CN116217618A - A kind of modified colorant with triazine structure and its application - Google Patents
A kind of modified colorant with triazine structure and its application Download PDFInfo
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- 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
- C09D17/00—Pigment pastes, e.g. for mixing in paints
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- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
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- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
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- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having three nitrogen atoms as the only ring hetero atoms
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- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B68/00—Organic pigments surface-modified by grafting, e.g. by establishing covalent or complex bonds, in order to improve the pigment properties, e.g. dispersibility or rheology
- C09B68/40—Organic pigments surface-modified by grafting, e.g. by establishing covalent or complex bonds, in order to improve the pigment properties, e.g. dispersibility or rheology characterised by the chemical nature of the attached groups
- C09B68/42—Ionic groups, e.g. free acid
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
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- C09D17/00—Pigment pastes, e.g. for mixing in paints
- C09D17/004—Pigment pastes, e.g. for mixing in paints containing an inorganic pigment
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Abstract
The invention belongs to the field of pigment color paste, and particularly relates to a modified colorant with a triazine structure and application thereof. The structure of the modified colorant is shown as a general formula D1, and the anchoring group L anchors the modified colorant on the surface of the pigment particles in a physical adsorption or chemical bond modeAnd (3) modifying the surface of the pigment. The modifier colorant of the invention realizes effective regulation and control of hydrophilicity or lipophilicity of pigment by adjusting the types and the numbers of triazine substituents, and the nano pigment color paste treated by the modifier has self-dispersion property, does not need other auxiliary agents, can effectively improve the dispersibility, the stability and the filterability of the nano pigment color paste, and has excellent coloring capability.
Description
Technical Field
The invention belongs to the field of pigment color paste, and particularly relates to a modified colorant with a triazine structure and application thereof.
Background
The pigment color paste is prepared by mixing pigment with water or solvent, adding additives such as dispersant, etc., making the mixture become liquid, mixing with a high-speed mixer, and adding into a nanometer grinder to cut with zirconium beads at high speed to meet the requirement of the finished product. The pigment can adjust the wettability of the pigment in a dispersion medium through pigment treatment, so that the high-quality color paste with stable property and excellent performance is prepared.
The development thinking of high-quality nano water-based pigment color paste is developed around formulation technology and modification technology, namely, an auxiliary agent is added into the color paste to assist in dispersing pigment and increasing tinting strength, or a modifier is attached to the surfaces of dispersed particles, so that pigment particles are uniformly dispersed in a medium through intermolecular force and the tinting strength is improved. For example, in CN112358749a patent, adding blue dye into carbon black paste, and improving jetness and tinting strength of the paste by blue light, the scheme makes the compatibility system more complex, and limits the application range of the product; JP2018070816a by the japanese Canon company proposes to mix a modifier with a pigment in a medium under heating so that the modifier adheres to the surface of the pigment particles. However, the process requires subsequent refining treatment to remove the influence of the organic solvent, and the process is complex. The cabot company patents US 5851800, US5672198, US6641656, US6328894 and US6506245 propose a series of modifiers for color paste modification, but the precise control of key parameters of pigment color paste under the action of a single modifier cannot be realized. In addition, the common problem of the process is that the rule of each index of the pigment color paste is not explored. Although the invention provides a method for modifying the pigment surface, the color paste and the ink product cannot have the dispersibility, the stability and the tinting capability. In addition, the modification method cannot construct a structure-effect relationship aiming at dispersibility, stability and tinting strength, so that various performance parameters of the pigment color paste are accurately controlled.
Disclosure of Invention
The invention aims to provide a modified colorant with a triazine structure and application thereof, and the modified colorant can be applied to preparation of nano water-based pigment color paste with various colors such as blue, red, yellow, black, white, orange, green, purple, brown and the like and pigment varieties contained therein.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a modified colorant with triazine structure is shown in a general formula D1:
wherein:
l is selected from-B-Z-NH 2 ；
B is selected from N or O;
z is selected from C1-C6 alkyl, aryl, heteroaryl, aralkyl, heteroaralkyl, alkylaryl, alkylheteroaryl, unsubstituted or further substituted with hydroxy, sulfonate, carboxylate, nitro, amino, secondary amino, tertiary amino, or halogen;
A 1 、A 2 which may be the same or different, are each selected from halogen, -X-Q, phosphate groups, phosphonate groups, geminal bisphosphonate groups;
x is selected from N or O;
q is selected from hydrogen, alkoxy, C1-C18 alkyl, C1-C18 acyl, aryl, heteroaryl, aralkyl, heteroaralkyl, alkylaryl, alkylheteroaryl, optionally further substituted with hydroxy, sulfo, carboxylic, nitro, amino, secondary amino, tertiary amino or halogen;
Or a salt of a compound of formula D1.
In the general formula D1:
l is selected from-B-Z-NH 2 ；
B is selected from N or O;
z is selected from C1-C6 alkyl, aryl, heteroaryl which is unsubstituted or further substituted by a sulfonic acid group, carboxylic acid group;
A 1 、A 2 may be the same or different and are each selected from chlorine, fluorine, bromine, -X-Q or a phosphoric acid group, a phosphonic acid group, a geminal bisphosphonic acid group;
x is selected from N or O;
q is selected from hydrogen, alkoxy, C1-C18 alkyl, C1-C18 acyl, aryl, heteroaryl, aralkyl, heteroaralkyl, alkylaryl, alkylheteroaryl, optionally further substituted with hydroxy, sulfo, carboxylic, nitro, amino, secondary amino, tertiary amino or halogen;
or a salt of a compound of formula D1.
The A is 1 、A 2 And may be the same or different, and is selected from chlorine, fluorine, bromine, -X-Q, formula (a), formula (b), formula (c), formula (d), formula (e), formula (f) and formula (g);
x is selected from N or O;
q is selected from hydrogen, alkoxy, C1-C18 alkyl, C1-C18 acyl, aryl, heteroaryl, aralkyl, heteroaralkyl, alkylaryl, alkylheteroaryl, optionally further substituted with hydroxy, sulfo, carboxylic, nitro, amino, secondary amino, tertiary amino or halogen;
Formula (a) is-B- [ (CH) 2 )m(PO 3 H 2 )] 2 Wherein B is N or O, m=1-10;
formula (B) is-B-cr=c (PO 3 H 2 )(CO 2 H) Wherein B is N or O, R is H, C-C6 alkyl or aryl, heteroaryl which is unsubstituted or further substituted by a group such as sulfonic acid, carboxylic acid;
formula (c) is-B-CQ (PO) 3 H 2 )(CO 2 H) Wherein B is N or O and Q is H, R, OR, SR or NR 1 R 2 R is selected from H, C-C18 alkyl, C1-C18 acyl, aralkyl, heteroaryl or aryl, R 1 、R 2 May be the same or different and are each selected from H, C C18 alkyl, C1C 18 acyl, aralkyl, heteroaryl or aryl;
formula (d) is-B-CR (PO) 3 H 2 ) (OH) wherein B is N or O and R is H, C C6 alkyl or aryl, heteroaryl;
formula (e) is-B-CQ (PO) 3 H 2 ) 2 Wherein B is N or O and Q is H, R, OR, SR or NR 1 R 2 R is selected from H, C-C18 alkyl, C1-C18 acyl, aralkyl, heteroaryl or aryl, R 1 、R 2 May be the same or different and are each selected from H, C C18 alkyl, C1C 18 acyl, aralkyl, heteroaryl or aryl;
formula (f) is-B- (CH 2) n CQ(PO 3 H 2 ) 2 Wherein B is N or O, n=1-9, q is H, R, OR, SR or NR 1 R 2 R is selected from H, C-C18 alkyl, C1-C18 acyl, aralkyl, heteroaryl or aryl, R 1 、R 2 May be the same or different and are each selected from H, C C18 alkyl, C1C 18 acyl, aralkyl, heteroaryl or aryl;
Formula (g) is-B-Sp- (CH 2) n CQ(PO 3 H 2 ) 2 Wherein B is N or O, sp is-CO 2 -、-O-、-NR’、CO-、-CONR’、-SO 2 NR’、-SO 2 CH 2 CH 2 O-、-SO 2 CH 2 CH 2 S-; n=1 to 9, Q is H, R, OR,SR or NR 1 R 2 R is selected from H, C-C18 alkyl, C1-C18 acyl, aralkyl, heteroaryl or aryl, R 1 、R 2 May be the same or different and are each selected from H, C C1-C18 alkyl, C1-C18 acyl, aralkyl, heteroaryl or aryl, R' is cyano or C1-C6 alkyl.
