CN112521768A - Oil-soluble dye, preparation method and application thereof - Google Patents

Oil-soluble dye, preparation method and application thereof Download PDF

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CN112521768A
CN112521768A CN202011127926.9A CN202011127926A CN112521768A CN 112521768 A CN112521768 A CN 112521768A CN 202011127926 A CN202011127926 A CN 202011127926A CN 112521768 A CN112521768 A CN 112521768A
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mpc
oil
soluble dye
dye
compound
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杜健军
于富强
樊江莉
彭孝军
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Dalian University of Technology
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    • 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
    • C09B47/00—Porphines; Azaporphines
    • C09B47/04—Phthalocyanines abbreviation: Pc
    • C09B47/08—Preparation from other phthalocyanine compounds, e.g. cobaltphthalocyanineamine complex
    • C09B47/24—Obtaining compounds having —COOH or —SO3H radicals, or derivatives thereof, directly bound to the phthalocyanine radical
    • 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

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  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Wood Science & Technology (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Developing Agents For Electrophotography (AREA)

Abstract

The invention discloses an oil-soluble blue dye, which has a C-A structure formed by an amine compound A with a long carbon chain, a branched chain or a benzene ring in a molecule except a color development matrix C, has high oil solubility, has the solubility in tetrahydrofuran or methanol of 17-19g/100mL, and can be used as a colorant in ink, coating, paint, toner for laser printing, markers, paper, ball-point pen oil, petroleum products, floor wax, glass, ceramics or polymers. Therefore, the copper phthalocyanine has good application prospect as a toner colorant.

Description

Oil-soluble dye, preparation method and application thereof
Technical Field
The invention relates to an oil-soluble dye and application thereof, in particular to a novel oil-soluble dye, a preparation method and application thereof.
Background
It is well known that dyes can be used in many fields, in the traditional industry, for inks, coatings, paints, markers, petroleum products, etc., such as printing inks, indoor or outdoor paints, and various colored paints, etc. In recent years, with the application of computer and digital camera technologies, the digital design of color information recording materials gradually replaces the conventional technologies, and has been rapidly developed. Dyes are increasingly used in ink jet printing inks and laser printing inks.
The solvent type dye is generally brighter than the water-soluble dye in color and stronger in tinting strength, and the prepared ink is better in transparency, better in printing effect, low in price and the like than organic pigment ink. In addition, the solvent-based ink has high drying speed and excellent compatibility, and is more suitable for various printing at present.
The copper phthalocyanine is a dye with bright cyan, and has good acid and alkali resistance and light stability. The unsubstituted phthalocyanine and the complex thereof have wide application in blue toner, but because the intermolecular acting force is stronger, the phthalocyanine is almost insoluble in most organic solvents, the application is limited to a great extent, in the process of preparing the toner, the dye is required to be dissolved in the organic solvent to be mixed with resin to form the toner, if the solubility of the dye is lower, the dye of the printing toner falls off, and the problem of reducing the printing effect is caused.
In recent years, many studies have been conducted around oil-soluble dyes, and there have been some advances.
U.S. Pat. No. 3,36, 451, filed in 1972, proposes a dye of the sulfonic acid ester type, which is synthesized from copper phthalocyanine as a raw material by chlorosulfonation with various dye phenolic derivatives. To improve the solubility properties, it is necessary to introduce lipophilic groups into the phenol, with branched or unbranched alkyl groups, alkoxy groups, hydroxy acid ester groups and halogen atoms, such as p-tert-butylphenol, p-isooctylphenol, dodecylphenol, 2-hexyl p-hydroxybenzoate. The dye is easy to dissolve in chloroform, toluene and dimethylformamide. The dyes have good coloring properties, but the cost of the phenolic polymers is too high, resulting in too high a cost for the preparation of the toner.
