Indolium-based novel organic compound and cationic dye composition containing the same

Abstract

The present invention relates to a novel indolium-based organic compound and a cationic dye composition containing the same. The novel indolium-based organic compound is synthesized using readily available starting materials, and the invention is provided as a cationic dye composition containing the novel organic compound. The dye composition is well soluble in all solvents and is also well soluble in dye dispersions, does not exhibit color variation depending on the type of dispersant, and can exhibit excellent color intensity. In addition, in addition to conventional fabric dyeing methods, it can be easily printed via inkjet printing, allowing it to be printed not only on fabric but also on paper.

Description

Technology Field

[0001] The present invention relates to a novel indolium-based organic compound and a cationic dye composition containing the same. Background Technology

[0002] Synthetic fibers such as acetate and polyester have very high hydrophobicity compared to conventional cellulose and protein fibers, making them very difficult to dye with conventional dyes that are highly hydrophilic.

[0003] For dyeing such hydrophobic fibers, disperse dyes have been used as dyes that do not contain water-soluble groups and are insoluble in water, which are dispersed in water. However, disperse dyes cannot sufficiently achieve excellent dye uptake and high lightfastness due to their characteristics, and furthermore, their affinity for polyester blended fibers is not clear.

[0004] To solve these problems, prior patents disclose dyes with excellent lightfastness; however, it has been confirmed that said dyes have poor dyeability and product concentration, or poor lightfastness.

[0005] Accordingly, although there have been attempts to mix disperse dye compositions to improve not only lightfastness but also color development and dyeing rate, dyes of various colors that exhibit excellent high lightfastness and dyeing rate, as well as excellent color development, have not been developed. Prior art literature

[0006] (Patent Document 0001) KR 10-2007-0004638 A1 The problem to be solved

[0007] The object of the present invention is to provide a novel indolium-based organic compound and a cationic dye composition containing the same.

[0008] Another objective of the present invention is to synthesize a novel indolium-based organic compound using readily available starting materials and to provide a cationic dye composition comprising the novel organic compound, wherein the dye composition is well soluble in all solvents and also soluble in dye dispersions, exhibits no variation in color depending on the type of dispersant, and can exhibit excellent color intensity.

[0009] Another objective of the present invention is to provide a dye composition that can be easily printed via inkjet printing in addition to conventional fabric dyeing methods, and thus can be printed not only on fabric but also on paper. means of solving the problem

[0010] To achieve the above objective, the present invention may be a compound represented by the following chemical formula 1:

[0011] [Chemical Formula 1]

[0012]

[0013] Here,

[0014] n is an integer from 1 to 4, and

[0015] X1 is C(R2) or N + (R3) and,

[0016] X2 is selected from the group consisting of C(R4)(R5), N(R6), O and S, and

[0017] L1 is selected from the group consisting of a single bond, a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 30 carbon atoms, and a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.

[0018] Ar1 is selected from the group consisting of a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 1 to 60 carbon atoms, and a substituted or unsubstituted heteroarylalkyl group having 2 to 30 carbon atoms.

[0019] R1 to R6 are identical or different from one another and each independently hydrogen, deuterium, cyano group, nitro group, halogen group, hydroxyl group, substituted or unsubstituted C1 to C4 alkylthio group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C3 to C20 cycloalkyl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C24 alkynyl group, substituted or unsubstituted C7 to C30 aralkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C1 to C60 heteroaryl group, substituted or unsubstituted C2 to C30 heteroarylalkyl group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C30 It is selected from the group consisting of an alkylamino group, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted aralkylamino group having 7 to 30 carbon atoms, a substituted or unsubstituted heteroarylamino group having 1 to 24 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms.

[0020] In addition, the compound represented by the above chemical formula 1 may be a compound represented by the following chemical formula 2:

[0021] [Chemical Formula 2]

[0022]

[0023] Here,

[0024] n, X1, R1, L1, and Ar1 are as defined in Chemical Formula 1 above, and

[0025] R7 and R8 are identical or different from each other and each independently hydrogen, deuterium, cyano group, nitro group, halogen group, hydroxyl group, substituted or unsubstituted C1 to C4 alkylthio group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C3 to C20 cycloalkyl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C24 alkynyl group, substituted or unsubstituted C7 to C30 aralkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C1 to C60 heteroaryl group, substituted or unsubstituted C2 to C30 heteroarylalkyl group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C30 of It is selected from the group consisting of an alkylamino group, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted aralkylamino group having 7 to 30 carbon atoms, a substituted or unsubstituted heteroarylamino group having 1 to 24 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms.

[0026] In addition, the compound represented by the above chemical formula 2 may be a compound represented by the following chemical formula 3:

[0027] [Chemical Formula 3]

[0028]

[0029] Here,

[0030] n, X1, R1, Ar 1, R7 and R8 are as defined in Chemical Formula 2 above.

[0031] In addition, the above Ar1 may be a substituent represented by the following chemical formulas 4 to 6:

[0032] [Chemical Formula 4]

[0033]

[0034] [Chemical Formula 5]

[0035]

[0036] [Chemical Formula 6]

[0037]

[0038] Here,

[0039] * is the part that is combined,

[0040] m is an integer from 0 to 5, and

[0041] p and q are identical or different from each other, and each is independently an integer from 0 to 4, and

[0042] X3 and X4 are identical or different from each other, and each independently C(R 12 )(R 13 ), N(R 14 Selected from the group consisting of ), O and S,

[0043] X5 is C(R 15 ) or N + (R 16 ) and,

[0044] R9 and R 16The groups are identical or different from one another and each independently hydrogen, deuterium, cyano group, nitro group, halogen group, hydroxyl group, substituted or unsubstituted C1 to C4 alkylthio group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C3 to C20 cycloalkyl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C24 alkynyl group, substituted or unsubstituted C7 to C30 aralkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C1 to C60 heteroaryl group, substituted or unsubstituted C2 to C30 heteroarylalkyl group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C30 alkylamino group, It is selected from the group consisting of a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted aralkylamino group having 7 to 30 carbon atoms, a substituted or unsubstituted heteroarylamino group having 1 to 24 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms.