Preferably, formula (a) is-B- [ (CH) 2 )m(PO 3 H 2 )] 2 Wherein B is selected from N, m=1-5;
formula (B) is-B-cr=c (PO 3 H 2 )(CO 2 H) Wherein B is selected from N, R is H, C1-C6 alkyl or aryl, heteroaryl which is unsubstituted or further substituted with a sulfonate group, a carboxylate group;
formula (c) is-B-CQ (PO) 3 H 2 )(CO 2 H) Wherein B is selected from N, Q is H, R, OR, SR or NR 1 R 2 R is selected from H, C-C6 alkyl, C1-C6 acyl, aralkyl, heteroaryl or aryl, R 1 、R 2 May be the same or different and are each selected from H, C C1-C6 alkyl, C1-C6 acyl, aralkyl or aryl;
formula (d) is-B-CR (PO) 3 H 2 ) (OH), wherein B is selected from N, R is H, C-C6 alkyl or aryl, heteroaryl;
formula (e) is-B-CQ (PO) 3 H 2 ) 2 Wherein B is selected from N, Q is H, R, OR, SR or NR 1 R 2 R is selected from H, C-C6 alkyl, C1-C6 acyl, aralkyl, heteroaryl or aryl, R 1 、R 2 May be the same or different and are each selected from H, C C1-C6 alkyl, C1-C6 acyl, aralkyl, heteroaryl or aryl;
Formula (f) is-B- (CH 2) n CQ(PO 3 H 2 ) 2 Wherein B is selected from N, n=1-6,Q is H, R, OR, SR or NR 1 R 2 R is selected from H, C-C6 alkyl, C1-C6 acyl, aralkyl, heteroaryl or aryl, R 1 R 2 May be the same or different and are each selected from H, C C1-C6 alkyl, C1-C6 acyl, aralkyl, heteroaryl or aryl;
formula (g) is-B-Sp- (CH 2) n CQ(PO 3 H 2 ) 2 Wherein B is selected fromFrom N, sp is-CO 2 -、-O-、-NR’、CO-、-CO NR’、-SO 2 NR’、-SO 2 CH 2 CH 2 O-、-SO 2 CH 2 CH 2 S-; n=1 to 9, q is H, R, OR, SR or NR 1 R 2 R is selected from H, C-C6 alkyl, C1-C6 acyl, aralkyl, heteroaryl or aryl, R 1 、R 2 May be the same or different and are each selected from H, C C1-C6 alkyl, C1-C6 acyl, aralkyl, heteroaryl or aryl, R' is cyano or C1-C6 alkyl.
Further, in formula D1;
l is selected from-B-Z-NH 2 ；
B is selected from N or O;
z is selected from C1-C6 alkyl, phenyl which is unsubstituted or further substituted by sulfonic acid groups, carboxylic acid groups;
A 1 、A 2 and may be the same or different, and is selected from chlorine, fluorine, bromine, -X-Q, formula (a), formula (b), formula (c), formula (d), formula (e), formula (f) and formula (g);
x is selected from N or O;
q is selected from hydrogen, alkoxy, C1-C18 alkyl, C1-C18 acyl, phenyl, pyridine, unsubstituted or further substituted with a sulfonate, carboxylate;
Formula (a) is-B- [ (CH) 2 )m(PO 3 H 2 )] 2 Wherein B is selected from N, m=1-3;
formula (B) is-B-cr=c (PO 3 H 2 )(CO 2 H) Wherein B is selected from N, R is H, C1-C6 alkyl or phenyl, pyridine which is unsubstituted or further substituted by a group such as sulfonic acid group, carboxylic acid group;
formula (c) is-B-CQ (PO) 3 H 2 )(CO 2 H) Wherein B is selected from N, Q is H, R, OR, SR or NR 1 R 2 R is selected from C1-C6 alkyl, phenyl, pyridine or benzyl, R 1 、R 2 May be the same or different and are each selected from C1-C6 alkyl, phenyl, pyridine or benzyl;
formula (d) is-B-CR (PO) 3 H 2 ) (OH) whereinB is selected from N, R is H, C-C6 alkyl or phenyl, pyridine;
formula (e) is-B-CQ (PO) 3 H 2 ) 2 Wherein B is selected from N, Q is H, R, OR, SR or NR 1 R 2 R is selected from C1-C6 alkyl, phenyl, pyridine or benzyl; r is R 1 、R 2 May be the same or different and are each selected from C1-C6 alkyl, phenyl, pyridine or benzyl;
formula (f) is-B- (CH 2) n CQ(PO 3 H 2 ) 2 Wherein B is selected from N, n=1-6,Q is H, R, OR, SR or NR 1 R 2 R is selected from C1-C6 alkyl, phenyl, pyridine or benzyl; r is R 1 、R 2 May be the same or different and are each selected from C1-C6 alkyl, phenyl, pyridine or benzyl;
formula (g) is-B-Sp- (CH 2) n CQ(PO 3 H 2 ) 2 Wherein B is selected from N, sp is-CO 2 -、-O-、-NR’、CO-、-CONR’、-SO 2 NR’、-SO 2 CH 2 CH 2 O-、-SO 2 CH 2 CH 2 S-; n=1 to 9, q is H, R, OR, SR or NR 1 R 2 R is selected from C1-C6 alkyl, phenyl, pyridine or benzyl; r is R 1 、R 2 May be the same or different and are respectively selected from C1-C6 alkyl, R is selected from C1-C6 alkyl, phenyl, pyridine or benzyl; r' is cyano or C1-C6 alkyl;
or a salt of a compound of formula D1.
Examples of some preferred specific substituents for compounds of formula D1 according to the invention are given in Table 1:
TABLE 1
In the application of the modified colorant, the anchoring group L anchors the modified colorant on the surface of pigment particles in a physical adsorption or chemical bond mode, so as to realize the surface modification of the pigment.
The specific modified colorant with triazine structure related to the invention can be applied to pigment modification of known various colors, such as black, red, green, blue, orange, purple, brown, yellow, orange and white, and comprises and is not limited to the following pigment varieties, such as pigment black 1, 7, 31, 32, carbon black, furnace black, lamp black, gas black and the like; pigment red 1, 2, 3, 4, 5, 7, 8, 9, 10, 11, 12, 13, 16, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 48: 1. 48: 2. 48: 3. 48: 4. 49: 1. 49: 2. 52: 1. 53: 1. 53: 2. 53: 3. 54, 57: 1. 55, 58: 1. 58: 2. 60, 62, 63: 1. 63: 2. 68, 81, 88, 90, 112, 122, 123, 140, 141, 142, 143, 144, 146, 148, 149, 150, 151, 163, 164, 166, 168, 170: 1. 171, 175, 176, 177, 178, 179, 181, 183, 184, 185, 188, 189, 190, 194, 195, 196, 201, 202, 207, 208, 209, 214, 217, 218, 220, 221, 223, 224, 242, 245, 247, 248, 251, 253, 254, 255, 256, 260, 264, 266, 268, 269, 272, 279, etc.; pigment violet 1, 3, 5: 1. 6, 7, 19, 20, 23, 27, 29, 31, 32, 33, 36, 37, 38, 39, 50, etc.; pigment yellow 1, 1: 1. 2, 3, 5, 6, 7, 9, 10, 12, 13, 14, 15, 16, 17, 23, 24, 55, 61, 62, 63, 65, 73, 74, 75, 81, 83, 93, 94, 95, 97, 98, 101, 108, 109, 110, 111, 113, 114, 117, 120, 121, 123, 124, 126, 127, 128, 129, 138, 139, 147, 150, 151, 153, 154, 155, 156, 166, 168, 170, 171, 173, 174, 175, 176, 177, 179, 180, 181, 182, 183, 185, 188, 190, 191): 1. 192, 194, 202, 203, 213, etc.; pigment blue 1, 10, 15: 1. 15: 6. 15: 3. 15: 4. 16, 17, 22, 26, 60, 61, 64, 65, 75, 79, 80, etc.; titanium white, calcium white, magnesium white, and the like; pigment orange 1, 5, 13, 14, 15, 16, 18, 19, 22, 24, 31, 34, 36, 38, 40, 43, 44, 49, 55, 59, 61, 62, 64, 65, 66, 67, 68, 69, 71, 73, 74, 77, etc.; pigment brown 1, 23, 26, 27, 28, 38, 41, 42, etc.; pigment green 1, 4, 7, 8, 36, 37, 47, 58, etc.