Figure BDA0002732923020000011
Figure BDA0002732923020000021
In recent years, as waterproof materials have been widely used in daily life, development of hydrophobic preventive materials has been rapidly advanced. Wang et al reacted 1, 4-diaminoanthraquinone dyes with trichloro-s-triazine derivatives to give anthraquinone hydrophobic dyes as shown in VII for the coloration of hydrophobic cotton. The trichloro-s-triazine group of the anthraquinone dye can be fixed on cotton fabric under alkaline conditions, and the long carbon chain on the group increases the oil solubility of the dye, and the carbon chain is too long, so that the cost is too high.
Figure BDA0002732923020000022
In chinese patent CN101580646A filed in 2008, a water-soluble weather-resistant dye is invented, which adopts a dye with the following formula, wherein R group has a hydrophilic group, and can be well dissolved in water, and the structure has very high weather resistance, but its oil solubility is very poor.
Figure BDA0002732923020000023
In conclusion, there is a need to develop a new dye with good oil solubility, poor weather resistance and low cost.
Disclosure of Invention
In order to overcome the problems of poor solubility, poor weather resistance and overhigh cost of the dye in an organic solvent in the prior art, the invention provides a method for synthesizing an oil-soluble dye with high solubility in the organic solvent, and researches the application of the dye.
In a first aspect, the present invention relates to an oil-soluble dye, in particular obtained by introducing some lipophilic substituents on the phthalocyanine molecule. The steric hindrance of the substituent groups is relatively large, the aggregation effect among phthalocyanine molecules can be damaged, the solubility of the dye in an organic solvent is increased, and the amine compound with the benzene ring structure can increase the weather resistance of the dye. The technical solution and the protection scope of the present invention are described as follows:
the first aspect of the invention is to protect an oil-soluble dye, wherein the molecular structure of the dye is C-SO2-a, wherein C is the color base of a phthalocyanine dye, a is an amine compound of a long carbon chain, branched chain or benzene ring with a carbon number of at least 4A compound A is connected with a color development matrix C to form C-SO2-a dye molecules.
Further, in a preferred technical scheme, the C-SO2-a dye is a metal complex phthalocyanine which is a compound having the general formula I:
Figure BDA0002732923020000031
wherein:
m is at least one of hydrogen atom, metal oxide, hydroxyl compound or halide;
pc is a phthalocyanine mother ring;
k' is at least one of H, metal ions, ammonium salt and organic ammonium salt;
a is at least one of long carbon chain with at least 4 carbon atoms, branched chain or amine compound with benzene ring;
a. b takes the values of 0, 1, 2, 3 or 4 respectively; and the sum of a and b is 3 or 4; preferably 0. ltoreq. a.ltoreq.2, more preferably 0. ltoreq. a.ltoreq.1; b is 0-3, preferably 2-3; the smaller the a value, the less water-soluble the dye, and the larger the b value, the greater the oil-soluble the dye.
Namely, MPc is a phthalocyanine parent body, and Pc in the MPc phthalocyanine parent body is a phthalocyanine parent body ring; said substituent SO3K' and SO2A is respectively connected to the phthalocyanine benzene rings of Pc. -SO2The A group has great effect on the oil solubility of the dye and is the main structure except the-SO of the dye matrix3The K' group has some effect on the water solubility of the dye.
Further, in a preferred technical scheme, in the general formula I of the invention, A is-NR1R2The general formula of the structure is shown as II;
Figure BDA0002732923020000041
wherein: r1And R2Are respectively selected from H, C2-20Alkyl of (C)6,12,18,24Aryl of (said C)6，12,18，24Aryl of (2) is preferably C18,24) Or phenyl or naphthyl with substituents selected from B, or (CR)3R4)nAt least one of B; wherein, said C2-20The number of C in the alkyl group of (2) to (20) is an integer; preferably, said R is1And R2Are respectively selected from C5-20More preferably C8-20Further preferred is C10-20The more the number of carbon atoms of the alkyl group is, the better the oil solubility of the dye is, wherein the number of C is an integer of 2-20, 5-20, 8-20 and 10-20. When R is1And R2Are each selected from C6-C18The aryl group of (1), the phenyl group or naphthyl group having a substituent of B, the oil solubility of the dye may be deteriorated.