[0045] A cationic dye composition according to another embodiment of the present invention may include the above compound.

[0046] An inkjet printing method according to another embodiment of the present invention may include the cationic dye composition and print through inkjet printing filled with the cationic dye composition.

[0047] In addition, the inkjet printing described above may be used to print a desired shape on paper or fabric.

[0048] A method for dyeing a fabric according to another embodiment of the present invention may involve dyeing the fabric in a dyeing device using the cationic dye composition.

[0049] In addition, the fabric may be a hydrophobic fabric.

[0050] In addition, the hydrophobic fabric may be selected from the group consisting of acrylic fibers, polyester fibers, nylon fibers, and modacrylic fibers.

[0051] In the present invention, “hydrogen” is hydrogen, light hydrogen, deuterium, or tritium.

[0052] In the present invention, the “halogen group” is fluorine, chlorine, bromine, or iodine.

[0053] In the present invention, “alkyl” refers to a monovalent substituent derived from a straight-chain or side-chain saturated hydrocarbon having 1 to 40 carbon atoms. Examples thereof include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, hexyl, etc.

[0054] In the present invention, “alkenyl” refers to a monovalent substituent derived from a straight-chain or side-chain unsaturated hydrocarbon having 2 to 40 carbon atoms and one or more carbon-carbon double bonds. Examples thereof include, but are not limited to, vinyl, allyl, isopropenyl, and 2-butenyl.

[0055] In the present invention, “alkynyl” refers to a monovalent substituent derived from a straight-chain or side-chain unsaturated hydrocarbon having 2 to 40 carbon atoms and one or more carbon-carbon triple bonds. Examples thereof include, but are not limited to, ethynyl and 2-propynyl.

[0056] In the present invention, “aryl” refers to a monovalent substituent derived from an aromatic hydrocarbon having 6 to 60 carbon atoms, consisting of a single ring or a combination of two or more rings. Additionally, forms in which two or more rings are simply pendent or condensed may also be included. Examples of such aryls include, but are not limited to, phenyl, naphthyl, phenanthryl, anthryl, fluoryl, dimethylfluorenyl, etc.

[0057] In the present invention, “heteroaryl” refers to a monovalent substituent derived from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 6 to 30 carbon atoms. In this case, one or more carbons in the ring, preferably 1 to 3 carbons, are substituted with heteroatoms such as N, O, S, or Se. Additionally, forms in which two or more rings are simply pendent or condensed with each other may be included, and furthermore, forms condensed with an aryl group may also be included. Examples of such heteroaryls include, but are not limited to, 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, and triazinyl; polycyclic rings such as phenoxathienyl, indolizinyl, indolyl, purinyl, quinolyl, benzothiazole, and carbazolyl; and 2-furanyl, N-imidazolyl, 2-isoxazolyl, 2-pyridinyl, and 2-pyrimidinyl.

[0058] In the present invention, "aralkyl" refers to an aryl-alkyl group such as aryl and alkyl as described above. Preferred aralkyls include lower alkyl groups. Non-limiting examples of suitable aralkyl groups include benzyl, 2-phenethyl, and naphthalenylmethyl. Bonding to the parent residue is made through alkyl groups.

[0059] In the present invention, “heteroarylalkyl group” refers to an aryl-alkyl group substituted with a heterocyclic group.

[0060] In the present invention, “condensed ring” means a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring, a condensed heteroaromatic ring, or a combination thereof.

[0061] In the present invention, "forming a ring by combining with adjacent groups" means combining with adjacent groups to form a substituted or unsubstituted aliphatic hydrocarbon ring; a substituted or unsubstituted aromatic hydrocarbon ring; a substituted or unsubstituted aliphatic heteroring; a substituted or unsubstituted aromatic heteroring; or a condensed ring thereof.

[0062] In the present invention, "substitution" means that a hydrogen atom bonded to a carbon atom of a compound is replaced with another substituent, and the substitution location is not limited to the location where the hydrogen atom is substituted, that is, any location where a substituent can be substituted, and in the case of two or more substitutions, the two or more substituents may be the same or different from each other.

[0063] In the present invention, the substituents are hydrogen, a cyano group, a trifluoromethyl group, a nitro group, a halogen group, a hydroxyl group, a carboxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkyl thio group having 1 to 4 carbon atoms, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 24 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 2 to 60 carbon atoms, a heteroarylalkyl group having 6 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkylamino group having 1 to 30 carbon atoms, an arylamino group having 6 to 30 carbon atoms, an aralkylamino group having 6 to 30 carbon atoms, and a heteroalkyl group having 2 to 24 carbon atoms Selected from the group consisting of an arylamino group, an alkylsilyl group having 1 to 30 carbon atoms, an arylsilyl group having 6 to 30 carbon atoms, and an aryloxy group having 6 to 30 carbon atoms, and when substituted with a plurality of substituents, these are identical or different from each other. Effects of the invention

[0064] The present invention synthesizes a novel indolium-based organic compound using readily available starting materials and can be provided as a cationic dye composition comprising the novel organic compound. The dye composition is well soluble in all solvents and is also well soluble in dye dispersions, does not show color variation depending on the type of dispersant, and can exhibit excellent color intensity.