Further, the pigment is a blue pigment, a black pigment, a brown pigment, a cyan pigment, a green pigment, a white pigment, a violet pigment, a red pigment, a yellow pigment, an orange pigment, or a mixture thereof.
In a further embodiment, the pigment is pigment blue 15, pigment blue 15:3, pigment blue 15:4, pigment red 122, pigment violet 19, pigment yellow 74, pigment yellow 155, pigment yellow 128, pigment yellow 218, pigment yellow 220, pigment yellow 211, or carbon black.
In order to ensure the modification efficiency and to avoid repeating the modification treatment a plurality of times, the primary particle diameter of the pigment selected should preferably be in the range of 5 to 100nm, more preferably 10 to 80nm, most preferably 20 to 75nm. The pigment coarse particles can be pretreated by adopting crushing methods such as acid precipitation, wet grinding, ball milling, mixing, ultrasonic dispersion and the like, so as to obtain pigment fine particles with proper primary particle size. Furthermore, the BET surface area of the pigment should preferably be 20m 2 /g-700m 2 Preferably 30m 2 /g-500m 2 Per g, most preferably 50m 2 /g-350m 2 Per g, this value can be determined by nitrogen adsorption experiments. The oil absorption of the pigment, which also has an effect on the modification efficiency, is preferably from 0.5g/100g to 3g/100g, more preferably from 0.7g/100g to 1.5g/100g, most preferably from 0.8g/100g to 1.1g/100g, using linseed oil as the test medium.
Compared with the prior art, the invention has the advantages that:
the pigment surface property has a great influence on the pigment application performance, and the surface modification of the pigment is realized by introducing various different functional groups to the pigment surface through physical adhesion or chemical bonding of the modified colorant and the pigment surface. For the nano water-based pigment color paste, the obtained color paste product can have dispersibility, stability and tinting capability by modifying the pigment surface, and the color paste product needs to be modified by using modified colorants containing different functional groups. The invention relates to a specific pigment modified colorant with a triazine structure, wherein the chlorine groups of the cyanuric chloride with an aromatic ring structure have good activity, are easy to generate substitution reaction to introduce various functional groups, can contain functional groups with multiple functions in one modified colorant structure, optimize the pigment modification process, simplify the formula of nano water-based pigment color paste, and avoid the application limitation, thereby expanding the application range and improving the suitability.
On one hand, the modified pigment color paste can effectively improve the modification efficiency, simplify the modification formula and optimize the pigment treatment process, and more importantly, the nano water-based pigment color paste obtained after the modified colorant treatment can realize the self-dispersion function, namely, the nano dispersion effect can be realized without adding auxiliary agents such as a surfactant, a dispersing agent, a wetting agent and the like, and can simultaneously have the stability and the coloring capability.
The modification method of the modified colorant with the special triazine structure can be a physical method, namely, pigment and the modified colorant are mixed in the processes of grinding, ball milling, ultrasonic dispersion, mixing and mechanical stirring, and the anchoring group of the modifier generates adsorption action with the conjugated structure of pigment molecules through Van der Waals force and dispersion force, so that the modified colorant is attached to the surface of pigment particles. In addition, the modified colorant can also be bonded with pigment molecules through chemical reactions such as diazotization, etherification, acylation, esterification and the like to generate modified pigment molecules, and the modified pigment molecules are coated on the outermost layer of the pigment particles in the pigment wetting process. The modified pigment particles have functional groups exposed out of the outer layers of the pigment particles, so that on one hand, ionization occurs in a dispersion medium, and an electric double layer is formed on the surfaces of the pigment particles, so that pigment particles are mutually repelled, and on the other hand, hydrophilic functional groups can promote the wetting action of the pigment particles and the dispersion medium, so that the dispersibility is improved. The pigment color paste prepared by the modified colorant has the advantages of good filterability, strong tinting strength, stable heat storage (small change rate of particle size after 7 days of heat storage) and the like, and has advantages in the application of code-spraying ink.
Functional group A 1 、A 2 Specific phosphoric acid groups, phosphonic acid groups, sulfonic acid groups, carboxylic acid groupsThe salt thereof can complex with metal ions, particularly calcium ions, to improve the coloring ability, and thus, the parameter of introducing a calcium index value is defined as the number of the complexing calcium ions per molecule of the modified colorant (for the case of the composite use of the modified colorant, the calculation is performed after weighting according to the mass ratio). The modified colorant preferably has a calcium index value of 1.2 to 8, more preferably 1.5 to 6, and most preferably 2.5 to 5. In addition to functional groups A 1 、A 2 The specific halogen, conjugated structure and polymer group have steric hindrance effect, and inhibit agglomeration and flocculation among pigment particles to a certain extent.
The modifier colorant realizes effective regulation and control on the hydrophilicity or lipophilicity of the pigment by adjusting the types and the numbers of triazine substituents. The nano pigment color paste treated by the modifier has self-dispersion performance, does not need to add other auxiliary agents, can effectively improve the dispersion, stability and filterability of the nano pigment color paste, and has excellent coloring capability.
Detailed Description
The embodiment of the invention relates to a specific pigment modified colorant with a triazine structure, which has a triazine main structure with an anchoring function, and the hydrophilic property or the lipophilic property of a pigment can be effectively regulated and controlled by adjusting the types and the numbers of triazine substituents. The invention discloses the modified colorant and the implementation scheme of the modified colorant applied to the preparation of the nano pigment color paste, the nano pigment color paste treated by the modified colorant has self-dispersion performance, no other auxiliary agent is needed, the dispersibility, the stability and the filterability of the nano pigment color paste can be effectively improved, and the nano pigment color paste has excellent coloring capability.
In the embodiment, the evaluation index and the evaluation method for the nano water-based pigment color paste comprise the following aspects:
(1) Particle size and particle size distribution
Diluting a small amount of color paste with distilled water to 300-500kcps, placing the sample in a cuvette with 1cm x 1cm, testing in a nanoBrook nanometer particle sizer, and averaging five groups of data under 25 deg.C
(2) Viscosity of the mixture
The color paste was placed in a sample cell and the viscosity of the color paste sample was measured using a Brookfield DV2T viscometer No. 0 spindle at 25 ℃.
(3) Filterability
The color paste sample is placed in a filter, and a polypropylene filter membrane with the aperture of 0.45 mu m and a glass fiber filter membrane are respectively used for filtering, and the time required for filtering 1L of color paste under the conditions of 25 ℃ and 0.3Mpa is recorded for measuring the filterability of the color paste sample.
(4) Coloring ability
The color paste sample is prepared into ink, the ink is applied by a printer, and the obtained ink-jet sample is subjected to Lab test on the coloring capability.
(5) Thermal storage and cold storage stability
Two groups of 20ml color paste samples are taken, respectively placed in two sample bottles made of PET materials and sealed by a screw cap, the sample bottles are respectively placed in an environment of 60 ℃ for 7 days, and then each parameter of the sample bottles is tested. And if the relative change rate of each physicochemical index is less than 10%, evaluating the stability of the color paste to be qualified.
