oxidation resistance, so that the dye disclosed by the application has excellent light resistance and oxidation resistance and good weather resistance.
In an embodiment, R in the general molecular structural formula I 1 、R 2 、R 3 、R 4 、R 5 Are respectively and independently selected from Li + 、Na + 、NH(C 2 H 4 OH) 3 + Any one of the following. Specifically, R 1 、R 2 、R 3 、R 4 、R 5 Can be identically or differently selected from Li + 、Na + 、NH(C 2 H 4 OH) 3 + . For example, R 1 Can be selected from Li + ，R 2 And R is 3 Can be selected from Na + ，R 4 And R is 5 Can be selected from NH (C) 2 H 4 OH) 3 + . Alternatively, R 1 Can be selected from Na + ，R 2 And R is 3 Can be selected from Li + ，R 4 And R is 5 Can be selected from NH (C) 2 H 4 OH) 3 + . Or, R 1 Can be selected from NH (C) 2 H 4 OH) 3 + ，R 2 And R is 3 Can be selected from Li + ，R 4 And R is 5 Can be selected from Na + . Or, R 1 Can be selected from NH (C) 2 H 4 OH) 3 + ，R 2 And R is 3 Can be selected from Na + ，R 4 And R is 5 Can be selected from Li + . Or, R 1 Can be selected from Na + ，R 2 And R is 3 Can be selected from NH (C) 2 H 4 OH) 3 + ，R 4 And R is 5 Can be selected from Li + . Or, R 1 Can be selected from Na + ，R 2 And R is 3 Can be selected from NH (C) 2 H 4 OH) 3 + ，R 4 And R is 5 Can be selected from Na + 。
In some embodiments, R in the general molecular structural formula I 1 、R 2 、R 3 、R 4 、R 5 Are all the same and can be selected from Li + 、Na + 、NH(C 2 H 4 OH) 3 + Any one of the following. Specifically, R 1 、R 2 、R 3 、R 4 、R 5 Are all selected from Li + The molecular structural formula of the dye is
R 1 、R 2 、R 3 、R 4 、R 5 Are all selected from Na + The molecular structural formula of the dye is
R 1 、R 2 、R 3 、R 4 、R 5 Are all selected from NH (C) 2 H 4 OH) 3 + The molecular structural formula of the dye is
In an embodiment, the dye may be selected from at least one of the following compounds of formula II, formula III, formula IV;
the second aspect of the embodiment of the application provides a preparation method of dye, which comprises the following steps:
carrying out coupling reaction on a first reactant shown in a formula V, a second reactant shown in a formula VI and 2-amino-8-naphthol-6-sulfonic acid in an alkaline solution to obtain a dye;
according to the preparation method of the dye, the dye with the molecular structural general formula I can be obtained by carrying out coupling reaction on the first reactant shown in the formula V, the second reactant shown in the formula VI and the 2-amino-8-naphthol-6-sulfonic acid in an alkaline solution, and the dye with the molecular structural general formula I has excellent light resistance and oxidation resistance due to the fact that the molecular structural general formula contains carbon-carbon double bonds and nitro groups.
In an embodiment, the preparing step of the first reactant comprises: mixing nitroaniline solution and first nitrite solution to perform a first diazonium reaction to obtain nitroaniline diazonium salt solution; the first reactant (formula V) is obtained by mixing the 1-amino-8-naphthol-3, 6-disulfonate solution and nitroaniline diazonium salt solution for a third coupling reaction. The conditions for the third coupling reaction include: the temperature is 18-20 ℃, the pH value is 3.5-5, the pH value is preferably 3.7-4.5, under the conditions of the temperature and the pH value, the 1-amino-8-naphthol-3, 6-disulfonate and nitroaniline diazonium salt can be synthesized, and the synthesis efficiency is high. Wherein, the process of the first diazonium reaction is as follows:
the second coupling reaction proceeds as follows:
in an embodiment, the first diazonium reaction is performed by mixing the nitroaniline solution and the nitrite solution, and the first nitrite solution may be added to the nitroaniline solution, and the first diazonium reaction is performed under acidic conditions and at a temperature of not more than 10 ℃. The nitrite may be selected from sodium nitrite, potassium nitrite, lithium nitrite, and the like. The first nitrite solution may be a first nitrite solution obtained by dissolving nitrite in a solvent, and the solvent may be a polar solvent commonly used in the art, such as water or the like.