Said (CR)3R4)nIn B, R3Or R4Are respectively selected from H, C2-C12One of (1); n is an integer selected from 1 to 20; n is preferably 5 to 20, more preferably 8 to 20, still more preferably 10 to 20, and the larger the value of n, the better the oil solubility of the dye;
said (CR)3R4)nIn B, the substituent B is selected from Cl, Br, I and NO2、CH＝CH2、-OCH3And a hydroxy ester group.
Further, In a preferred embodiment, the metal atom is at least one selected from the group consisting of Li, Na, K, Mg, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Si, Ge, Sn, Pb, Sb and Bi; at least one of copper, iron, nickel, zinc, aluminum, and silicon is preferred, and copper is more preferred. The metal oxide is selected from MgO and Al2O3、Fe2O3CuO, ZnO; the hydroxyl compound is selected from Zn (OH)2、Mg(OH)2、Cu(OH)2、Al(OH)3And/or AgOH; the halide being selected from ZnCl2、FeCl2、 AlCl3、CuCl2、MgCl2、SnCl2、PbCl2At least one of (1).
Further, in a preferred embodiment, the present invention is applied toIn the formula I, K' is selected from H, Li, Na, K and NH4、 N(CH3)4、NH(CH3)3、NH2(CH3)2、NH3CH3More preferably H, Li, Na, K, NH4、N(CH3)4At least one of (1).
Further, in a preferred embodiment, the structural formula of MPc is phthalocyanine of formula iii:
Figure BDA0002732923020000042
further, in a preferred technical scheme, the compound of the general formula I is represented by a general formula iv:
Figure BDA0002732923020000051
the second aspect of the invention discloses a preparation method of the oil-soluble dye, which comprises the following steps: the MPc is first chlorosulfonated or a reactive sulfonyl chloride is introduced to form phthalocyanine sulfonyl chloride intermediate 1: [ MPc (SO)3H)P(SO2Cl)q](ii) a The regulation of the cation K' is achieved by adding a basic reagent during the reaction with the phthalocyanine sulfonyl chloride intermediate 1.
Further, in a preferred technical scheme of the preparation method, the preparation method comprises the following steps:
(1) reacting MPc with chlorosulfonic acid in varying molecular ratios;
(2) reacting the MPC with chlorosulfonic acid with different molecular ratios and compounds V with different molecular ratios to obtain MPC sulfonate; the compound V is selected from thionyl chloride, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride or phosgene;
(3) reacting the MPC sulfonate with compounds V with different molecular ratios to obtain MPC sulfonyl chloride 1;
the reaction formulae of the steps (1), (2) and (3) are as follows:
MPc+d HSO3Cl→MPc(SO3H)p(SO2Cl)q
MPc+eHSO3Cl+fSO2Cl/PCl3/PCl5/POCl3/COCl2→MPc(SO3H)p(SO2Cl)q
MPc(SO3H)p+q+g HSO3Cl+h SO2Cl/PCl3/PCl5/POCl3/COCl→MPc(SO3H)p(SO2Cl)q1
wherein: d is more than or equal to 1 and less than or equal to 500; e, f, g and h are more than or equal to 0 and less than or equal to 500; d, e, f, g and h are integers;
(4) reaction of MPC sulfonyl chloride 1 with NHR under action of alkaline reagent1R2Reacting to form structure 2;
the reaction formula of the step (4) is as follows:
Figure BDA0002732923020000052
the molecular ratios d, e, f, g, h, i can be adjusted as required for p and q, which are determined as required for a and b in the target product 1.
In practical applications, the synthesized compounds are usually mixtures, the separation of the mixtures and the purification of the individual compounds can be carried out by column chromatography, and furthermore, the synthesized dyes may not be separated if the properties of the ultraviolet-visible spectrum after separation are approximately the same.
In the technical solution of the preparation method described above, particularly preferably, the alkaline reagent in step (4) is selected from one of potassium hydroxide, sodium carbonate, potassium carbonate and triethylamine.