Example 1 preparation of modified colorant 1
200ml of distilled water and 21g (0.1 mol) of sodium 2, 4-diaminobenzenesulfonate were charged into a 500ml four-necked flask, and the mixture was cooled to 0-5℃with stirring, 18.41g (0.1 mol) of cyanuric chloride was added in portions, and the reaction was continued for 3 hours. The reaction solution was heated to 20-25℃and 29.7g (0.1 mol) of p- (1, 1-diphosphate-1-hydroxyethane) aniline was added in portions, followed by stirring for 3 hours under heat preservation, and then the pH of the reaction solution was adjusted to less than 1 using concentrated hydrochloric acid to precipitate a reddish brown solid. The filter cake was filtered, washed with water and dried at 60℃for 5 hours to give 56.2g (0.91 mol) of a brown solid of modified colorant 1 with an HPLC content of 98.55% in 91% yield. m.p.265-268 ℃. M/z= 596.00
1 H-NMR(600MHz，DMSO-D6)δ:1.49-1.52ppm(s，2H,CH 2 ),2.71ppm(s，1H,COH),3.35ppm(t，2H,NHCH2CH 2 ),4.88ppm(s，4H,POH),5.90ppm(s，2H,NH 2 ),6.05ppm(d，1H,CHCH)，6.60ppm(d，1H,CHCH)，7.11ppm(s，1H,NH 2 ),7.36ppm(d，1H,CHCH)，8.33ppm(s，H,NH)；
Example 2 preparation of modified colorant 2
200ml of distilled water, 18.8g (0.1 mol) of 2, 4-diaminobenzenesulfonic acid, 8.4g (0.1 mol) of sodium bicarbonate were added to a 500ml four-necked flask, and the mixture was cooled to 0-5℃with stirring, 18.41g (0.1 mol) of cyanuric chloride was added in portions, and the mixture was reacted at a constant temperature for 6 hours. The reaction solution was heated to 20-25℃and 32.6g (0.1 mol) of (4-amino-1-hydroxy-1-phosphate-butyl) -phosphate sodium salt trihydrate was added in portions, followed by stirring for 8 hours under heat preservation, and then the pH of the reaction solution was adjusted to less than 1 using concentrated hydrochloric acid to precipitate a tan solid. The filter cake was filtered, washed with water and dried at 60℃for 5 hours to give 55g (0.086 mol) of a pale yellow solid of modified colorant 2, with an HPLC content of 97.36% and a yield of 86%. m.p.245-247 ℃. M/z= 548.79
1 H-NMR(600MHz，DMSO-D6)δ:1.49-1.52ppm(m，4H,CH 2 CH 2 ),2.21ppm(s，1H,COH),3.35ppm(t，2H,NHCH2CH 2 ),4.88ppm(s，4H,POH),5.90ppm(s，2H,NH 2 ),6.05ppm(d，1H,CHCH)，6.60ppm(d，1H,CHCH)，7.11ppm(s，1H,NH 2 ),7.36ppm(d，1H,CHCH)，8.33ppm(s，1H,NH)；
Example 3 preparation of modified colorant 3
200ml of distilled water, 7.51g (0.1 mol) of glycine, 8.4g (0.1 mol) of sodium bicarbonate were added to a 500ml four-necked flask, and the mixture was cooled to 0-5℃with stirring, 18.41g (0.1 mol) of cyanuric chloride was added in portions, and the mixture was reacted at a constant temperature for 2 hours. The reaction mixture was heated to 10-15℃and 29.7g (0.1 mol) of (1, 1-diphosphate-1-hydroxyethane) ylamine was added in portions, and after stirring for 4 hours under heat preservation, the pH of the reaction mixture was adjusted to less than 1 using concentrated hydrochloric acid to precipitate a tan solid. Filtering the water washing filter cake, placing the wet filter cake into a 500ml four-neck flask, adding 200ml distilled water for pulping, adding 10.8g (0.1 mol) of p-phenylenediamine in batches, adding for 15 minutes, stirring, heating to 20-25 ℃ and preserving heat for reaction for 3 hours. The filter cake was filtered and washed to give 34.7g (0.0749 mol) of modified colorant 3 as a reddish brown solid. HPLC content 95.88%, yield 74.9%.
m.p.245-247℃。M/Z＝548.79
1 H-NMR(600MHz，DMSO-D6)δ:1.12ppm(s，3H,CCH 3 ),4.02ppm(s，2H,NHCH 2 ),4.88ppm(s，4H,POH),5.90ppm(s，2H,NH),6.05ppm(d，2H,CHCH)，6.25ppm(d，2H,CHCH)，7.11ppm(s，2H,PhNH 2 ),7.36ppm(d，1H,CHCH)，8.33ppm(s，1H,Ph NH)；
Example 4 preparation of modified colorant 4
200ml of distilled water, 28.26g (0.1 mol) of L-glutamic acid and 16.8g (0.2 mol) of sodium bicarbonate were added to a 500ml four-necked flask, and the mixture was cooled to 0-10℃with stirring, 18.41g (0.1 mol) of cyanuric chloride was added in portions, and the mixture was reacted at a constant temperature for 6 hours. Heating the reaction solution to 25-30 ℃, adding 6.0g (0.1 mol) of ethylenediamine in batches, keeping the temperature and stirring for 4 hours, and then adjusting the pH of the reaction solution to be less than 1 by using concentrated hydrochloric acid to separate out yellowish solid. The filter cake was filtered and washed with water and dried at 60℃for 5 hours to give 38.5g (0.089 mol) of a pale yellow solid of the modified colorant 4. HPLC content 97.82%, yield 89%. m.p.295-297 ℃.