[0065] In addition, in addition to conventional fabric dyeing methods, it can be easily printed via inkjet printing, allowing it to be printed not only on fabric but also on paper. Brief explanation of the drawing

[0066] Figure 1 shows the TGA, DSC, FTIR, and XRD spectra of a compound according to one embodiment of the present invention. Figure 2 shows the visual color of an ethanol solution of a compound according to one embodiment of the present invention. Figure 3 is a UV-Visible absorbance spectrum for an ethanol solution of a compound according to one embodiment of the present invention. Figure 4 is the result of calculating the decomposition rate after dissolving a compound according to one embodiment of the present invention in ethanol and exposing it to UV light. FIG. 5 relates to the dye degradation estimate in the C / C0 versus time (h) graph, the reduction kinetic estimate in the -ln(C / C0) versus time (h) graph, and the rate constant graph of a compound according to one embodiment of the present invention. FIG. 6 is an image of the preparation of a disperse dye according to one embodiment of the present invention. FIG. 7 is a color and UV-Visible absorbance spectrum for a dispersion solution containing a compound according to one embodiment of the present invention. FIG. 8 is a photograph of a modacrylic fabric dyed with a compound according to one embodiment of the present invention. FIG. 9 is a bar diagram of the color and K / S values ​​of a compound according to one embodiment of the present invention. FIG. 10 is a UV-Visible spectrum of a fabric dyed with a compound according to one embodiment of the present invention. Figure 11 shows the dye depletion % value of a compound according to one embodiment of the present invention. FIG. 12 illustrates a process of inkjet printing using a compound according to one embodiment of the present invention. FIG. 13 is an image printed on paper and an image printed on fabric using a compound according to one embodiment of the present invention. FIG. 14 is the HOMO-LUMO energy level for a compound according to one embodiment of the present invention. Specific details for implementing the invention

[0067] Hereinafter, embodiments of the present invention are described in detail so that those skilled in the art can easily implement the invention. However, the present invention may be embodied in various different forms and is not limited to the embodiments described herein.

[0068] In the textile industry, dyeing and printing are diverse and important methods used to introduce color and design to textile fabrics and other materials. The textile industry is expanding and producing a wide range of textile products to meet fashion, wear, and marketing demands, while facing increasingly competitive technological challenges such as appearance, texture, strength, gloss, weight, flexibility, cost-effectiveness, and dye capabilities for dyeing and printing. With the rising demand for textiles today, the production of chemical and woven fibers has nearly multiplied, raising concerns about the ecological impact of textile manufacturing and subsequent removal processes. However, expectations for innovation and growth conflict with the high levels of environmental pollution and massive wastewater generation resulting from these industrial activities. Many recent studies indicate that the textile industry poses a risk of harming freshwater and atmospheric microbial systems due to the industrial production of hazardous and toxic chemicals and the release of these chemicals during the production process.

[0069] Modern society is now seeking luxurious, high-value-added textiles that possess ordinary softness and elegant fabrics. The production of synthetic fibers, particularly polyester, acrylic, and blends of the two, is increasing globally and plays a major role in fabrics and various patterns. Acrylic fiber is the most important artificial fiber, followed by polyester and nylon. Acrylic fabric is lightweight, soft, and warm, possessing characteristics most similar to wool, and can be used to mimic other fibers such as cotton when spun on short-staple equipment. It has also been widely used in clothing, materials, home furniture, convertible vehicles, awnings, paint roller covers, hand-knitting and knitting yarns, screens, stuffed animals, and more. Acrylic fiber possesses other properties such as hydrophilicity, chemical resistance, conductivity, antibacterial properties, fire resistance, and elastic strength. Acrylic fabric is acidic, reactive, and anionic, and is very difficult to print or dye using direct dyes, so it is not primarily used for acrylic coloring. The repulsive effect between the ionic functional groups of the fiber and the dye molecules affects dyeing.

[0070] Disperse dyes have poor quality in relation to fibers, resulting in dull colors and poor washing characteristics. Additionally, since the dyeing process is performed at approximately 190°C, the fibers turn yellow. In the above-mentioned acrylic fibers, dyes with good water solubility and cationic properties produce intense hue and high tint strength, while brightness decreases. The present invention aims to improve the transferability of dye molecules when printing on various substrates using an inkjet printer and dyeing acrylic fabrics. Accordingly, in the present invention, indolium-based cationic dye derivatives were synthesized to satisfy the above-mentioned problem.

[0071] Specifically, the novel indolium-based compound may be a compound represented by the following chemical formula 1:

[0072] [Chemical Formula 1]

[0073]

[0074] Here,

[0075] n is an integer from 1 to 4, and

[0076] X1 is C(R2) or N + (R3) and,

[0077] X2 is selected from the group consisting of C(R4)(R5), N(R6), O and S, and

[0078] L1 is selected from the group consisting of a single bond, a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 30 carbon atoms, and a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.

[0079] Ar1 is selected from the group consisting of a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 1 to 60 carbon atoms, and a substituted or unsubstituted heteroarylalkyl group having 2 to 30 carbon atoms.

