Triarylmethane dyes

Abstract

The present invention provides a modified triarylmethane dye comprising a structure represented by Formula 3, wherein R1, R2, R3, R4, R5, R6, R7, A1, A2, A1'and A2 'are as defined herein. # imgabs0 #

Description

[0001] Related Applications

[0002] This application claims the benefit of U.S. Provisional Application No. 63 / 391,864, filed on July 25, 2022. The entire teachings of the above application are incorporated herein by reference. Technical Field

[0003] The invention relates to a triarylmethane dye and application of the triarylmethane dye. Background Art

[0004] The triarylmethane dye series produces brilliant colors that are adjustable over a wide range of the visible spectrum. Triarylmethane (TAM) dyes are widely used in the production of paper dyes, printing inks, ballpoint pen pastes, foods, cosmetics and an increasing number of consumer products. Most of the known triarylmethane dyes have been developed from central cores in order to improve resistance to discoloration. An object of the present invention is to provide triarylmethane dyes in which the range of the aromatic system and the corresponding optical behavior are controlled. BRIEF DESCRIPTION OF THE DRAWINGS

[0005] The above and other objects, features and advantages of the present invention will become apparent from the following more specific description of the preferred embodiments of the present invention, as shown in the accompanying drawings, in which the same reference numerals refer to the same parts in different views. The accompanying drawings are not necessarily drawn to scale, emphasis instead being placed on illustrating the principles of the present invention.

[0006] Figure 1 A mass spectrum demonstrating the mass-to-charge ratio of one embodiment of an acidic triarylmethane (TAM) dye molecule according to the present invention is shown.

[0007] Figure 2 The acid TAM dye 1 H NMR spectroscopy confirmed the atomic structure of the dye.

[0008] Figure 3 By assigning the proton shifts observed in the spectrum to the molecule, further 1 H NMR confirmed the atomic structure of the acidic TAM dye compound.

[0009] Figure 4 A mass spectrum demonstrating the mass-to-charge ratio of one embodiment of a PEG TAM dye molecule according to the present invention is shown.

[0010] Figure 5 The PEG TAM dye compound is shown 1 H NMR spectroscopy confirmed the atomic structure.

[0011] Figure 6By assigning the proton shifts observed in the spectrum to the molecule, further 1 H NMR confirmed the atomic structure of the PEGTAM dye compound. In the structure shown, one PEG chain shows the proton labeling; the same labeling can be applied to all four PEG chains.

[0012] Figure 7 UV spectra of equimolar (25 μM) solutions of Acid Green 9, triarylmethane metachloroate, and triarylmethane metachloroPEG are depicted, showing significant changes in relative absorbance and peak positions, as shown in Table 6. Triarylmethane metachloroate exhibits a greener hue than Acid Green 9 in aqueous solution.

[0013] Figure 8 The results show that the 25 μM dye solution in phosphate buffer (pH = 8, 0.1 M) max The normalized absorbance versus time plot shows the difference in base resistance between Acid Green 9, metachlorotriarylmethane, and metachloroPEGtriarylmethane.

[0014] Fig. 9 A 1:1 solution of 25 μM unbuffered dye and 0.5% HO is depicted. 2 O 2 In λ max Figure 1 shows the normalized absorbance versus time for m-chlorotriarylmethane. The graph shows that the oxygen fast rate for m-chlorotriarylmethane is significantly lower than its closest related analog, while the oxygen fast rate for m-chloroPEGtriarylmethane is even lower. Hydrogen peroxide itself is not a strong enough oxidant to fade most triarylmethane dyes. Acid Green 9 is susceptible to rapid fading by hydrogen peroxide only at high pH values. Fig. 9 It is shown that even in a system that is not buffered at an alkaline pH, meta-chlorotriarylmethane and meta-chloroPEGtriarylmethane still fade in the presence of hydrogen peroxide. Summary of the invention

[0015] Triarylmethanes are a class of molecules known to those skilled in the art and are generally represented by Formula 1, wherein any combination of R groups are aromatic groups that may have additional functionalizations, including but not limited to amino (primary, secondary or tertiary), hydroxyl, halogen (bromine, chloride, fluorine, iodine), nitro, methoxy, carboxyl, alkyl, aryl, alkoxy and sulfonic acid. The counterion X may be provided by an external molecule or an inner sphere charged group associated with any R group.