M/Z＝429.16
1 H-NMR(600MHz，DMSO-D6)δ:2.01ppm(q，4H,CHCH 2 CH 2 ),2.33ppm(t，4H,CHCH 2 CH 2 ),2.73ppm(t，2H,CH 2 CH 2 NH 2 ),3.50ppm(t，2H,NHCH 2 CH 2 NH 2 ),3.74ppm(t，2H,NHCHCH 2 )5.32ppm(s，2H,NHPh),5.62ppm(s，1H,NHPh),5.62ppm(s，2H,NHCH 2 CH 2 NH 2 )，8.12ppm(s，2H,OH)；8.35ppm(s，1H,OH)；
Example 5 preparation of modified colorant 5
200ml of distilled water, 13.8g (0.1 mol) of 3-amino-2-carboxylic pyridine, 8.4g (0.1 mol) of sodium bicarbonate, and 18.41g (0.1 mol) of cyanuric chloride were added in portions to a 500ml four-necked flask, and the mixture was stirred and cooled to 0-5℃and reacted for 4 hours. The reaction mixture was heated to 25-30℃and 6.0g (0.1 mol) of ethylenediamine was added in portions, stirred for 4 hours at a constant temperature, and then heated to 50℃and kept at that temperature for 1 hour. The pH of the reaction solution was adjusted to less than 1 with concentrated hydrochloric acid, and a white solid was precipitated. The filter cake was filtered and washed with water and dried at 60℃for 5 hours to give 22.2g (0.763 mol) of modified colorant 5 as a white solid. HPLC content 98.32%, yield 76.3%. m.p.154-156 ℃. M/z= 291.11
1 H-NMR(600MHz，DMSO-D6)δ:2.25ppm(s，2H,CH 2 CH 2 NH 2 ),2.73ppm(t，2H,CH 2 CH 2 NH 2 ),3.50ppm(t，2H,NHCH 2 CH 2 NH 2 ),6.52ppm(s，2H,NHCH 2 CH 2 NH 2 )7.83ppm(d，1H,CHPh),7.93ppm(d，1H,CHPh),8.12ppm(s，1H,NHPh)8.51ppm(s，1H,OHPh)。
Example 6 preparation of modified colorant 6
200ml of methanol, 27.2g of water and 16.8g (0.2 mol) of sodium bicarbonate are added into a 500ml four-necked flask, stirred and cooled to-5-0 ℃, 39.85g (0.216 mol) of cyanuric chloride is added in portions, the reaction is carried out for 8 hours under heat preservation, filtration and washing of a filter cake with 100ml of cold water are carried out, and 29.54g (0.164 mol) of white powdery solid is obtained; HPLC content 94.30%, yield 82%. m.p.124-125 ℃. M/z= 178.97
14.86g (0.083 mol) of solid compound (1 a), 40g of acetone, 11.2g (0.0896 mol) of taurine, 50ml of water and 9.0g (0.0849 mol) of sodium carbonate are sequentially added into a 250ml four-neck flask, the mixture is stirred at room temperature, a reaction solution is clarified first and then white solid is separated out, the reaction solution is filtered after 5 hours of reaction, and a filter cake is washed by acetone to obtain 22.29g (0.0829 mol) of white powdery solid compound (1 b); HPLC content 98.30% with 92.59% yield. m.p.221-223 ℃. M/z= 268.00
1 H-NMR(600MHz，DMSO-D6)δ:2.53ppm(s，1H,SO 3 H),3.62ppm(t，2H,CH 2 CH 2 SO 3 H),3.78ppm(t，2H,CH 2 CH 2 SO 3 H),3.83ppm(s，3H,PhOCH 3 )。
Into a 250ml four-neck flask, 11.0g (0.041 mol) of compound (1 b) and 100ml of water are added, the mixture is stirred to be completely dissolved, 4.32g (0.041 mol) of p-phenylenediamine is added in portions at room temperature, the addition is completed for 15min, the reverse solution changes from reddish to brown in the process of addition, the reaction is stirred for 3h, and white solid is precipitated in the reaction solution. The filter cake was filtered and washed with water, and the wet cake was air dried naturally to give 8.62g (0.025 mol) of a gray powdery solid as modified colorant 6.HPLC content 96.26%, yield 63.38%. m.p.258-260 ℃. M/z= 340.10
1 H-NMR(600MHz，DMSO-D6)δ:2.53ppm(s,1H,SO 3 H),3.62ppm(t,2H,CH 2 CH 2 SO 3 H),3.78ppm(t,2H,CH 2 CH 2 SO 3 H),3.83ppm(s,3H,PhOCH 3 ),6.05ppm(d，2H,CHPh，6.25ppm(d，2H,CHPh)，7.11ppm(s，2H,PhNH 2 ),7.36ppm(d，1H,CHPh)，8.33ppm(s，1H,Ph NH)。
EXAMPLE 7 preparation of modified colorant 7
To a 500ml four-necked flask, 18.42g (0.1 mol) of cyanuric chloride, 200g of distilled water, 21.6g (0.257 mol) of sodium hydrogencarbonate were added, and stirred at 15℃for 10 minutes, followed by adding 50.0g (0.025 mol) of polyetheramine (Mw=2000) to the four-necked flask at constant temperature, and stirring at constant temperature for 2 hours. Then, 32.7g of (4-amino-1-hydroxy-1-phosphate-butyl) -phosphate sodium salt trihydrate and 21.0g (0.25 mol) of sodium hydrogencarbonate were added to the reaction system, and the mixture was stirred and heated to 35-40℃and kept for 5 hours. 10.8g (0.1 mol) of p-phenylenediamine and 9.0g (0.083 mol) of sodium carbonate are added into the system, stirred and heated to 90 ℃ and then the temperature is kept for 12 hours. Then cooling to 25 ℃, dropwise adding hydrochloric acid, adjusting the pH of the reaction solution to 1.0, stirring for 1h at a constant temperature, filtering, and placing the filter cake in a blast drying oven at 80 ℃ for drying for 2h to obtain 72.5g of 7-purple powder solid of the modified colorant. Yield 76.23%
Example 8 preparation of K-1 from carbon black-modified color paste
Into a 2L four-necked flask, 100g of carbon black pigment dry powder, 34g (0.057 mol) of modified colorant 1, 700g of distilled water and 6.83g (0.068 mol) of concentrated hydrochloric acid were added, and after stirring uniformly, 23.23g (0.0673 mol) of 20% sodium nitrite aqueous solution was slowly dropped, and the dropping was completed within 1 hour. Then the temperature is raised to 40-45 ℃ with stirring and the mixture is kept for 16 hours. Cooling the color paste to room temperature, and adjusting the pH to 8.0-9.0 with 30% sodium hydroxide aqueous solution. Then the nano water-based carbon black pigment color paste K-1 is obtained after membrane filtration treatment.
Example 9 preparation of K-2 from modified color paste of Nano carbon black
Into a 2L four-necked flask, 100g of a dry powder of a carbon black pigment, 27g (0.0453 mol) of a modified colorant 2, 700g of distilled water and 4.77g (0.047 mol) of concentrated hydrochloric acid were added, and after stirring uniformly, 19.0g of a 20% (0.055 mol) aqueous solution of sodium nitrite was slowly dropped, and the dropping was completed within 1 hour. Then stirring and heating to 35-40 ℃ and preserving heat for 16 hours. Cooling the color paste to room temperature, and adjusting the pH to 8.0-9.0 by using 30% sodium hydroxide aqueous solution. Then the nano water-based carbon black pigment color paste K-2 is obtained after membrane filtration treatment.
Example 10 preparation of K-3 from modified color paste of Nano carbon black
Into a 2L four-necked flask, 100g of carbon black pigment dry powder, 16.8g (0.036 mol) of modified colorant 3, 700g of distilled water and 6.9g (0.069 mol) of concentrated hydrochloric acid were added, and after stirring uniformly, 12.4g (0.036 mol) of 20% sodium nitrite aqueous solution was slowly dropped, and the dropping was completed within 1 hour. Then the temperature is raised to 40-45 ℃ with stirring and the mixture is kept for 16 hours. Cooling the color paste to room temperature, and adjusting the pH to 8.0-9.0 by using 30% sodium hydroxide aqueous solution. Then the nano water-based carbon black pigment color paste K-3 is obtained after membrane filtration treatment.
Example 11 preparation of K-4 from modified color paste of Nano carbon black
Into a 2L four-necked flask, 100g of a dry powder of a carbon black pigment, 54g (0.090 mol) of a modified colorant 4, 700g of distilled water and 9.62g (0.0962 mol) of concentrated hydrochloric acid were added, and after stirring uniformly, 31.5g (0.09 mol) of a 20% aqueous solution of sodium nitrite was slowly dropped, and the dropping was completed within 1 hour. Then the temperature is raised to 40-45 ℃ with stirring and the mixture is kept for 16 hours. Cooling the color paste to room temperature, and adjusting the pH to 8.0-9.0 by using 30% sodium hydroxide aqueous solution. Then the nano water-based carbon black pigment color paste K-4 is obtained after membrane filtration treatment.
Example 12 preparation of K-5 from modified color paste of Nano carbon black
Into a 2L four-necked flask, 100g of carbon black pigment dry powder, 16.8g (0.036 mol) of modified colorant 5, 700g of distilled water and 4.77g (0.0477 mol) of concentrated hydrochloric acid were added, and after stirring uniformly, 12.42g (0.056 mol) of 20% sodium nitrite aqueous solution was slowly dropped, and the dropping was completed within 1 hour. Then the temperature was raised to 40℃with stirring and kept for 16 hours. Cooling the color paste to room temperature, and adjusting the pH to 8.0-9.0 by using 30% sodium hydroxide aqueous solution. Then the nano water-based carbon black pigment color paste K-5 is obtained after membrane filtration treatment.
Example 13 preparation of K-6 from modified color paste of Nano carbon black
Into a 2L four-necked flask were charged 100g of a carbon black pigment dry powder, 700g of distilled water, and 19.4g (0.0322 mol) of a modified colorant 6. 19.14g (0.055 mol) of 20% sodium nitrite solution are subsequently heated with stirring to 40℃and incubated for 16 hours. Cooling the color paste to room temperature, and adjusting the pH to 8.0-9.0 by using 30% sodium hydroxide aqueous solution. Then the nano water-based carbon black pigment color paste K-6 is obtained after membrane filtration treatment.