In the above-mentioned technical solution of the preparation method, it is particularly preferable that when the compound of the general formula I is a copper phthalocyanine cyan dye, and when the compound of the general formula I is a copper phthalocyanine cyan dye, the synthesis procedure of CuPc is the same as the synthesis procedure of MPc, and the compound of the general formula I may be chlorosulfonated or a reactive sulfonyl chloride is introduced to form the phthalocyanine sulfonyl chloride intermediate 3: [ CuPc (SO)3H) P(SO2Cl)q]The control of the cation K' can be realized by adding an alkaline reagent during the reaction, namely the MPC in the step (1) is CuPc; the compound V is thionyl chloride. The specific operation steps are as follows:
(1) reacting CuPc with chlorosulfonic acid of different molecular ratios;
(2) CuPc reacts with chlorosulfonic acid with different molecular ratios and thionyl chloride with different molecular ratios;
(3) reacting a CuPc sulfonate with thionyl chloride with different molecular ratios;
CuPc+d HSO3Cl→CuPc(SO3H)Pp(SO2Cl)q
CuPc+e HSO3Cl+fSO3Cl→CuPc(SO3H)p(SO2Cl)q
CuPc(SO3H)p+q+gHSO3Cl+hSO2Cl→CuPc(SO3H)p(SOiCl)q3
wherein d is 1-500; e. f, g and h are 0-500, the numerical values are the same or different, and d, e, f, g and h are integers.
CuPc sulfonyl chloride 3 can be preferably reacted with NHR under the action of alkaline reagent1R2React to form the final structure 4
Figure BDA0002732923020000061
The molecular ratios d, e, f, g, h, i can be adjusted as required for p and q, which are determined as required for a and b in the target product 1.
In a third aspect, the present invention relates to the use of the oil-soluble dyes according to the invention.
Preferably, the applications described above include the use of the oil-soluble dyes described above in combination with dyes of other colors, as colorants for other materials or in ink products.
Preferably, the applications described above include: the oil-soluble dye can form bright colors, particularly the cyan dye is one of the traditional three primary colors, can be compounded with other various cyan dyes for use, and also can be compounded with dyes of other colors to form various required colors, such as being compounded with yellow dye to form green, being compounded with magenta dye to form purple, and being compounded with yellow dye and magenta dye to form black.
Preferably, the applications described above include: the dye of the present invention can be used in various applications, and is useful as a colorant for the following materials: inks, coatings, paints, markers, ball-point pen oils, petroleum products, laser printing toners, fuels, waxes, paper, glass, ceramics or polymers.
In a preferred embodiment of the above-described use, an ink is used, which is a printing ink, a coating ink or an inkjet ink. The ink-jet ink is solvent-based ink-jet ink, and can also be water-based ink-jet ink.
In a fourth aspect, the present invention is directed to an inkjet solvent-based ink composition comprising: 5-10 wt% of the oil-soluble dye of the present invention for changing the color of a toner; 70-80 wt% of resin for binding all components, 5-7 wt% of charge regulator for regulating the electrical property and charge quantity of the ink powder, and 10-15 wt% of auxiliary agent for improving various performances.
The ink may optionally be supplemented with various other additives, i.e. conventional adjuvants, for example with at least one of the following conventional adjuvants: 0-3 wt% of surfactant, 0-3 wt% of ultraviolet absorbent, 0-3 wt% of antioxidant, 0-3 wt% of preservative, 0-3 wt% of bactericide, 0-3 wt% of PH regulator, 0-2 wt% of metal ion complexing agent, 0-15 wt% of humectant, 0-5 wt% of drier, 0-5 wt% of waterproof agent and the like, wherein the common surfactant comprises: nonionic surfactants, anionic surfactants, polymeric surfactants, cationic surfactants, and the like.
Adjuvants of the above-mentioned type are described in many prior art and patents, for example, in US7034149, US6086955, US6148722, US6235097, US7087107, US7211134, and the like.
The ink is prepared by adopting a conventional method in the ink-jet ink industry, and when the ink is prepared, raw materials are required to be mixed, fully stirred and heated, and then micron-sized particles are formed by spray drying.
The invention has the beneficial effects that:
1. the oil-soluble dye synthesized by the invention belongs to copper phthalocyanine amine derivatives, has extremely high oil solubility, and the improvement of the oil solubility can improve the solubility of the dye in the toner and greatly reduce the preparation cost of the toner.