[0080] R1 to R6 are identical or different from one another and each independently hydrogen, deuterium, cyano group, nitro group, halogen group, hydroxyl group, substituted or unsubstituted C1 to C4 alkylthio group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C3 to C20 cycloalkyl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C24 alkynyl group, substituted or unsubstituted C7 to C30 aralkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C1 to C60 heteroaryl group, substituted or unsubstituted C2 to C30 heteroarylalkyl group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C30 It is selected from the group consisting of an alkylamino group, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted aralkylamino group having 7 to 30 carbon atoms, a substituted or unsubstituted heteroarylamino group having 1 to 24 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms.

[0081] In addition, the compound represented by the above chemical formula 1 may be a compound represented by the following chemical formula 2:

[0082] [Chemical Formula 2]

[0083]

[0084] Here,

[0085] n, X1, R1, L1, and Ar1 are as defined in Chemical Formula 1 above, and

[0086] R7 and R8 are identical or different from each other and each independently hydrogen, deuterium, cyano group, nitro group, halogen group, hydroxyl group, substituted or unsubstituted C1 to C4 alkylthio group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C3 to C20 cycloalkyl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C24 alkynyl group, substituted or unsubstituted C7 to C30 aralkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C1 to C60 heteroaryl group, substituted or unsubstituted C2 to C30 heteroarylalkyl group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C30 of It is selected from the group consisting of an alkylamino group, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted aralkylamino group having 7 to 30 carbon atoms, a substituted or unsubstituted heteroarylamino group having 1 to 24 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms.

[0087] In addition, the compound represented by the above chemical formula 2 may be a compound represented by the following chemical formula 3:

[0088] [Chemical Formula 3]

[0089]

[0090] Here,

[0091] n, X1, R1, Ar 1, R7 and R8 are as defined in Chemical Formula 2 above.

[0092] In addition, the above Ar1 may be a substituent represented by the following chemical formulas 4 to 6:

[0093] [Chemical Formula 4]

[0094]

[0095] [Chemical Formula 5]

[0096]

[0097] [Chemical Formula 6]

[0098]

[0099] Here,

[0100] * is the part that is combined,

[0101] m is an integer from 0 to 5, and

[0102] p and q are identical or different from each other, and each is independently an integer from 0 to 4, and

[0103] X3 and X4 are identical or different from each other, and each independently C(R 12 )(R 13 ), N(R 14 Selected from the group consisting of ), O and S,

[0104] X5 is C(R 15 ) or N + (R 16 ) and,

[0105] R9 and R 16The groups are identical or different from one another and each independently hydrogen, deuterium, cyano group, nitro group, halogen group, hydroxyl group, substituted or unsubstituted C1 to C4 alkylthio group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C3 to C20 cycloalkyl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C24 alkynyl group, substituted or unsubstituted C7 to C30 aralkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C1 to C60 heteroaryl group, substituted or unsubstituted C2 to C30 heteroarylalkyl group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C30 alkylamino group, It is selected from the group consisting of a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted aralkylamino group having 7 to 30 carbon atoms, a substituted or unsubstituted heteroarylamino group having 1 to 24 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms.

[0106] The above X1 is N + (R3) It could be

[0107] The compound represented by the above chemical formula 1 may be a compound represented by the following chemical formula:

[0109]

[0110] Experimental Example

[0111] Instruments used for analysis

[0112] NMR analysis of the novel compounds of the present invention was performed using a Bruker AVANCE III 600. Ultraviolet-visible data for dye molecules in solution and solid states were obtained using an Agilent 8453 spectrometer. Spectroscopically characterized dye molecules, R1-R6 and their intermediates (1H, 13C-NMR and HRMS), the Bruker AVANCE III 600 MHz spectrometer used to record NMR spectra, and DMSO-d6 and CDCl3 were the solvents used for the measurements. A Bruker Microtope-Q was used to record the mass spectra of all samples.

[0113] Synthesis of 5-carboxy-2-(4-(dimethylamino)styryl)-1,3,3-trimethyl-3H-indol-1-ium iodide (R1)

[0114] Under a nitrogen atmosphere, 4-(dimethylamino)benzaldehyde (2.5 g, 16.7 mmol) and the iodide salt of intermediate 3 (5.8 g, 16.7 mmol) were placed in 25 mL of ethanol solvent. 2 to 3 drops of piperidine were added, and the reaction was continued at 80°C for 6 hours while stirring. Then, the mixture was cooled to form a precipitate, which was filtered, washed with a minimal amount of cold ethanol for further purification, and completely dried to obtain pure product R1 (5.1 g, 63.9%).

[0115] 1H-NMR; 600 MHz (DMSO-d6): 13.19 (1H, s); 8.38 (1H, d, J= 15.6 Hz); 8.29 (1H, d, J= 1.8 Hz); 8.09 (3H, m); 7.75 (1H, d, J= 8.4 Hz); 7.24 (1H, d, J= 15.6 Hz); 6.90 (2H, d, J= 9.0 Hz); 3.97 (3H, s); 3.20 (6H, s); 1.79 (6H, s). 13 C-NMR; 150 MHz (DMSO-d6): δ 181.05; 167.20; 155.80; 155.45; 146.05, 143.03; 135.25; 130.85; 129.70; 123.97; 123.02; 113.70; 112.93; 105.30; 51.08; 33.67; 26.73. HRMS: m / z calcd. for C 22 H 25 N2O2[M] + : 349.1911, found 349.1918.