In an embodiment, the step of preparing the second reactant comprises: the solution of 4,4 '-diaminostilbene-2, 2' -disulfonate (DSD acid salt) and the second nitrite solution are mixed to perform a second diazonium reaction, to obtain a second reactant (formula VI). Specifically, the first nitrite solution is added into DSD acid salt solution, and the second diazonium reaction is carried out under the conditions of acidity and not more than 10 ℃ to obtain a second reactant. The nitrite may be selected from sodium nitrite, potassium nitrite, lithium nitrite, and the like. The second nitrite solution may be a second nitrite solution obtained by dissolving nitrite in a solvent, and the solvent may be a polar solvent commonly used in the art, such as water, etc. Wherein, the process of the second diazonium reaction is as follows:
in an embodiment, the step of coupling the first reactant of formula V, the second reactant of formula VI, and 2-amino-8-naphthol-6-sulfonic acid (gamma acid) in an alkaline solution comprises: the first and second reactants are subjected to a first coupling reaction in an alkaline solution, and then 2-amino-8-naphthol-6-sulfonic acid is added to perform a second coupling reaction. Specifically, the reaction equation for the first coupling reaction of the first reactant and the second reactant in an alkaline solution is as follows:
finally, adding 2-amino-8-naphthol-6-sulfonic acid to carry out a second coupling reaction, wherein the process of the second coupling reaction is as follows:
in the embodiment, the temperature of the first coupling reaction is 20-30 ℃, the pH value is 6-7, the reaction time is 5-15 min, and under the conditions of the temperature and the pH value of the first coupling reaction, the first reactant and the second reactant are favorable for fully carrying out the coupling reaction, and side reactions are reduced. The temperature of the second coupling reaction is 20-30 ℃, the pH value is 6-7, and the time is 3.5-4.5 h. Under the conditions of the temperature and the pH value of the second coupling reaction, the further coupling reaction is facilitated, and side reactions are reduced.
In an embodiment, the alkaline solution includes sodium hydroxide solution (NaOH), lithium hydroxide solution (LiOH), triethanolamine solution (N (C) 2 H 4 OH) 3 ) At least one or more of the following. When the alkaline solution is sodium hydroxide solution, the reaction process of mixing the first reactant and the sodium hydroxide solution, adding the second reactant for the first coupling reaction, and then adding the 2-amino-8-naphthol-6-sulfonic acid for the second coupling reaction to obtain the direct black dye is as follows:
when the alkaline solution is lithium hydroxide solution, the first reactant and sodium hydroxide solution are mixed, then the second reactant is added for the first coupling reaction, and then the 2-amino-8-naphthol-6-sulfonic acid is added for the second coupling reaction, so that the direct black dye is obtained by the following reaction process:
the third aspect of the embodiment of the application provides an application of the dye provided by the application and/or the dye prepared by the preparation method of the dye provided by the application in black digital ink-jet printing ink.
The dye provided by the embodiment of the application is applied to black digital ink-jet printing ink, and the molecular structure of the dye is generalIn formula I, contains both a carbon-carbon double bond (C=C) and a nitro group (NO 2 ) The dye has excellent light resistance and oxidation resistance, so that the black digital ink-jet printing ink has good weather resistance.
According to a fourth aspect of the embodiment of the application, a black digital ink-jet printing ink is provided, which comprises the following components in percentage by weight, based on 100% of the total weight of the black digital ink-jet printing ink:
1 to 15 percent of dye,
5-40% of organic solvent,
40-70% of water;
wherein the dye is the dye provided by the application and/or the dye prepared by the preparation method of the dye provided by the application.
The black digital ink-jet printing ink provided by the embodiment of the application has excellent light resistance and oxidation resistance and good weather resistance because 1-15% of dye is the dye provided by the application and/or the dye prepared by the preparation method provided by the application.
The following description is made with reference to specific embodiments.
Example 1
The application provides a dye and a preparation method thereof.