2. The oil-soluble dye synthesized by the invention solves the problem that the colorant is easy to fall off when the compatibility of the color powder resin prepared by an emulsion polymerization method and the colorant is poor. The dye dissolved in organic solvent and initiator in water phase are made into stable emulsion through membrane emulsification process under the action of membrane emulsifier, and the core of the process is dye with relatively high solubility in organic solution as coloring agent. Oil-soluble dyes are obtained, in particular, by introducing some lipophilic substituents on the phthalocyanine molecule. The steric hindrance of the substituent groups is relatively large, the aggregation effect among phthalocyanine molecules can be damaged, the solubility of the dye in an organic solvent is increased, and the amine compound with the benzene ring structure can increase the weather resistance of the dye.
3. Compared with water-soluble dyes, oil-soluble dyes have higher stability and are widely applied.
Drawings
FIG. 1: ultraviolet absorption spectra of copper phthalocyanine in DMF at different concentrations; wherein: the absorbance increased with increasing concentration, with a maximum absorption wavelength at 671 nm.
Detailed Description
The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way. The synthesis of the dyes of the present invention, and their solubility in organic solvents, is illustrated below by way of example, but not limited thereto.
Example 1
5.8g of copper phthalocyanine was added in portions to 11.4mL of chlorosulfonic acid, and the mixture was stirred at about 145 ℃ for reaction for 5 hours, cooled to 50 ℃, then 3mL of thionyl chloride was added, and the mixture was refluxed at 70 to 80 ℃ for reaction for 1 hour, then cooled to room temperature, poured into ice water, filtered, and the filter cake was washed with ice water three times.
3g of PC-SO was added2Adding Cl into 20mL of tetrahydrofuran solvent, dropwise adding 2.3mL of diisooctylamine, stirring at the temperature of 60 ℃ for reaction for 5 hours, and removing the tetrahydrofuran solution by rotary evaporation. Detecting the reaction product by thin layer chromatography, and separating V (methanol) by column chromatography: v (dichloromethane) 1:1 to obtain a Dye1 mixture of three products, and after separation, obtaining Dye1-1, Dye1-2 and Dye1-3 respectively.
Figure BDA0002732923020000081
Example 2
5.8g of copper phthalocyanine was added in portions to 11.4mL of chlorosulfonic acid, and the mixture was stirred at about 145 ℃ for reaction for 5 hours, cooled to 50 ℃, then 3mL of thionyl chloride was added, and the mixture was refluxed at 70 to 80 ℃ for reaction for 1 hour, then cooled to room temperature, poured into ice water, filtered, and the filter cake was washed with ice water three times.
3g of PC-SO was added2Adding Cl into 20mL of tetrahydrofuran solvent, dropwise adding 2.3mL of di-n-octylamine, stirring at the temperature of 60 ℃ for reaction for 5 hours, and removing the tetrahydrofuran solution by rotary evaporation. Detecting the reaction product by thin layer chromatography, and separating V (methanol) by column chromatography: v (dichloromethane) 1:1 to obtain a Dye2 mixture of 2 products, and after separation, Dye2-1 and Dye2-2 are respectively obtained.
Figure BDA0002732923020000091
Example 3
5.8 copper phthalocyanine was added in portions to 11.4mL of chlorosulfonic acid, stirred at about 145 ℃ for reaction for 5 hours, cooled to 50 ℃, then 3mL of thionyl chloride was added, reflux reaction was carried out at 70-80 ℃ for 1 hour, then cooled to room temperature, poured into ice water, filtered, and the filter cake was washed with ice water three times.
3g of PC-SO was added2Adding Cl into 20mL tetrahydrofuran solvent, and dropwise adding 4-n-butyl1.2mL of aniline, stirring and reacting at 60 ℃ for 6h, and removing the tetrahydrofuran solution by rotary evaporation. Detecting the reaction product by thin layer chromatography, and separating V (methanol) by column chromatography: v (dichloromethane) 1:1 to obtain a Dye3 mixture of two products, and after separation, Dye3-1 and Dye3-2 are respectively obtained.