[0016]

[0017] Due to the presence of resonance within the molecule, the structure of the triarylmethane dye can be represented in different ways, as shown in Formula 2, where structures 1, 1' and 1" are all equivalent. By convention, structure 1 is used herein.

[0018]

[0019] The present invention provides a modified triarylmethane dye comprising a structure shown in Formula 3

[0020]

[0021] in

[0022] R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are independently selected from hydrogen, halogen, C 1 -C 16 Alkyl, amino, nitro, methoxy, carboxyl, aryl, alkoxy, and sulfonic acid;

[0023] A 1 , A 2 , A 1 ' and A 2 ' is independently selected from hydrogen, alkyl, aryl, alkaryl or alkoxy, provided that A 1 , A 2 , A 1 ' and A 2 ' is at least one of an alkyl group, an aryl group, an alkaryl group or an alkoxy group.

[0024] In some embodiments, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are independently selected from hydrogen, halogen, C 1 -C 16 Alkyl, amino, nitro, methoxy, carboxyl, aryl, alkoxy and sulfonic acid, provided that R 1 , R 2 or R 3 At least one of them is a halogen.

[0025] In one embodiment, the modified triarylmethane dye comprising the structure shown in Formula 4,

[0026]

[0027] in

[0028] R 1 , R 2 , R 3 , R 4 and R 5 are independently selected from hydrogen, halogen, C 1 -C 16 Alkyl, amino, nitro, methoxy, carboxyl, aryl, alkoxy and sulfonic acid, provided that R 1 , R 2 or R 3 At least one of them is a halogen;

[0029] A 1 , A 2 , A 1 ' and A 2 ' is independently selected from hydrogen, alkyl, aryl, alkaryl or alkoxy, provided that A 1 , A 2 , A 1 ' and A 2 ' is at least one of an alkyl group, an aryl group, an alkaryl group or an alkoxy group.

[0030] In some embodiments, R 1 , R 2 , R 3 , R 4 and R 5 are independently selected from hydrogen, halogen, C 1 -C 16 Alkyl, amino, nitro, methoxy, carboxyl, aryl, alkoxy and sulfonic acid, provided that R 1 , R 2 or R 3 At least one of them is a halogen.

[0031] In any embodiment herein, halogen is selected from fluorine, bromine, chlorine or iodine. In any embodiment herein, halogen is fluorine. In any embodiment herein, halogen is bromine. In any embodiment herein, halogen is chlorine. In any embodiment herein, halogen is iodine.

[0032] In any embodiment herein, the amino group is a primary amino group, a secondary amino group, or a tertiary amino group. In any embodiment herein, the amino group is a primary amino group. In any embodiment herein, the amino group is a secondary amino group. In any embodiment herein, the amino group is a tertiary amino group.

[0033] In some embodiments, R 1 , R 2 or R 3 In some embodiments, when R 1 When it is a halogen, R2 and R 3 is hydrogen and R 1 is selected from fluorine, bromine, chlorine or iodine. 2 When it is a halogen, R 1 and R 3 is hydrogen and R 2 is selected from fluorine, chlorine, bromine or iodine. 3 When it is a halogen, R 1 and R 2 is hydrogen and R 3 is selected from fluorine, bromine or iodine.

[0034] In some embodiments, R 4 and R 5 For hydrogen.

[0035] In some embodiments, R 6 and R 7 For hydrogen.

[0036] In one embodiment, the modified triarylmethane dye comprising the structure shown in Formula 4,

[0037]

[0038] in

[0039] R 1 , R 2 and R 3 are independently selected from hydrogen or halogen, provided that R 1 , R 2 or R 3 Only one of them is a halogen, and the condition is that

[0040] When R 1 When it is a halogen, R 2 and R 3 is hydrogen and R 1 is selected from fluorine, bromine or iodine,

[0041] When R 2 When it is a halogen, R 1 and R 3 is hydrogen and R 2 is selected from fluorine, chlorine, bromine or iodine, and

[0042] When R 3 When it is a halogen, R 1 and R 2 is hydrogen and R 3 is selected from fluorine, bromine or iodine;

[0043] R 4 and R 5 is hydrogen; and

[0044] A 1 , A 2 , A 1 ' and A 2 ' is independently selected from hydrogen, alkyl, aryl, alkaryl or alkoxy, provided that A 1 , A 2 , A 1 ' and A 2 ' is at least one of an alkyl group, an aryl group, an alkaryl group or an alkoxy group.