[0116] Synthesis of 5-carboxy-2-(4-(diethylamino)styryl)-1,3,3-trimethyl-3H-indol-1-ium iodide (R2)

[0117] 4-(diethylamino)benzaldehyde (2.5 g, 14.1 mmol) and the iodide salt of intermediate 3 (4.9 g, 14.1 mmol) were dissolved in 25 mL of ethanol solvent under a nitrogen atmosphere. 2 to 3 drops of piperidine were added, and the reaction was continued at 80°C for 6 hours while stirring. Then, the mixture was cooled to form a precipitate, filtered, washed with a minimal amount of cold ethanol for further purification, and completely dried to obtain pure product R2 (5.3 g, 74.4%).

[0118] 1H-NMR; 600 MHz (DMSO-d6): 13.18 (1H, s); 8.35 (1H, d, J= 15.6 Hz); 8.28 (1H, d, J= 1.8 Hz); 8.09 (3H, m); 7.74 (1H, d, J= 8.4 Hz); 7.20 (1H, d, J= 15.0 Hz); 6.90 (2H, d, J= 9.0 Hz); 3.95 (3H, s); 3.56 (4H, q); 1.78 (6H, s); 1.17 (6H, t, J= 7.2 Hz). 13 C-NMR; 150 MHz (DMSO-d6): δ 180.74; 167.22; 155.57; 153.64; 146.09, 142.93; 130.86; 129.56; 129.70; 123.95; 122.82; 113.56; 112.76; 104.85; 50.96; 45.09; 33.57; 26.78; 13.08. HRMS: m / z calcd. for C 24 H 29 N2O2[M] + : 377.2224, found 377.2220.

[0119] Synthesis of 5-carboxy-2-(4-(diphenylamino)styryl)-1,3,3-trimethyl-3H-indole-1-iodide (5-carboxy-2-(4-(diphenylamino)styryl)-1,3,3-trimethyl-3H-indol-1-ium iodide (R3)

[0120] 4-(diphenylamino)benzaldehyde (2.5 g, 9.1 mmol) and the iodide salt of intermediate 3 (3.2 g, 9.1 mmol) were dissolved in 25 mL of ethanol solvent under a nitrogen atmosphere. 2 to 3 drops of piperidine were added, and the reaction was continued at 80°C for 6 hours while stirring. Then, the mixture was cooled to form a precipitate, which was filtered, washed with a minimal amount of cold ethanol for further purification, and completely dried to obtain pure product R3 (3.6 g, 65.5%).

[0121] 1H-NMR; 600 MHz (DMSO-d6): 13.32 (1H, s); 8.43 (1H, d, J= 16.2 Hz); 8.37 (1H, d, J= 1.2 Hz); 8.13 (3H, m); 7.89 (1H, d, J= 8.4 Hz); 7.42 (5H, m); 7.25 (6H, m); 6.87 (2H, d, J= 8.4 Hz); 4.07 (3H, s); 1.81 (6H, s). 13 C-NMR; 150 MHz (DMSO-d6): δ 182.99; 167.09; 155.03; 153.36; 145.75, 145.42; 143.71; 133.97; 130.88; 130.61; 127.08; 126.86; 126.62; 124.14; 118.59; 114.86; 109.19; 56.49; 52.01; 34.59; 26.18; 19.02. HRMS: m / z calcd. for C 32 H 29 N2O2[M] + : 473.2224, found 473.2223.

[0122] Synthesis of 5-carboxy-2-(4-(dibenzylamino)styryl)-1,3,3-trimethyl-3H-indol-1-ium iodide (R4)

[0123] 4-(dibenzylamino)benzaldehyde (2.5 g, 8.3 mmol) and the iodide salt of intermediate 3 (2.9 g, 8.3 mmol) were dissolved in 25 mL of ethanol solvent under a nitrogen atmosphere. 2 to 3 drops of piperidine were added, and the reaction was continued at 80°C for 6 hours while stirring. Then, the mixture was cooled to form a precipitate, which was filtered, washed with a minimal amount of cold ethanol for further purification, and completely dried to obtain pure product R4 (2.9 g, 55.6%).

[0124] 1H-NMR; 600 MHz (DMSO-d6): 13.26 (1H, s); 8.35 (1H, d, J= 15.6 Hz); 8.31 (1H, s); 8.06 (3H, m); 7.79 (1H, d, J= 8.4 Hz); 7.29 (11H, m); 6.94 (2H, d, J= 9.0 Hz); 4.97 (4H, s); 3.97 (3H, s); 1.77 (6H, s). 13 C-NMR; 150 MHz (DMSO-d6): δ 181.79; 167.18; 155.79; 154.36; 145.90, 143.23; 137.80; 134.89; 130.85; 130.26; 129.19; 127.69; 127.47; 127.10; 124.02; 123.70; 114.08; 113.64; 106.41; 56.49; 54.72; 51.37; 33.85; 26.53; 19.02. HRMS: m / z calcd. for C 34 H 33 N2O2[M] + : 501.2537, found 501.2522.

[0125] Synthesis of 5-carboxy-2-(2-(9-ethyl-9H-carbazol-3-yl)vinyl)-1,3,3-trimethyl-3H-indole-1-iodide (5-carboxy-2-(2-(9-ethyl-9H-carbazol-3-yl)vinyl)-1,3,3-trimethyl-3H-indol-1-ium iodide, R5)

[0126] 9-ethyl-9H-carbazole-3-carbaldehydride (2.5 g, 11.1 mmol) and the iodide salt of intermediate 3 (3.9 g, 11.1 mmol) were dissolved in 25 mL of ethanol solvent under a nitrogen atmosphere. 2 to 3 drops of piperidine were added, and the reaction was continued at 80°C for 6 hours while stirring. Then, the mixture was cooled to form a precipitate, filtered, washed with a minimal amount of cold ethanol for further purification, and completely dried to obtain pure product R5 (4.1 g, 63.9%).