The dye has a molecular structural general formula shown in the following formula II:
a method for preparing a dye comprising the steps of:
s11: preparing a first reactant;
first diazonium reaction: 200mL of water, paranitroaniline (16.56 g,0.12mol, 100%) and 20g of 30% hydrochloric acid solution were added to a 500mL reaction flask, and the mixture was cooled to below 10℃with ice; then adding sodium nitrite solution (8.7 g,0.126mol, 100%) to react at a temperature not exceeding 10 ℃, and stirring for 15min (taking the trace existence of sodium nitrite as the end point) after the addition to obtain p-nitroaniline diazonium salt solution;
third coupling reaction: 200mL of water, 15g of sodium bicarbonate and H acid (45.2 g,0.126mol and 100%) are added into a 300mL dissolution bottle, so that H acid is dissolved to form H acid salt solution, the H acid salt solution is added into p-nitroaniline diazonium salt solution and stirred for a third coupling reaction for 1H within 15min, wherein the temperature of the third coupling reaction is 19 ℃, 10% sodium carbonate solution is added to adjust the pH to 3.5-5 (Congo red test paper becomes purple) so that the p-nitroaniline diazonium salt is basically disappeared to terminate the reaction, and a first reactant shown in the following formula V is obtained;
s12: preparing a second reactant;
second diazonium reaction: DSD acid (49.3 g,0.133mol, 100%), 300mL water and 70g hydrochloric acid are added into a 500mL diazo bottle, pulped for half an hour, and ice is added to cool to below 10 ℃; then adding sodium nitrite solution (19.3 g,0.279mol, 100%) to perform a second diazotization reaction for 2 hours, removing residual sodium nitrite by sulfamic acid, and filtering to obtain a second reactant (DSD acid diazonium salt filter cake) shown in the following formula VI;
s13: first coupling reaction and second coupling reaction: 200mL of water is added into a 500mL coupling bottle, then a second reactant (DSD acid diazonium salt filter cake) is added, a sodium hydroxide solution is dropwise added under stirring, the pH is regulated to 6-7, a first reactant is added within 5-8min for carrying out a first coupling reaction, a gamma acid solution (30.1 g,0.126mol, 100%) is added within 10min after the first reactant is added, the pH is controlled to 6-7 after the addition, and stirring is carried out for carrying out a second coupling reaction for 4h, so that the dye shown in the formula II is obtained.
Example 2
The application provides a dye and a preparation method thereof.
The chemical structural general formula of the dye is shown in the following formula III:
a method for preparing a dye comprising the steps of:
s11: preparing a first reactant;
first diazonium reaction: 200mL of water, paranitroaniline (16.56 g,0.12mol, 100%) and 20g of 30% hydrochloric acid solution were added to a 500mL reaction flask, and the mixture was cooled to below 10℃with ice; then adding sodium nitrite solution (8.7 g,0.126mol, 100%) to react at a temperature not exceeding 10 ℃, and stirring for 15min (taking the trace existence of sodium nitrite as the end point) after the addition to obtain p-nitroaniline diazonium salt solution;
third coupling reaction: 200mL of water, 15g of sodium bicarbonate and H acid (45.2 g,0.126mol and 100%) are added into a 300mL dissolution bottle, so that H acid is dissolved to form H acid salt solution, the H acid salt solution is added into p-nitroaniline diazonium salt solution and stirred for a third coupling reaction for 1H within 15min, wherein the temperature of the third coupling reaction is 18 ℃, 10% sodium carbonate solution is added to adjust the pH to 3.5-5 (Congo red test paper becomes purple) so that the p-nitroaniline diazonium salt is basically disappeared to terminate the reaction, and a first reactant shown in the following formula V is obtained;
s12: preparing a second reactant;
second diazonium reaction: DSD acid (49.3 g,0.133mol, 100%), 300mL water and 70g hydrochloric acid are added into a 500mL diazo bottle, pulped for half an hour, and ice is added to cool to below 10 ℃; then adding sodium nitrite solution (19.3 g,0.279mol, 100%) to perform a second diazotization reaction for 2 hours, removing residual sodium nitrite by sulfamic acid, and filtering to obtain a second reactant (DSD acid diazonium salt filter cake) shown in the following formula VI;
s13: first coupling reaction and second coupling reaction: 200mL of water is added into a 500mL coupling bottle, then a second reactant (DSD acid diazonium salt filter cake) is added, a lithium hydroxide solution is dropwise added under stirring, the pH is regulated to 6-7, a first reactant is added within 5-8min for carrying out a first coupling reaction, a gamma acid solution (30.1 g,0.126mol, 100%) is added within 10min after the first reactant is added, the pH is controlled to 6-7 after the addition, and stirring is carried out for carrying out a second coupling reaction for 4h, so as to obtain the dye shown in the formula III.
Example 3
The application provides a dye and a preparation method thereof.