[0045] In some embodiments, A 1 , A 2 , A 1 ' and A 2 ' is independently selected from hydrogen, alkyl, aryl, alkaryl or alkoxy, provided that A 1 , A 2 , A 1 ' and A 2 ' is at least one of an alkyl group, an aryl group, an alkaryl group or an alkoxy group.

[0046] In some embodiments, when R 1 When it is a halogen, A 1 , A 2 , A 1 ' and A 2 ' is independently selected from hydrogen, alkyl, aryl, alkaryl or alkoxy.

[0047] As used in any embodiment herein, the term halogen refers to any element from the group consisting of fluorine, chlorine, bromine and iodine.

[0048] As used in any embodiment herein, the term "alkyl" describes substituted or unsubstituted straight and branched carbon chains. Preferred alkyl groups are those containing 1 to 15 carbon atoms (i.e., C 1 -C 15 Alkyl), more preferably C 1 -C 10 Alkyl, more preferably C 1 -C 5 Alkyl. In some embodiments, the alkyl group is selected from methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, wherein each alkyl group may be optionally substituted. Preferably, the alkyl group is a substituted or unsubstituted ethyl group. Preferably, the alkyl group is an unsubstituted ethyl group.

[0049] As used in any embodiment herein, the term "aryl" or "aromatic group" is used interchangeably to describe a substituted or unsubstituted monocyclic or polycyclic system. Polycyclic rings may have two or more rings, wherein two adjacent rings ("fused" rings) have two carbon atoms in common, wherein at least one ring is aromatic, e.g., the other rings may be cycloalkyl, cycloalkenyl, aryl, heterocyclic and / or heteroaryl. Preferred aryl groups contain 6 to 30 carbon atoms (i.e., C 6 -C 30 Aryl), preferably 6 to 20 carbon atoms (i.e. C 6 -C 20 Aryl), more preferably 6 to 12 carbon atoms (i.e. C 6 -C 12 aryl). In some embodiments, the aryl group contains 6 carbon atoms, 10 carbon atoms or 12 carbon atoms. Suitable aryl groups include, but are not limited to, phenyl, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenanthren, fluorene, pyrene, chrysene, perylene and azulene, preferably phenyl, biphenyl, triphenyl, benzylsulfonic acid, triphenylene, fluorene and naphthalene, wherein each aryl group can be optionally substituted.

[0050] As used herein in any embodiment, the term "aralkyl" describes an alkyl group consisting of 1 to 15 carbon atoms having an aromatic group as a substituent. Additionally, the aralkyl group may be optionally substituted.

[0051] As used in any embodiment herein, the term "alkoxy" describes any alkyl group bonded to an oxygen group. In some embodiments, alkoxy includes, but is not limited to, ethers, esters, amides, carboxylic acids, or alcohols. Also included in this definition are structures characterized by periodic insertion of oxygen atoms into carbon chains less than 20 carbon atoms and terminated with alcohols or alkyl groups, such as, but not limited to, polyethylene glycol. Preferred alkoxy groups are polyethylene glycol chains, preferably having 1 to 10 ethylene glycol repeating units, more preferably 2 to 8 ethylene glycol repeating units. In some embodiments, the polyethylene glycol chain comprises 5 ethylene glycol repeating units.

[0052] In any of the embodiments herein, A 1 , A 2 , A 1 ' and A 2 'Provide a solubilizing group for the structure of Formula I. As used herein, the term "solubilizing group" describes a terminal carboxylic acid, sulfonate, benzylsulfonic acid, ester, or alcohol group introduced to increase solubility in polar solvents (water, alcohol).