[0127] 1 H-NMR; 600 MHz (DMSO-d6): 13.33 (1H, s); 9.19 (1H, s); 8.73 (1H, d, J= 15.6 Hz); 8.40 (2H, m); 8.27 (1H, d, J= 7.8 Hz); 8.17 (1H, m); 7.93 (1H, d, J= 8.4 Hz); 7.85 (1H, d, J= 8.4 Hz); 7.74 (2H, m); 7.57 (1H, m); 7.37 (1H, m); 4.54 (2H, q); 4.18 (3H, s); 1.89 (6H, s); 1.37 (3H, t, J= 7.2 Hz). 13 C-NMR; 150 MHz (DMSO-d6): δ 183.41; 167.10; 155.28; 145.75; 143.81, 143.79; 140.90; 131.01; 130.89; 129.97; 127.56; 126.31; 125.98; 124.17; 123.74; 122.88; 121.30; 121.20; 114.97; 110.80; 109.67; 56.49; 52.18; 38.07; 34.80; 26.23; 19.02; 14.33. HRMS: m / z calcd. for C 28 H 27 N2O2[M] + : 423.2067, found 423.2058.

[0128] Synthesis of 2-3-(5-carboxy-1,3,3-trimethylindolin-2-ylidene)prop-1-en-1-yl-1,3,3-trimethyl-3H-indol-1-ium iodide (R6)

[0129] Under a nitrogen atmosphere, 2-(1,3,3-trimethylindoline-2-ylidene)acetaldehyde (2.5 g, 12.4 mmol) and the iodide salt of intermediate 3 (4.3 g, 12.4 mmol) were added to 25 mL of ethanol solvent. 2 to 3 drops of piperidine were added, and the reaction was continued at 80°C for 6 hours while stirring. Then, the mixture was cooled to form a precipitate, filtered, washed with a minimal amount of cold ethanol for further purification, and completely dried to obtain pure product R6 (3.5 g, 53.3%).

[0130] 1 H-NMR; 600 MHz (DMSO-d6): 13.02 (1H, s); 8.34 (1H, t, J= 13.8 Hz); 8.13 (1H, d, J= 1.2 Hz); 8.02 (1H, m); 7.68 (1H, d, J= 7.2 Hz); 7.54 (1H, d, J= 7.8 Hz); 7.48 (2H, m); 7.35 (1H, m); 6.60 (1H, d, J= 13.2 Hz); 6.46 (1H, d, J= 13.2 Hz); 3.72 (3H, s); 3.64 (3H, s); 1.72 (6H, s); 1.71 (6H, s). 13 C-NMR; 150 MHz (DMSO-d6): δ 176.17; 174.39; 167.43; 150.34; 146.90, 142.96; 131.06; 129.12; 127.40; 126.34; 123.74; 122.95; 112.57; 111.22; 104.95; 103.19; 49.78; 48.72; 32.31; 27.79; 27.54. HRMS: m / z calcd. for C 26 H 29 N2O2[M] + : 401.2224, found 401.2225.

[0131] Experimental results

[0132] Design and Synthesis

[0133] Derivatives of highly reactive indole cationic dyes were synthesized for modacrylic fabric dyeing and printing applications. The Fischer-Indole condensation process was performed by treating 4-aminobenzoic acid with hydrazine under ice bath conditions. Additionally, 4-hydrazine benzoic acid was reacted with 3-methyl-2-butanone under acidic (AcOH) conditions overnight at 100°C to form an indole molecule. The nitrogen group of indoline 2 was formed by N-alkylation using methyl iodide to produce a quadrupole flame 3. Aldehydes such as 4-(diphenylamino)benzaldehyde, 6,4-(dibenzylamino)benzaldehyde, 7,9-ethyl-9H-carbazole-3-carbaldehydride, and 2-(1,3,3-trimethylindoline-2-ylidene)acetaldehyde were readily prepared using POCl3 and DMF. Finally, the active methyl group of indolenium salt 3 was combined with the corresponding aldehydes 4-9 via the Knoevenagel reaction method using ethanol as a solvent and piperidine as a catalyst at 80°C for 6 hours to form the desired dyes R1-R6, respectively.

[0134] The reaction scheme for the above synthesis method is as follows:

[0135]

[0137] Thermal stability, FTIR, and XRD studies

[0138] To confirm the physical properties of the synthesized dye molecules R1-R6, TGA and DSC analyses were performed while increasing the temperature from 25°C to 500°C at a rate of 10°C / min in the presence of an N2 atmosphere, and the results are as shown in Figure 1A.

[0139] In the above experimental results, the thermal gravimetric weight loss values ​​were found to be at a minimum value (less than 3% of the weight loss ratio of R4-R6 dyes at temperatures of 50–80°C). After 250°C, the total weight loss rates of dyes R1, R2, and R6 were 78.87%, 84.67%, and 75.88%, respectively, recording 78.87%, 84.67%, and 75.88% of the total weight loss. However, dyes R3, R4, and R5 exhibited two stages of thermal decomposition temperature (Td): above 200°C (R3 weight loss rate 36.51%, R4 weight loss rate 24.03%, R5 weight loss rate 36.07%) and above 300°C (R3 weight loss rate 20.87%, R4 weight loss rate 41.03%, R5 weight loss rate 18.95%). Based on the above measurement results, it was concluded that all dyes are thermally stable up to 200°C. In addition, the endothermic peak characteristics of the DSC studies for dyes R1 to R6 were measured, and the transition melting temperatures (Tm) were 285.03°C (R1), 230.03°C (R2), 264.07°C (R3), 213.63°C (R4), 275.27°C (R5), and 306.75°C (R6), respectively, and the results are shown in Fig. 1B.