The chemical structural general formula of the dye is shown as the following formula IV:
a method for preparing a dye comprising the steps of:
s11: preparing a first reactant;
first diazonium reaction: 200mL of water, paranitroaniline (16.56 g,0.12mol, 100%) and 20g of 30% hydrochloric acid solution were added to a 500mL reaction flask, and the mixture was cooled to below 10℃with ice; then adding sodium nitrite solution (8.7 g,0.126mol, 100%) to react at a temperature not exceeding 10 ℃, and stirring for 15min (taking the trace existence of sodium nitrite as the end point) after the addition to obtain p-nitroaniline diazonium salt solution;
third coupling reaction: 200mL of water, 15g of sodium bicarbonate and H acid (45.2 g,0.126mol and 100%) are added into a 300mL dissolution bottle, so that H acid is dissolved to form H acid salt solution, the H acid salt solution is added into p-nitroaniline diazonium salt solution and stirred for a third coupling reaction for 1H within 15min, wherein the temperature of the third coupling reaction is 18 ℃, 10% sodium carbonate solution is added to adjust the pH to 3.5-5 (Congo red test paper becomes purple) so that the p-nitroaniline diazonium salt is basically disappeared to terminate the reaction, and a first reactant shown in the following formula V is obtained;
s12: preparing a second reactant;
second diazonium reaction: DSD acid (49.3 g,0.133mol, 100%), 300mL water and 70g hydrochloric acid are added into a 500mL diazo bottle, pulped for half an hour, and ice is added to cool to below 10 ℃; then adding sodium nitrite solution (19.3 g,0.279mol, 100%) to perform a second diazotization reaction for 2 hours, removing residual sodium nitrite by sulfamic acid, and filtering to obtain a second reactant (DSD acid diazonium salt filter cake) shown in the following formula VI;
s13: first coupling reaction and second coupling reaction: in a 500mL coupling flask, 200mL of water was added followed by the second reactant (DSD acid diazonium salt cake) and NH (C) was added dropwise with stirring 2 H 4 OH) 3 And (3) regulating the pH of the solution to be 6-7, adding a first reactant for carrying out a first coupling reaction within 5-8min, adding a gamma acid solution (30.1 g,0.126mol and 100%) within 10min after the first reactant is added, controlling the pH to be 6-7 after the addition, and stirring for carrying out a second coupling reaction for 4h to obtain the dye shown in the formula IV.
Comparative example 1
The chemical structural formula of the dye (C.I. direct black 19) of the comparative example is as follows:
comparative example 2
The chemical structural formula of the dye (C.I. direct black 168) of the comparative example is as follows:
comparative example 3
The chemical structural formula of the dye (C.I. direct black 154) of the comparative example is as follows:
correlation performance test analysis:
weather resistance test: the weather resistance is reduced mainly by ultraviolet rays in sunlight and ozone in the atmosphere, so that a simple light fastness testing method and an ozone resistance testing method are provided. The test process is gradually perfected through repeated tests, quantitative evaluation is added to the method by utilizing the color difference principle, the relation between the color difference, the light fastness level and the ozone resistance level is established through analysis, and the light fastness level and the ozone resistance level can be calculated through the attenuation rate or the color difference value delta E.
The dyes provided in examples 1 to 3, the colorant provided in comparative example 1 using c.i. direct black 19, the colorant provided in comparative example 2 using c.i. direct black 168, the colorant provided in comparative example 3 using c.i. direct black 154 were formulated into black dye inks, which were then printed on photographic papers on the market using a Canon MG7780 model inkjet printer.
1. Sun-proof test: the color densities of the color patches printed on the photographic paper of example 1, example 2, example 3, comparative example 1, comparative example 2, comparative example 3 were measured with an optical perspective Eye-one, then the color densities were measured under a UV lamp for 3 hours, and the color density decay rates of the color patches before and after the irradiation of the UV lamp were calculated. The greater the color density decay rate, the worse the light fastness is indicated; conversely, the lower the color density decay rate, the better the light fastness. Wherein, the rate of decay of the solar-fast color density= (color density before UV irradiation-color density after UV irradiation)/color density before UV irradiation is 100%; test result data are shown in table 1 below.
2. Ozone resistance test: the color densities of the color patches printed on the photographic paper of example 1, example 2, example 3, comparative example 1, comparative example 2, comparative example 3 were measured with an optical perspective Eye-one, then the color densities thereof were measured under an ozone atmosphere (ozone sterilizer) for 3 hours, and the color density decay rates of the color patches before and after the storage of the ozone sterilizer were calculated. The larger the color density attenuation rate is, the ozone tolerance is improved; the lower the inverse color density decay rate, the better the ozone resistance. Wherein, ozone-resistant color density decay rate= (color density before ozone disinfection cabinet storage-color density after ozone disinfection cabinet storage)/color density before ozone disinfection cabinet storage is 100%; test result data are shown in table 2 below.