[0053] Dye molecules in R 1 -R 3 Selective halogenation at the position changes the electronic structure, making the pi system more susceptible to disruption or fragmentation, leading to color loss, effectively regulating the decolorization rate.

[0054] In some embodiments, the amine group can be substituted to produce a molecule such that:

[0055] i)A 1 and A 2 It can be the same or different;

[0056] ii) A 1 and A 2 'It can be the same or different;

[0057] iii) A 1 and A 1 'It can be the same or different;

[0058] iv) A 2 and A 1 'It can be the same or different;

[0059] v)A 2 and A 2 'may be the same or different; or

[0060] vi) A 1 ' and A 2 'It can be the same or different.

[0061] As used herein, the term "optionally substituted" means that the group concerned may be substituted at one or more positions with any one or more combinations of the following: halogen, hydrogen, alkyl, aryl, alkoxy, aralkyl, solubilizing groups.

[0062] In any of the embodiments herein, A 1 and A 1 'Same and A 2 and A 2 ' is the same. In some embodiments, A 1 and A 1 ' is an alkyl group, A 2 and A 2 ' is aryl. In some embodiments, A 1 and A 1 ' is C 1 -C 5 Alkyl, A 2 and A 2 ' is C 6 -C 12 In some embodiments, A 1 =A 1 '=ethyl and A 2 =A 2 ' = benzylsulfonic acid.

[0063] In any of the embodiments herein, A 1, A 1 '、A 2 and A 2 ' is an alkoxy group. In some embodiments, A 1 , A 1 '、A 2 and A 2 ' is polyethylene glycol (PEG). Preferably, A 1 , A 1 '、A 2 and A 2 ' is independently a polyethylene glycol having 1 to 10 ethylene glycol repeating units. Preferably, A 1 , A 1 '、A 2 and A 2 ' is independently polyethylene glycol having 2 to 8 ethylene glycol repeating units. In some embodiments, A 1 , A 1 '、A 2 and A 2 ' is a polyethylene glycol comprising 5 ethylene glycol repeating units. In some embodiments, A 1 , A 1 '、A 2 and A 2 ' are the same.

[0064] Non-limiting examples of compounds according to the invention are shown in Tables 1-4.

[0065] Table 1

[0066]

[0067] Table 2

[0068]

[0069] Table 3

[0070]

[0071] wherein n is 1 to 10, preferably 2 to 8.

[0072] Table 4

[0073]

[0074] Materials and methods

[0075] Material

[0076] Acid Green 9 was purchased from TCI Chemicals and used without further purification. N-Ethyl-N-benzylaniline-3'-sulfonic acid was purchased from AK Scientific, USA. Ethoxylated aniline was purchased from Ethox Chemicals. Haloaldehydes and p-toluenesulfonic acid (PTSA) were purchased from Sigma Aldrich. N,N-Dimethylformamide (DMF), ethanol, and tetrachlorobenzoquinone were purchased from VWR. Deuterated solvents were purchased from Cambridge Isotope Laboratories, Inc., USA. Hydrogen peroxide stock solution was purchased from Evonik and diluted to 0.5% w / w with deionized water (DI) before use.

[0077] Synthesis of triarylmethane metachloride

[0078] In a three-necked round-bottom flask equipped with a condenser, 2 eq of N-ethyl-N-benzylaniline-3'-sulfonic acid, 1 eq of PTSA and DMF were mixed and heated in an oil bath until the solid was completely dissolved. 1 eq of haloaldehyde was added and the mixture was stirred overnight to produce a colorless dye. 1 eq of tetrachlorobenzoquinone was added to the crude mixture. After 2.5 hours, the round bottom was removed from the heat source. The solvent was removed in vacuo and the resulting solid was redissolved in methanol and purified by chromatography to obtain the pure dye material.

[0079]

[0080] Scheme 1: Example of a general reaction scheme.