Examples 14-21 were conducted in the same manner as in examples 8-13 to obtain nano aqueous carbon black pigment pastes K-7 to K-15.
EXAMPLE 22 nanopigment modification of M-16
43g (0.0721 mol) of modified colorant 1, 100g of distilled water and 14.42g (0.144 mol) of concentrated hydrochloric acid are added into a 1L four-necked flask, and stirred in an ice bath, and the temperature of the reaction solution is controlled to be 0-5 ℃. Then 37.37g (0.0879 mol) of 20% potassium nitrite aqueous solution was slowly added dropwise, and the temperature of the reaction solution was controlled at 5-10 ℃. Into a 2L four-necked flask, 100g (0.294 mol) of pigment Red 122 dry powder and 600g of distilled water were further charged, and the temperature was raised to 70℃with stirring. And adding the diazonium solution of the modified colorant 1 into the pigment red 122 dispersion, keeping the reaction temperature at 70-75 ℃ in the adding process, and keeping the temperature for 12-14 hours after the dripping is completed within 1 hour. Cooling to room temperature, and regulating pH to 8.0-9.0 with 30% potassium hydroxide water solution. Then the nanometer water-based pigment red 122 color paste 16 is obtained after membrane filtration treatment.
Example 23 preparation of color paste sample M-17 by pigmenting modification
Into a 1L four-necked flask, 33g (0.060 mol) of modified colorant 2, 100g of distilled water and 12g (0.12 mol) of concentrated hydrochloric acid were charged, and the temperature was lowered to 0-5℃in an ice bath. Then 28.66g (0.06 mol) of 20% potassium nitrite aqueous solution is slowly added dropwise, the temperature of the reaction solution is controlled between 0 ℃ and 10 ℃ and the reaction is carried out for 1 hour, thus obtaining the modifier diazonium solution.
Into another 2L four-necked flask, 100g (0.294 mol) of pigment Red 122 dry powder and 600g of distilled water were charged, and the temperature was raised to 70℃and stirred. Adding the diazonium solution of the modifier in batches, controlling the temperature to be 70-75 ℃ and keeping the temperature, and after the addition is completed within 1 hour, keeping the temperature and reacting for 12-14 hours. Cooling to room temperature, and regulating pH to 8.0-9.0 with 30% potassium hydroxide water solution. Then the nanometer water-based pigment red 122 color paste 17 is obtained after membrane filtration treatment.
Examples 24-27 were operated in the same manner as examples 22-23 to prepare nano aqueous pigment red 122 paste M18-M21.
Example 28 preparation of color paste sample V-22 by pigmenting modification
43g (0.0721 mol) of modified colorant 1, 100g of distilled water and 14.42g (0.144 mol) of concentrated hydrochloric acid are added into a 1L four-necked flask, and stirred in an ice bath, and the temperature of the reaction solution is controlled to be 0-5 ℃. Then 37.37g (0.0879 mol) of 20% potassium nitrite aqueous solution was slowly added dropwise thereto, and the temperature of the reaction solution was controlled at 0-10 ℃. And reacting for 1 hour to obtain the modifier diazonium solution.
Into another 2L four-necked flask, 100g (0.263 mol) of pigment violet 19 dry powder and 600g of distilled water were charged, and the temperature was raised to 70-75 ℃. Adding the diazonium solution of the modifier in batches, controlling the temperature to be 70-75 ℃ and keeping the temperature, and after the addition is completed within 1 hour, keeping the temperature and reacting for 10-14 hours. Cooling to room temperature, and regulating pH to 8.0-9.0 with 30% potassium hydroxide water solution. And then the nano water-based pigment violet 19 color paste 22 is obtained after membrane filtration treatment.
Example 29 preparation of color paste sample V-23 by pigmenting modification
Into a 1L four-necked flask, 39.0g (0.114 mol) of a modified colorant 6, 100g of distilled water and 22.4g (0.228 mol) of concentrated hydrochloric acid were charged, and the mixture was stirred in an ice bath to control the temperature of the reaction solution to 0-5 ℃. Then 37.37g (0.133 mol) of 20% potassium nitrite aqueous solution is slowly added dropwise, the temperature of the reaction solution is controlled between 0 ℃ and 5 ℃ in the process, and the reaction is carried out for 1 hour, thus obtaining the modifier diazonium solution.
Into another 2L four-necked flask, 100g (0.263 mol) of pigment violet 19 dry powder and 600g of distilled water were charged, and the temperature was raised to 70-75℃and stirred. Adding the diazonium solution of the modifier in batches, controlling the temperature to be 70-75 ℃ and keeping the temperature, and after the addition is completed within 1 hour, keeping the temperature and reacting for 12-14 hours. Cooling to room temperature, and regulating pH to 8.0-9.0 with 30% potassium hydroxide water solution. Then membrane filtration treatment is carried out, and then membrane filtration treatment is carried out, thus obtaining the nano water-based pigment violet 19 color paste 23.
Example 30 preparation of color paste sample M-24 by pigmenting modification
43.0g (0.0721 mol) of modified colorant 1, 100g of distilled water and 22.4g (0.228 mol) of concentrated hydrochloric acid are added into a 1L four-necked flask, and the mixture is stirred in an ice bath, and the temperature of the reaction solution is controlled to be 0-5 ℃. Then 37.37g (0.133 mol) of 20% potassium nitrite aqueous solution is slowly added dropwise, the temperature of the reaction solution is controlled between 0 ℃ and 5 ℃ in the process, and the reaction is carried out for 1 hour, thus obtaining the modifier diazonium solution.
Into another 2L four-necked flask, 80.0g (0.233 mol) of pigment Red 122 dry powder, 20.0g (0.052 mol) of pigment Violet 19 dry powder, 600g of distilled water were charged, and the temperature was raised to 70-75℃and stirred. And adding a diazonium solution of a modifier into the pigment red 122/pigment violet 19 mixed dispersion liquid, controlling the temperature to be 70-75 ℃, keeping the temperature, and carrying out heat preservation reaction for 12-14 hours after the addition is completed within 1 hour. Cooling to room temperature, and regulating pH to 8.0-9.0 with 30% potassium hydroxide water solution. And then, the nano water-based pigment red 122/pigment violet 19 composite color paste 24 is obtained after membrane filtration treatment.
Example 31 preparation of color paste sample C-25 by pigmenting modification
43.0g (0.0721 mol) of modified colorant 1, 100g of distilled water and 22.4g (0.228 mol) of concentrated hydrochloric acid are added into a 1L four-necked flask, and the mixture is stirred in an ice bath, and the temperature of the reaction solution is controlled to be 0-5 ℃. Then 19.0g (0.0721 mol) of 20% potassium nitrite aqueous solution is slowly added dropwise, the temperature of the reaction solution is controlled between 0 ℃ and 5 ℃ in the process, and the reaction is carried out for 1 hour, thus obtaining the modifier diazonium solution.
Into a further 2L four-necked flask was charged 100g (0.1721 mol) of pigment blue 15:3 dry powder, 600g distilled water, and heating to 70 ℃ and stirring. And adding a modifier diazonium solution into the pigment blue 15:3 dispersion, controlling the temperature to be 70-75 ℃, keeping the temperature, and carrying out heat preservation reaction for 12-14 hours after the addition is completed within 1 hour. Cooling to room temperature, and regulating pH to 8.0-9.0 with 30% potassium hydroxide water solution. And then, after membrane filtration treatment, obtaining nano water-based pigment blue 15:3 color paste 25.
Example 32 preparation of color paste sample C-26 by pigmenting modification
43.0g (0.0721 mol) of modified colorant 9, 100g of distilled water and 22.4g (0.228 mol) of concentrated hydrochloric acid are added into a 1L four-neck flask, the mixture is stirred in an ice bath, the temperature of the reaction solution is controlled to be 0-5 ℃, 19.0g (0.0721 mol) of 20% potassium nitrite aqueous solution is slowly added dropwise, the temperature of the reaction solution is controlled to be 5-10 ℃ in a process control manner, and the reaction is carried out for 1 hour, so as to obtain a modifier diazonium solution.