Figure BDA0002732923020000092
Example 4
Testing of dye solubility:
the dyes were tested for solubility in four organic solvents, dichloromethane, tetrahydrofuran, methanol, ethyl acetate, respectively. Weighing 2g of dye respectively, adding the dye into a test tube containing 10mL of the solvent, adding the dye into the solvent at room temperature until the dye is dissolved in the solvent, sealing the opening of the test tube by using a sealing film, standing at 25 ℃ for 24h, filtering by using a filter membrane (0.22 mu m) for three times, and spin-drying the filtrate. Then weighing and calculating the dye solubility S by using a formula difference method.
Figure BDA0002732923020000101
Wherein W1Drying to obtain bottle weight in g; w2The weight of the bottle after the solvent is dried by spinning is g; v0Is the volume of the test tube, which is 100 mL; s is the solubility unit of the dye in g/100 mL.
TABLE 1 solubility of dyes in different solvents
Figure BDA0002732923020000102
The Dye1-1 connecting structure is diisooctylamine, has a long carbon chain and a branched chain structure, and has the highest solubility in an organic solvent.
The Dye2-1 connecting structure is di-n-butylamine, the chain length has four carbon structures, and the chain length is short.
The Dye3-1 connecting structure is n-butyl aniline, and the solubility is minimum due to the short alkyl chain of a benzene ring structure, but the weather resistance is strong. The solubility of the oil-soluble Dye prepared according to the method in the paper "synthesis and application of oil-soluble printing Dye" of the university of great courseware, Zhang-Dai, is less than 10%, while the solubility of the Dye1-1 Dye is improved by more than 8% per 100mL of solvent, and the solubility of the other two dyes is also improved to a certain extent.
In conclusion, the copper phthalocyanine dye can be used as a dye of materials such as toner powder and the like by improving the solubility, and has good application prospect.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed.

Claims (15)

1. An oil-soluble dye characterized by: the dye has a molecular structure of C-SO2-a, wherein C is the color base of the phthalocyanine dye, a is an amine compound of a long carbon chain, branched chain or benzene ring with a carbon number of at least 4, a being linked to the color base C.
2. An oil-soluble dye as claimed in claim 1, wherein: the C-SO2-a dye is a compound having the general formula I:
Figure FDA0002732923010000011
wherein:
m is at least one of hydrogen atom, metal oxide, hydroxyl compound or halide;
pc is a phthalocyanine mother ring;
k' is at least one of H, metal ions, ammonium salt and organic ammonium salt;
a is at least one of long carbon chain with at least 4 carbon atoms, branched chain or amine compound with benzene ring;
a. b takes the values of 0, 1, 2, 3 or 4 respectively; and the sum of a and b is 3 or 4.
3. The oil-soluble dye according to claim 2, characterized in that: a is-NR1R2The general formula of the structure is shown as II;
Figure FDA0002732923010000012
wherein: r1And R2Are respectively selected from H, C2-20Alkyl of (C)6,12,18,24Or phenyl or naphthyl with substituents selected from B, or (CR)3R4)nAt least one of B; wherein, said C2-20The number of C in the alkyl group of (2) to (20) is an integer;
said (CR)3R4)nIn B, R3Or R4Are respectively selected from H, C2-C12One of (1); n is an integer selected from 1 to 20; b is selected from Cl, Br, I, NO2、CH＝CH2、-OCH3And a hydroxy ester group.
4. The oil-soluble dye according to claim 2, characterized in that: the metal atom is at least one selected from Li, Na, K, Mg, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Si, Ge, Sn, Pb, Sb and Bi; the metal oxide is selected from MgO and Al2O3、Fe2O3CuO, ZnO; the hydroxyl compound is selected from Zn (OH)2、Mg(OH)2、Cu(OH)2、Al(OH)3And/or AgOH; the halide being selected from ZnCl2、FeCl2、AlCl3、CuCl2、MgCl2、SnCl2、PbCl2At least one of (1).