[0081] Synthesis of m-chloropolyethylene glycol (PEG) triarylmethane

[0082] In a beaker, 1 eq of ethanol was mixed with 3 eq of water and the pH of the mixture was adjusted to 0.7 using concentrated HCl. In a three-necked round-bottom flask equipped with a condenser, 2 eq of ethoxylated aniline and 1 eq of haloaldehyde were dissolved in the acidic ethanol / water mixture. The mixture was heated and stirred to produce a colorless dye. 1.1 eq of chlorobenzoquinone was added to the crude mixture. After 18 hours, the round bottom was removed from the heat source. The solvent was removed in vacuo and the dye was redissolved in methanol and purified by chromatography to obtain the pure dye substance.

[0083]

[0084] Scheme 2: Example of a general reaction scheme for PEG triarylmethane dyes

[0085] Fading test

[0086] Light absorption measurements were performed using a Shimadzu UV-VIS 1900i spectrometer.The dye was dissolved in unbuffered deionized water to prepare a 10 mM stock solution.

[0087] To measure the dye fading rate under alkaline conditions, 25 μL of the dye stock solution was added to 10 mL of 0.1 M pH = 8 potassium phosphate buffer. Then 3 mL of the pH = 8 diluted dye solution was transferred into a clean quartz cuvette and inserted into the spectrometer. For each investigated dye, its λ was measured every second. max Absorbance intensity for 400 s.

[0088] To measure the sensitivity of the dye to hydrogen peroxide, 25 μL of the dye stock solution was added to 10 mL of deionized water. 1.5 mL of the diluted stock solution was added to a clean quartz cuvette. 1.5 mL of a 0.5% w / w hydrogen peroxide solution was added to the same cuvette. The cuvette was then briefly vortexed to ensure even mixing and loaded into the spectrometer. For each investigated dye, its λ was measured every second. max Absorbance intensity for 400 s.

[0089] NMR characterization

[0090] Will 1 H NMR samples were dissolved in methanol D-4 and scanned using 300 MHz NMR.

[0091] Mass spectrometry analysis

[0092] Mass characterization data were acquired using a high-resolution mass spectrometer.

[0093] result

[0094] pass 1 H NMR and high-resolution mass spectrometry analysis showed that the triarylmethane metachloride has the theoretical mass and structure ( Figure 1-Figure 3 and Table 5 (below)).

[0095] pass 1 H NMR and high-resolution mass spectrometry analysis showed that m-chloroPEG triarylmethane has the theoretical mass and structure ( Figure 4-Figure 6 and Table 6 (below)).

[0096] In solution, both meta-chlorotriarylmethane and meta-chloroPEGtriarylmethane exhibit a greener blue color than Acid Green 9. Figure 7and Table 7 (below) depict the distinct changes in maximum absorbance and relative absorbance intensity between meta-chlorotriarylmethane, meta-chloroPEGtriarylmethane, and Acid Green 9. This difference in the absorbance spectra likely corresponds to a change in perceived color in solution.

[0097] Compared to Acid Green 9, both metachlorotriarylmethane and metachloroPEGtriarylmethane showed reduced stability under alkaline pH conditions. In a 25 μM solution at pH 8, both metachlorotriarylmethane and metachloroPEGtriarylmethane showed considerable fading within a 400 second time window, while Acid Green 9 showed negligible fading under the same conditions ( Figure 8 and Table 8 (below)).

[0098] Both metachlorotriarylmethane and metachloroPEGtriarylmethane exhibited enhanced fading in hydrogen peroxide compared to Acid Green 9. Unbuffered solutions of metachlorotriarylmethane and metachloroPEGtriarylmethane exhibited considerable fading within a 400 second time window when mixed with 0.5% w / w hydrogen peroxide. Acid Green 9 exhibited negligible fading within the same time window when combined with such low concentrations of hydrogen peroxide ( Fig. 9 and Table 9 (see below)).