[0140] The absorption bands perturbed by functional group vibrations of the synthetic dye were confirmed through FT-IR analysis. 1706–1720 cm⁻¹ -1 A strong peak appeared in the range, which corresponds to the carboxylic acid (C=O) elongation of the dye. Also, 1450–1620 cm⁻¹ -1 At this point, the aromatic C=C stretching was enhanced, and the aromatic ring was substituted with an imidazole group, resulting in a weak bending peak. The presence of the imidazole-aromatic C=N stretching was observed at 1260–1350 cm⁻¹. -1 It was observed in the range. The imidazole and aldehyde functional groups connecting the C=C bending peak points of vinylidene are 810–930 cm⁻¹. -1It appeared within the range (Fig. 1C). In addition, powder XRD was analyzed for dyes R1 and R6 as representative cases to confirm the morphological characteristics of the dyes. The results showed that both dyes exhibited a clear crystallinity pattern. As shown in Fig. 1D, both dyes showed nearly similar patterns in the XRD. Furthermore, the dyes can be used for dyeing and printing purposes suitable for fabrics and paper.

[0141] Visual color and ultraviolet-visible light measurement

[0142] To synthesize a magenta dye, a series of molecules were created with slight differences in the electron donor unit while maintaining the acceptor unit (carboxyindolium group) of all molecules constant. The preliminary colors of the synthesized dye molecules R1-R6 were determined by dissolving them in an ethanol solution. The colors of each molecule are shown in Fig. 2. It was observed that N-methyl (R1) and N-ethyl (R2) exhibited a vivid purple color, N-phenyl (R3) a bluish-pink color, N-benzyl (R4) and indoline (R6) moiety a pink color, and the carbazole (R5) molecule fused with the carboxyindolium probe a reddish-orange color. All of these cyanine dyes produced vivid colors and dissolved very well in ethanol (Fig. 2). The UV-visible absorption spectra of all these dye molecules were recorded and are shown in Fig. 3. Dye R1 λ max The absorbance spectra of were observed at 559 nm for R, R2 at 562 nm, R3 at 547 nm, R4 at 550 nm, R5 at 513 nm, and R6 at 553 nm. The absorbance peaks of all dyes, excluding dye molecule R5, were in the range of 547–562 nm. λ max The hue changes due to a small difference. The color of the dye molecule is λ max In addition, it is also determined by the peak width of the head and tail portions of the peak. The color change and corresponding UV data are as shown in Figures 2 and 3.

[0143] Ultraviolet-visible light study for lightfastness measurement

[0144] The lightfastness of dyes R1-R6 was determined through ultraviolet-visible spectrum studies. All dye concentrations (1 x 10⁻⁶ -5 M) and the solvent (ethanol) were kept constant. After transferring the solution to a vial, it was exposed to strong ultraviolet light. Dye R1 λ max The absorbance spectra of were observed at 559 nm, R2 at 562 nm, R3 at 547 nm, R4 at 550 nm, R5 at 513 nm, and R6 at 553 nm. The corresponding dye λ max Measurements were taken after irradiating with ultraviolet light every hour, and changes were monitored using UV-visible spectrum studies for at least 6 hours. The observed spectral changes are shown in Fig. 4. Dyes R1 degraded at approximately 4%, followed by R2 (13%), R3 (35%), R4 (10%), R5 (38%), and R6 (2.5%). The results obtained from all of the above dyes confirmed that dyes R1 and R6 exhibited much lower degradation rates compared to other dyes. The degradation rates of dyes R1-R6 over time were calculated, and the results are shown in Fig. 5.

[0145] Estimation of dye degradation rate

[0146] The dye degradation rate of the dyes of the present invention was measured from data before and after UV irradiation. Dye degradation was confirmed in the order of R6 > R1 > R4 > R2 > R3 > R5. A plot of C / C0 against time was measured and shown in Fig. 6A, where C is the concentration of the dye over time and C0 is the initial concentration of the dye. As shown in Figs. 6B and C, a linear relationship between -ln(C / C0) and time (h) was obtained for all dyes. From this data, the rate constant (k) for all dye molecules was obtained using the equation -ln(C / C0) = kt, and the result is shown in Fig. 6D. The measurement results indicate that dyes R1 and R6 exhibit lower dye degradation compared to other dyes. Therefore, dye molecules R1 and R6 are much more stable than all other dye molecules.

[0147] Preparation of R1-R6 cyanine dye mixed dispersion

[0148] First, to prepare a uniform mixture of cationic ink dye and dispersant, a commercially available dispersion was prepared by converting it to weight as follows: the dispersant was prepared with a 1:1 ratio of dispersant to deionized water. Then, it was ultrasonically treated at 50°C for 30 minutes. A highly reactive indole cationic derivative ink was taken at 3% (w / w, total weight, 0.030 g) according to the weight of the acrylic fabric (w / w, fabric weight 1 g). This indole cationic ink was dissolved in 10% ethanol and 3% ethylene glycol (w / w, cationic ink weight, 0.03 g), and 10 mL of dispersant was added to the mixture. Additionally, this dye dispersion mixture was heated by ultrasonical treatment at 50°C for 30 minutes. Thus, this uniformly dispersed dye solution can be used to dye acrylic fabric (Fig. 7).