TABLE 1
TABLE 2
From the test results shown in tables 1 and 2, the dyes prepared in examples 1, 2 and 3 have good light fastness and ozone resistance, that is, the dyes of the examples of the present application have good weather resistance. However, the dyes provided in comparative examples 1, 2 and 3 have a large attenuation rate, and have poor light fastness and ozone resistance, that is, the dyes provided in comparative examples 1, 2 and 3 have poor weather resistance. The c.i. direct black 19 of comparative example 1, the c.i. direct black 168 of comparative example 2, and the c.i. direct black 154 of comparative example 3 each do not contain the stilbenedisulfonic acid structure and the nitrobenzene group of the present application, and their weather resistance is significantly inferior to that of the present application. Compared with the structural formulas of c.i. direct black 19 of comparative example 1, c.i. direct black 168 of comparative example 2 and c.i. direct black 154 of comparative example 3, the dye provided by the application contains a stilbenedisulfonic structure (c=c bond), which indicates that the dye provided by the application contains a specific stilbenedisulfonic structure, and imparts good light fastness to the dye. The dye provided by the application also contains nitrobenzene groups, which indicates that the dye provided by the application contains specific nitrobenzene groups, and has good ozone resistance.
The foregoing description of the preferred embodiments of the application is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the application.
Claims (10)
1. The dye is characterized by having a molecular structural general formula I as follows:
wherein R in the general molecular structural formula 1 、R 2 、R 3 、R 4 、R 5 Are respectively and independently selected from alkali metal ions and NH [ (CH) 2 ) n OH] 3 + Any one of n is 1 to 5.
2. The dye of claim 1, wherein R 1 、R 2 、R 3 、R 4 、R 5 Are respectively and independently selected from Li + 、Na + 、NH(C 2 H 4 OH) 3 + Any one of them; and/or
R 1 、R 2 、R 3 、R 4 、R 5 All the same.
3. The dye according to claim 1 or 2, characterized in that it is selected from at least one of the following compounds of formula II, formula III, formula IV;
4. a process for the preparation of a dye according to any one of claims 1 to 3, comprising the steps of:
carrying out coupling reaction on a first reactant shown in a formula V, a second reactant shown in a formula VI and 2-amino-8-naphthol-6-sulfonic acid in an alkaline solution to obtain the dye;
5. the method of preparing as claimed in claim 4, wherein the step of coupling the first reactant of formula V, the second reactant of formula VI, and 2-amino-8-naphthol-6-sulfonic acid in a basic solution comprises:
the first reactant and the second reactant are subjected to a first coupling reaction in an alkaline solution, and then the 2-amino-8-naphthol-6-sulfonic acid is added to perform a second coupling reaction.
6. The process according to claim 5, wherein the first coupling reaction is carried out at a temperature of 20 to 30℃and a pH of 6 to 7 for a period of 5 to 15 minutes; and/or
The temperature of the second coupling reaction is 20-30 ℃, the pH value is 6-7, and the time is 3.5-4.5 h.
7. The method of preparing as claimed in claim 4, wherein the preparing step of the first reactant comprises: mixing nitroaniline solution and first nitrite solution to perform a first diazonium reaction to obtain nitroaniline diazonium salt solution; mixing a 1-amino-8-naphthol-3, 6-disulfonate solution and the nitroaniline diazonium salt solution for a third coupling reaction to obtain the first reactant; and/or
The preparation steps of the second reactant comprise: and mixing the 4,4 '-diaminostilbene-2, 2' -disulfonate solution with a second nitrite solution for a second diazonium reaction to obtain the second reactant.
8. The method of claim 7, wherein the conditions of the third coupling reaction comprise: the temperature is 18-20 ℃, and the pH value is 3.5-5; and/or
The alkaline solution comprises at least one of sodium hydroxide solution, lithium hydroxide solution and triethanolamine solution.
9. Use of a dye according to any one of claims 1 to 3 and/or a dye obtainable by a process according to any one of claims 4 to 8 in black digital inkjet printing ink.
10. The black digital ink-jet printing ink is characterized by comprising the following components in percentage by weight, based on 100% of the total weight of the black digital ink-jet printing ink:
1 to 15 percent of dye,
5-40% of organic solvent,
40-70% of water;
wherein the dye is a dye according to any one of claims 1 to 3 and/or a dye produced by the process for producing a dye according to any one of claims 4 to 8.
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