[0099] Table 5 NMR peak assignments of triarylmethane metachloride dyes

[0100] dye A / A' Deviation (ppm) B / B′ Deviation (ppm) C / C′ Deviation (ppm) D* Deviation (ppm) Triarylmethane metachloride 1.35 3.80 4.98 NA

[0101] Table 6 NMR peak assignments of m-chloroPEG triarylmethane dyes

[0102] dye A Deviation (ppm) B offset (ppm) C Deviation (ppm) D Deviation (ppm) m-ChloroPEG triarylmethane 3.98 3.61 3.82 NA

[0103] Table 7 λmax position and absorbance value of triarylmethane methylene chloride dye and acid green 9

[0104] dye λmax(nm) Absorbance Acid Green 9 635 1.969 Triarylmethane metachloride 628 1.728 m-ChloroPEG triarylmethane 630 1.074

[0105] Table 8 Fading rate of 25 μM dye solution at λmax in pH=8 buffer

[0106] dye Fading rate in pH 8 buffer (mAbs / min) Acid Green 9 -0.001 Triarylmethane metachloride -0.014 m-ChloroPEG triarylmethane -0.048

[0107] Table 9 Fading rate of 25 μM dye mixed with 0.5% hydrogen peroxide

[0108] dye <![CDATA[Fading rate w / 0.5%(w / w)H 2 O 2 > Acid Green 9 0.000 Triarylmethane metachloride -0.013 m-ChloroPEG triarylmethane -0.663

[0109] While the invention has been particularly shown and described with reference to preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the scope of the invention as encompassed by the appended claims.

Claims

1. A modified triarylmethane dye comprising a structure shown in Formula 3, in R1, R2, R3, R4, R5, R6 and R7 are independently selected from hydrogen, halogen, C1-C 16 Alkyl, amino, nitro, methoxy, carboxyl, aryl, alkoxy or sulfonic acid; and A1, A2, A1' and A2' are independently selected from hydrogen, alkyl, aryl, alkaryl or alkoxy, provided that at least one of A1, A2, A1' and A2' is alkyl, aryl, alkaryl or alkoxy.

2. The modified triarylmethane dye according to claim 1, wherein R1, R2, R3, R4, R5, R6 and R7 are independently selected from hydrogen, halogen, C1-C 16 Alkyl, amino, nitro, methoxy, carboxyl, aryl, alkoxy or sulfonic acid, provided that at least one of R1, R2 or R3 is halogen.

3. The modified triarylmethane dye according to claim 1 or 2, wherein R4 and R5 are hydrogen.

4. The modified triarylmethane dye according to any one of claims 1 to 3, wherein R6 and R7 are hydrogen.

5. The modified triarylmethane dye according to any one of claims 1 to 4, wherein A1, A1', A2 and A2' are alkoxy groups.

6. The modified triarylmethane dye according to claim 5, wherein A1, A1', A2 and A2' are polyethylene glycols.

7. The modified triarylmethane dye according to claim 6, wherein A1, A1', A2 and A2' are independently polyethylene glycols having 1 to 10 ethylene glycol repeating units.

8. The modified triarylmethane dye according to claim 7, wherein A1, A1', A2 and A2' are polyethylene glycols having 5 ethylene glycol repeating units.

9. The modified triarylmethane dye according to any one of claims 1 to 8, wherein R2 is halogen.

10. The modified triarylmethane dye according to claim 9, wherein R2 is chlorine.

11. The modified triarylmethane dye according to claim 9 or 10, wherein R1 and R3 are hydrogen.

12. A modified triarylmethane dye comprising a structure shown in Formula 4, in R1, R2, R3, R4 and R5 are independently selected from hydrogen, halogen, C1-C 16 Alkyl, amino, nitro, methoxy, carboxyl, aryl, alkoxy or sulfonic acid, provided that at least one of R1, R2 or R3 is halogen; and A1, A2, A1' and A2' are independently selected from hydrogen, alkyl, aryl, alkaryl or alkoxy, provided that at least one of A1, A2, A1' and A2' is alkyl, aryl, alkaryl or alkoxy.

13. The modified triarylmethane dye according to claim 12, wherein R1, R2, R3, R4 and R5 are independently selected from hydrogen, halogen, C1-C 16 Alkyl, amino, nitro, methoxy, carboxyl, aryl, alkoxy or sulfonic acid, provided that at least one of R1, R2 or R3 is halogen.

14. The modified triarylmethane dye according to claim 12 or 13, wherein only one of R1, R2 or R3 is a halogen.

15. The modified triarylmethane dye according to claim 14, wherein (i) when R1 is halogen, R2 and R3 are hydrogen and R1 is selected from fluorine, bromine, chlorine or iodine, (ii) when R2 is halogen, R1 and R3 are hydrogen and R2 is selected from fluorine, bromine, chlorine or iodine, or (iii) When R3 is halogen, R1 and R2 are hydrogen and R3 is selected from fluorine, bromine, chlorine or iodine.