Into a further 2L four-necked flask was charged 100g (0.1721 mol) of pigment blue 15:4 dry powder, 600g distilled water, and heating to 70 ℃ and stirring. Pigment violet pigment blue 15:4 adding a modifier diazonium solution into the dispersion liquid, controlling the temperature to be 70-75 ℃ and keeping the temperature, and after the addition is completed within 1 hour, keeping the temperature and reacting for 12-14 hours. Cooling to room temperature, and regulating pH to 8.0-9.0 with 30% potassium hydroxide water solution. And then, after membrane filtration treatment, obtaining nano water-based pigment blue 15:4 color paste 26.
Examples 33-37 operate the same as examples 31-32.
Example 38 preparation of color paste sample Y-32 by pigmenting modification
43.0g (0.0721 mol) of modified colorant 1, 100g of distilled water and 22.4g (0.228 mol) of concentrated hydrochloric acid are added into a 1L four-necked flask, and the mixture is stirred in an ice bath, and the temperature of the reaction solution is controlled to be 0-5 ℃. Then 19.0g (0.0721 mol) of 20% potassium nitrite aqueous solution is slowly added dropwise, the temperature of the reaction solution is controlled between 5 ℃ and 10 ℃ in the process, and the reaction is carried out for 1 hour, thus obtaining the modifier diazonium solution.
Into another 2L four-necked flask, 100g (0.259 mol) of pigment yellow 74 dry powder and 600g of distilled water were charged, and the temperature was raised to 70-75℃and stirred. Adding the diazonium solution of the modifier in batches, controlling the temperature to be 70-75 ℃ and keeping the temperature, and after the addition is completed within 1 hour, keeping the temperature and reacting for 12-14 hours. Cooling to room temperature, and regulating pH to 8.0-9.0 with 30% potassium hydroxide water solution. And then the nano water-based pigment yellow 74 color paste 32 is obtained after membrane filtration treatment.
Example 39 preparation of color paste sample Y-33 by pigmenting modification
Into a 1L four-necked flask, 40g (0.06 mol) of modified colorant 9, 100g of distilled water and 12g (0.12 mol) of concentrated hydrochloric acid were added, and the mixture was stirred in an ice bath, wherein the temperature of the reaction solution was controlled to be 0-5 ℃. Then 19.0g (0.0721 mol) of 20% potassium nitrite aqueous solution is slowly added dropwise, the temperature of the reaction solution is controlled between 5 ℃ and 10 ℃ in the process, and the reaction is carried out for 1 hour, thus obtaining the modifier diazonium solution.
Into another 2L four-necked flask, 100g (0.139 mol) of pigment yellow 155 dry powder and 600g of distilled water were charged, and the temperature was raised to 70-75℃and stirred. Adding the diazonium solution of the modifier in batches, controlling the temperature to be 70-75 ℃ and keeping the temperature, and after the addition is completed within 1 hour, keeping the temperature and reacting for 12-14 hours. Cooling to room temperature, and regulating pH to 8.0-9.0 with 30% potassium hydroxide water solution. Then the nanometer water-based pigment yellow 155 color paste 33 is obtained after membrane filtration treatment.
Examples 40-43 were operated in the same manner as examples 38-39 to obtain nano aqueous yellow pastes 34-37.
Example 44 preparation of color paste sample G-38 by pigmenting modification
43.0g (0.0721 mol) of modified colorant 1, 100g of distilled water and 12.0g (0.12 mol) of concentrated hydrochloric acid are added into a 1L four-necked flask, and the mixture is stirred in an ice bath, and the temperature of the reaction solution is controlled to be 0-5 ℃. Subsequently, 20.18g (0.0721 mol) of 20% aqueous potassium nitrite solution was slowly added dropwise thereto, and the temperature of the reaction solution was controlled at 0 to 5 ℃. And reacting for 1 hour to obtain the modifier diazonium solution.
Into another 2L four-necked flask, 100g (0.060 mol) of pigment green 36.0 dry powder and 600g of distilled water were charged, heated to 70-75℃and stirred. Then adding the diazonium solution of the modified colorant 1 into the pigment green 36 dispersion, stirring the mixture at 70-75 ℃ for heat preservation, and controlling the pH of the color paste to be in a range of 6-7 by using 30% potassium hydroxide aqueous solution. The diazo liquid of the modified colorant 1 is added for 12 to 14 hours. Cooling the color paste to room temperature, and adjusting the pH to 8.0-9.0 by using 30% potassium hydroxide aqueous solution. And then the nano water-based pigment green 36 color paste 38 is obtained after membrane filtration treatment.
Example 45 preparation of color paste sample W-39 by pigmenting modification
Into a 1L four-necked flask, 40.0g (0.06 mol) of modified colorant 9, 100.0g of distilled water and (0.12 mol) of concentrated hydrochloric acid were added, and the mixture was stirred in an ice bath, and the temperature of the reaction solution was controlled to be 0-5 ℃. Then, 20.18g (0.0721 mol) of 20% potassium nitrite aqueous solution was slowly added dropwise thereto, and the temperature of the reaction solution was controlled at 5-10 ℃. And reacting for 1 hour to obtain the modifier diazonium solution.
To a 2L four-necked flask, 100.0g of titanium white powder and 600g of distilled water were further added, and the temperature was raised to 70℃and stirred. And adding the modified colorant 9 diazonium solution into the titanium white dispersion, stirring at 70-75 ℃ for heat preservation, and controlling the pH of the color paste to be in a range of 6-7 by using 30% potassium hydroxide aqueous solution. The diazo liquid of the modified colorant 9 is added for 12 to 14 hours. Cooling the color paste to room temperature, and adjusting the pH to 8.0-9.0 by using 30% potassium hydroxide aqueous solution. After subsequent membrane filtration treatment, a nano-aqueous titanium white paste 39 is obtained.
Examples 46-49 the same procedure as in example 45 was followed to produce nano aqueous titanium white pastes W-40 to W-43.
Comparative example 1
Into a 2L four-necked flask, 100g of carbon black pigment dry powder, 13.0g (0.072 mol) of p-aminophenyl n-butyric acid, 700g of distilled water and 14.4g (0.144 mol) of concentrated hydrochloric acid were added, and after stirring uniformly, 23.23g (0.0721 mol) of a 20% aqueous solution of sodium nitrite was slowly dropped, and the dropping was completed within 1 hour. Then the temperature was raised to 40℃with stirring and kept for 16 hours. Cooling the color paste to room temperature, and adjusting the pH to 8.0-9.0 by using 30% sodium hydroxide aqueous solution. And then the nano water-based carbon black pigment color paste K-16 is obtained after membrane filtration treatment.
Comparative example 2
Into a 2L four-necked flask, 100g of carbon black pigment dry powder, 11.7g (0.1 mol) of sulfanilic acid, 700g of distilled water and 20g (0.2 mol) of concentrated hydrochloric acid were added, and after stirring uniformly, 34.5g (0.1 mol) of a 20% aqueous solution of sodium nitrite was slowly dropped, and the dropping was completed within 1 hour. Then stirring and heating to 35-40 ℃ and preserving heat for 16 hours. The color paste is cooled to room temperature, and the pH is adjusted to 8.0-9.0 by using 30% sodium hydroxide aqueous solution. Then the nano water-based carbon black pigment color paste 1 is obtained after membrane filtration treatment.
Comparative example 3
Into a 2L four-necked flask, 100g of carbon black pigment dry powder, 13.7g (0.1 mol) of p-aminobenzoic acid, 700g of distilled water and 20g (0.2 mol) of concentrated hydrochloric acid were added, and after stirring uniformly, 34.5g (0.1 mol) of a 20% aqueous solution of sodium nitrite was slowly dropped, and the dropping was completed within 1 hour. Then stirring and heating to 35-40 ℃ and preserving heat for 16 hours. Cooling the color paste to room temperature, and adjusting the pH to 8.0-9.0 by using 30% sodium hydroxide aqueous solution. Then the nano water-based carbon black pigment color paste 1 is obtained after membrane filtration treatment.