5. The oil-soluble dye according to claim 2, characterized in that: in the general formula I, K' is selected from Li, Na, K and NH4、N(CH3)4、NH(CH3)3、NH2(CH3)2、NH3CH3At least one of (1).
6. The oil-soluble dye according to claim 2, characterized in that: the structural formula of the MPC is shown as a general formula III:
Figure FDA0002732923010000021
7. the oil-soluble dye according to claim 2, characterized in that: the compound of the general formula I is shown as a general formula IV:
Figure FDA0002732923010000022
8. the method for preparing an oil-soluble dye according to claim 2, which comprises the steps of: the MPc is first chlorosulfonated or a reactive sulfonyl chloride is introduced to form phthalocyanine sulfonyl chloride intermediate 1: [ MPc (SO)3H)P(SO2Cl)q](ii) a The regulation of the cation K' is achieved by adding a basic reagent during the reaction with the phthalocyanine sulfonyl chloride intermediate 1.
9. The method of claim 8, wherein: the method comprises the following steps:
(1) reacting MPc with chlorosulfonic acid in varying molecular ratios;
(2) reacting the MPC with chlorosulfonic acid with different molecular ratios and compounds V with different molecular ratios to obtain MPC sulfonate; the compound V is selected from thionyl chloride, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride or phosgene;
(3) reacting the MPC sulfonate with compounds V with different molecular ratios to obtain MPC sulfonyl chloride 1;
the reaction formulae of the steps (1), (2) and (3) are as follows:
MPc+dHSO3Cl→MPc(SO3H)p(SO2Cl)q
MPc+eHSO3Cl+fSO2ClPCl3/PCl5/POCl3/COCl2→MPc(SO3H)p(SO2Cl)q
MPc(SO3H)p+q+gHSO3Cl+hSO2Cl/PCl3/PCl5/POCl3/COCl2→MPc(SO3H)p(SO2Cl)q 1
wherein: d is more than or equal to 1 and less than or equal to 500; e, f, g and h are more than or equal to 0 and less than or equal to 500; d, e, f, g and h are integers;
(4) reaction of MPC sulfonyl chloride 1 with NHR under action of alkaline reagent1R2Reacting to form structure 2;
the reaction formula of the step (4) is as follows:
Figure FDA0002732923010000031
10. the method of claim 8, wherein: the alkaline reagent in the step (4) is selected from one of potassium hydroxide, sodium carbonate, potassium carbonate and triethylamine.
11. The method of claim 8, wherein: when the compound of the general formula I is a copper phthalocyanine cyan dye, the MPC in the step (1) is CuPc; the compound V is thionyl chloride.
12. Use of the oil-soluble dye according to claim 2, which comprises compounding the oil-soluble dye according to claim 2 with dyes of other colors, as colorants for other materials or in ink products; preferably, the material as a colorant includes inks, coatings, paints, markers, ball-point pen oil, petroleum products, laser printing toners, fuels, waxes, paper, glass, ceramics or polymers.
13. An inkjet solvent-based ink composition characterized by: the raw materials of the composition comprise: 5-10 wt% of the oil-soluble dye according to claim 1 or 2, 70-80 wt% of resin, 5-7 wt% of charge regulator, and 10-15 wt% of auxiliary agent.
14. An inkjet solvent-based ink composition according to claim 13, wherein: the auxiliary agent comprises: 0-3 wt% of surfactant, 0-3 wt% of ultraviolet absorbent, 0-3 wt% of antioxidant, 0-3 wt% of preservative, 0-3 wt% of bactericide, 0-3 wt% of pH regulator, 0-2 wt% of metal ion complexing agent, 0-15 wt% of humectant, 0-5 wt% of drier and 0-5 wt% of waterproofing agent; wherein the surfactant comprises: nonionic surfactant, anionic surfactant, polymeric surfactant, cationic surfactant.
15. A method of preparing an inkjet solvent-based ink composition according to claim 13, wherein: the raw materials are fully stirred and heated after being mixed, and then micron-sized particles are formed through spray drying.
CN202011127926.9A 2020-10-20 2020-10-20 Oil-soluble dye, preparation method and application thereof Pending CN112521768A (en)

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