16. The modified triarylmethane dye according to claim 14 or 15, wherein R1 is halogen.

17. The modified triarylmethane dye according to claim 14 or 15, wherein R2 is halogen.

18. The modified triarylmethane dye according to claim 14 or 15, wherein R3 is halogen.

19. The modified triarylmethane dye according to any one of claims 12 to 18, wherein A1 and A1' are the same, and A2 and A2' are the same.

20. The modified triarylmethane dye according to claim 19, wherein A1 and A1' are alkyl groups, and A2 and A2' are alkaryl groups.

21. The modified triarylmethane dye according to claim 20, wherein A1 and A1' are C1-C5 alkyl groups, and A2 and A2' are C6-C5 alkyl groups connected to N via a bridging alkyl carbon. 12 Aryl.

22. The modified triarylmethane dye according to claim 21, wherein A1 and A1' are ethyl groups, and A2 and A2' are benzylsulfonic acid.

23. The modified triarylmethane dye according to any one of claims 19 to 22, wherein R2 is halogen.

24. The modified triarylmethane dye according to claim 23, wherein R2 is chlorine.

25. The modified triarylmethane dye according to any one of claims 12 to 18, wherein A1, A1', A2 and A2' are alkoxy groups.

26. The modified triarylmethane dye according to claim 25, wherein A1, A1', A2 and A2' are polyethylene glycols.

27. The modified triarylmethane dye according to claim 26, wherein A1, A1', A2 and A2' are independently polyethylene glycols having 1 to 10 ethylene glycol repeating units.

28. The modified triarylmethane dye according to claim 27, wherein A1, A1', A2 and A2' are polyethylene glycols having 5 ethylene glycol repeating units.

29. The modified triarylmethane dye according to any one of claims 25 to 28, wherein R2 is halogen.

30. The modified triarylmethane dye according to claim 29, wherein R2 is chlorine.

31. A modified triarylmethane dye according to claim 29 or 30, wherein R1 and R3 are hydrogen.

32. A modified triarylmethane dye comprising a structure shown in Formula 4, in R1, R2 and R3 are independently selected from hydrogen or halogen, provided that only one of R1, R2 or R3 is halogen, and provided that When R1 is halogen, R2 and R3 are hydrogen and R1 is selected from fluorine, bromine, chlorine or iodine, When R2 is halogen, R1 and R3 are hydrogen and R2 is selected from fluorine, chlorine, bromine or iodine, and When R3 is halogen, R1 and R2 are hydrogen and R3 is selected from fluorine, bromine, chlorine or iodine, R4 and R5 are hydrogen; and A1, A2, A1' and A2' are independently selected from hydrogen, alkyl, aryl, alkaryl or alkoxy, provided that at least one of A1, A2, A1' and A2' is alkyl, aryl, alkaryl or alkoxy.

33. The modified triarylmethane dye according to claim 32, wherein R1 is halogen.

34. The modified triarylmethane dye of claim 32, wherein R2 is halogen.

35. The modified triarylmethane dye of claim 32, wherein R3 is halogen.

36. The modified triarylmethane dye according to any one of claims 32 to 35, wherein A1 and A1' are the same, and A2 and A2' are the same.

37. The modified triarylmethane dye according to claim 36, wherein A1 and A1' are alkyl groups, and A2 and A2' are alkaryl groups.

38. The modified triarylmethane dye according to claim 37, wherein A1 and A1' are C1-C5 alkyl groups, and A2 and A2' are C6-C5 alkyl groups connected to N via a bridging alkyl carbon. 12 Aryl.

39. The modified triarylmethane dye according to claim 38, wherein A1 and A1' are ethyl groups, and A2 and A2' are benzylsulfonic acid.

40. A modified triarylmethane dye according to any one of claims 36 to 39, wherein R2 is halogen.

41. The modified triarylmethane dye of claim 40, wherein R2 is chlorine.

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