Comparative example 4
Into a 1L four-necked flask, 11.7g (0.1 mol) of sulfanilic acid, 100.0g of distilled water and 20.0g (0.2 mol) of concentrated hydrochloric acid were charged, and the mixture was stirred in an ice bath to control the temperature of the reaction solution to 0-5 ℃. 28.0g (0.1 mol) of 20% aqueous potassium nitrite solution was then slowly added dropwise, the temperature of the reaction solution being controlled to be less than 10 ℃. And reacting for 1 hour to obtain the modifier diazonium solution.
Into another 2L four-necked flask, 100.0g (0.294 mol) of pigment Red 122 dry powder and 600g of distilled water were charged, and the temperature was raised to 70℃and stirred. And adding a modifier diazonium solution into the pigment red 122 dispersion, stirring at 70-75 ℃ for heat preservation, and controlling the pH of the color paste to be in a range of 6-7 by using 30% potassium hydroxide aqueous solution. The diazo liquid of the modifier is added for 12-14 hours. Cooling the color paste to room temperature, and adjusting the pH to 8.0-9.0 by using 30% potassium hydroxide aqueous solution. Then the nanometer water-based pigment red 122 color paste is obtained after membrane filtration treatment.
Comparative example 5
Into a 1L four-necked flask, 11.7g (0.1 mol) of sulfanilic acid, 100g of distilled water and 20g (0.2 mol) of concentrated hydrochloric acid were charged, and stirred in an ice bath, and the temperature of the reaction solution was controlled to be 0-5 ℃. 28.0g (0.1 mol) of 20% aqueous potassium nitrite solution was then slowly added dropwise, the temperature of the reaction solution being controlled to be less than 10 ℃. And reacting for 1 hour to obtain the modifier diazonium solution.
Into another 2L four-necked flask, 100g (0.294 mol) of pigment violet 19.0 dry powder and 600g of distilled water were charged, and the temperature was raised to 70℃and stirred. And adding a modifier diazonium solution into the pigment violet 19 dispersion, stirring at 70-75 ℃ for heat preservation, and controlling the pH of the color paste to be in a range of 6-7 by using 30% potassium hydroxide aqueous solution. The diazo liquid of the modifier is added for 12-14 hours. Cooling the color paste to room temperature, and adjusting the pH to 8.0-9.0 by using 30% potassium hydroxide aqueous solution. Then the nano water-based pigment violet 19 color paste is obtained after membrane filtration treatment.
Comparative example 6
Into a 1L four-necked flask, 11.7g (0.1 mol) of sulfanilic acid, 100g of distilled water and 20.0g (0.2 mol) of concentrated hydrochloric acid were charged, and the mixture was stirred in an ice bath at a temperature of 0 to 5 ℃. Then 28.0g (0.1 mol) of 20% potassium nitrite aqueous solution is slowly added dropwise, the temperature of the reaction solution is controlled to be 5-10 ℃ in a process, and the reaction is carried out for 1 hour, thus obtaining the modifier diazonium solution.
Into a further 2L four-necked flask was charged 100g (0.1721 mol) of pigment blue 15:3 dry powder, 600g distilled water, and heating to 70 ℃ and stirring. And adding a modifier diazonium solution into the pigment blue 15:3 dispersion, stirring at 70-75 ℃ for heat preservation, and controlling the pH of the color paste to be in a range of 6-7 by using a 30% potassium hydroxide aqueous solution. The diazo liquid of the modifier is added for 12-14 hours. Cooling the color paste to room temperature, and adjusting the pH to 8.0-9.0 by using 30% potassium hydroxide aqueous solution. And then, after membrane filtration treatment, obtaining nano water-based pigment blue 15: and 3, color paste.
Comparative example 7
Into a 1L four-necked flask, 11.7g (0.1 mol) of sulfanilic acid, 100g of distilled water and 20.0g (0.2 mol) of concentrated hydrochloric acid are added, the mixture is stirred in an ice bath, the temperature of the reaction solution is controlled to be 0-5 ℃, then 28.0g (0.1 mol) of 20% potassium nitrite aqueous solution is slowly added dropwise, and the temperature of the reaction solution is controlled to be less than 10 ℃ in a process. And reacting for 1 hour to obtain the modifier diazonium solution.
Into another 2L four-necked flask, 100g (0.259 mol) of pigment yellow 74 dry powder and 600g of distilled water were charged, and the temperature was raised to 70℃and stirred. And adding a diazonium solution of a modifier into the pigment yellow 74 dispersion liquid, preserving heat at 70-75 ℃, and controlling the pH of the color paste to be 6.0-7.0 by using a 30% potassium hydroxide aqueous solution. The diazo liquid of the modifier is added for 12-14 hours. Cooling the color paste to room temperature, and adjusting the pH to 8.0-9.0 by using 30% potassium hydroxide aqueous solution. And then the nano water-based pigment yellow 74 color paste 32 is obtained after membrane filtration treatment.
Comparative example 8
Into a 1L four-necked flask, 11.7g (0.1 mol) of sulfanilic acid, 100g of distilled water and 20.0g (0.2 mol) of concentrated hydrochloric acid were charged, and the mixture was stirred in an ice bath at a temperature of 0 to 5 ℃. Then 28.0g (0.1 mol) of 20% potassium nitrite aqueous solution is slowly added dropwise, the temperature of the reaction solution is controlled to be less than 10 ℃ in a process, and the reaction is carried out for 1 hour, thus obtaining the modifier diazonium solution.
Into another 2L four-necked flask, 100.0g (0.139 mol) of pigment yellow 155 dry powder and 600.0g of distilled water were charged, and the temperature was raised to 70℃and stirred. Then adding a diazonium solution of a modifier into the dispersibility of pigment yellow 155, preserving heat at 70-75 ℃, and controlling the pH of the color paste to be in a range of 6-7 by using 30% potassium hydroxide aqueous solution. The diazo liquid of the modifier is added for 12-14 hours. Cooling the color paste to room temperature, and adjusting the pH to 8.0-9.0 by using 30% potassium hydroxide aqueous solution. Then the nanometer water-based pigment yellow 155 color paste 33 is obtained after membrane filtration treatment.
The detection results of the color paste examples and the comparative examples are shown in Table 1:
TABLE 1
As can be seen from the data of the above examples and comparative examples, the pigment paste prepared by using the modified colorant of the invention has the advantages of good filterability, strong tinting strength, stable heat storage (small change rate of particle size after 7 days of heat storage), and the like, and has advantages in the application of code-spraying ink, in particular, the modified colorant of the invention has a triazine main structure and has an anchoring group L and a functional group A 1 、A 2 The anchoring group L can be anchored on the pigment surface through the form fastness of chemical bonds, and the external temperature and the auxiliary agent are not dropped off due to the change, so that the pigment has good stability, and the functional group A 1 、A 2 Can be realized by regulating the types and the numbers of the functional groupsThe hydrophilicity or lipophilicity of the pigment can be effectively regulated. The functional groups of the modified colorant are exposed on the outer layer of the pigment particles, so that on one hand, ionization occurs in a dispersion medium, and an electric double layer is formed on the surfaces of the pigment particles, so that pigment particles are mutually repelled, and on the other hand, hydrophilic functional groups can promote the wetting action of the pigment particles and the dispersion medium, so that the dispersibility is improved. Functional group A of triazine host structure 1 、A 2 The pigment contains the co-diphosphate group with higher calcium index, can be complexed with calcium ions in an application system, and is densely gathered on the surface of the application system, so that the coloring strength is improved.
The above embodiments are provided to illustrate the technical concept and features of the present invention and are intended to enable those skilled in the art to understand the content of the present invention and implement the same, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
Claims (8)
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