[0149] Visual and UV-Visible Spectral Study of R1-R6 Dye Dispersion Solutions

[0150] The six synthesized dyes R1-R6 were dispersed in a dyeing solution by the dyeing process described above. The color of the dispersant solution is indicated in Fig. 8A, and the corresponding UV-visible spectrum is as shown in Fig. 8B. Dyes R1 λ max The absorbance spectra of are at 552 nm for R, 558 nm for R2, 541 nm for R3, 541 nm for R4, 510 nm for R5, and 550 nm for R6. No clear peak appeared for dye molecule R5, while the absorbance peaks for the other dyes were in the 540–550 nm range. The UV-visible spectra of dyes R1–R6 recorded in the presence of solution and dispersant are λ max It shows slight changes, implying that there is some kind of interaction between the dyes. These dyes of the dispersant were additionally used in dyeing modacrylic fabrics.

[0151] dyeing

[0152] For the dyeing test of the acrylic fabric experiment using uniformly dispersed ink samples, an infrared dyeing machine (Korea) of the Hanbat Automatic Control Co., Ltd. Model ACE-6000T was used. An untreated modacrylic fabric (5 x 10 cm, approx. 1 g) was placed in a sealed stainless steel tube container, and the prepared cationic dispersion dye was added. The cationic dye was then applied to the modacrylic fabric using traditional techniques. In this case, the fabric was immersed in the dye solution and placed appropriately in the container of the dyeing device to maintain an initial temperature of 25°C. Additionally, the dyeing machine was sealed, and the temperature was gradually raised to 100°C at a rate of 2°C per minute, after which the dyeing process was continued for 60 minutes. Finally, the dye bath was slowly cooled to room temperature at a rate of 2°C / min. Then, soaping was performed on the same dyeing machine, the ACE-6000T. Soaping was performed at 100°C for 15 minutes, after which the fabric was slowly cooled to room temperature, and then the fabric was washed with water to remove unbound dye and the soaping solution from the fabric. The dyed modacrylic fabric was dried outdoors for one day. Further research was conducted on the dyed fabric and the remaining undyed materials shown in Fig. 9.

[0153] CIE color coordinates and color evaluation of intensity

[0154] The color index coefficients of dyed and jet-printed fabrics were measured using a DataColor spectrophotometer in the 400–700 nm range, and the absorption-scattering ratio was determined by calculating the Kubelka-Munk coefficient from the average reflectance of the dyed fabric. The Kubelka-Munk coefficient (K / S) values ​​were calculated using the following formula:

[0155] [Absorption-Scattering Ratio Equation]

[0156]

[0157] Here, K is the absorption coefficient of the dyed fabric, S is the scattering coefficient of the dyed fabric, and Rmin is the spectral reflectance representing the optical properties of the color quality of the dyed fabric.

[0158] The K / S value indicates the correlation between the dyeing quality of the fabric and the dyeing color intensity of the fabric yield results. In this case, the K / S values ​​of cationic dyes R1, R2, and R6 are the highest, which means that the dye derivatives exhibit excellent color development values, as shown in Table 1 below. In fact, the remaining cationic dyes were found to have the lowest and most acceptable K / S values ​​due to solubility issues with these cationic inks when preparing the dye dispersion solution. Solubility issues may occur if large or heavy phenyl additives are present in the cationic inks R3-R5. However, these dyes (R3-R5) produced colorful acrylic fabrics after dyeing, showing high lightness (L*) values, low red-green (a*), and the lowest yellow-blue (b*) values, but were found to have poor fiber dyeability. Color values ​​were measured using a data color spectrophotometer as indicated in Table 1 and Figure 10A. Based on the L*a*b* and K / S values ​​in Fig. 10B, the staining properties were in the following order: R1>R2>R6>R5>R4>R3. All dyes had positive L* and C* values, which indicates that the color tone shifts from light to dark.

[0159] a Positive values ​​of the dye color hue were shifted along the redness direction of the red-green axis. b At negative values, the hue, excluding dye R5, was shifted along the bluish direction of the yellow-blue axis.

[0160] L* a* b* C* h (K / S) R1 32.60 47.78 -37.14 60.53 322.15 9.89 R2 42.20 43.23 -37.97 57.53 318.70 9.55 R3 61.74 12.24 -15.36 19.64 308.55 1.24 R4 61.05 49.65 -10.25 50.69 348.83 2.57 R5 62.77 51.63 13.70 53.42 14.86 2.75 R6 54.09 69.46 -5.35 69.67 355.59 9.11

[0161] L* = Brightness axis, a* = Red-Green axis, b* = Yellow-Blue axis, C* = Saturation, h = Hue angle, K / S = Color intensity

[0162] Study of Ultraviolet Visible Light and Reflectance Spectra of Dyed Fabrics

[0163] The dyed fabric is shown in Fig. 9. Cyanine dyes R1–R6 exhibit excellent solubility in most organic solvents, particularly common organic solvents such as water, toluene, dichloromethane, chloroform, tetrahydrofuran, and acetone. All six dye molecules changed from purple to magenta in these solvents. These dye molecules are also electron-donor-acceptor chromophores, in which the amino and carboxyl groups, respectively, act as electron donors and acceptors. The ultraviolet-visible spectrum of the ethanol solution was measured at 200–900 nm (Fig. 4). The absorbance λ of the dye max At 559 nm: R1 is 559 nm, R2 is 562 nm, R3 is 547 nm, R4 is 550 nm, R5 is 513 nm, and R6 is 553 nm. This originates from the n-π transition of the molecule. Additionally, as a result of recording the UV visible light spectrum of the dyed fabric, broad peaks appeared for the dyed fabric R1 at 530–588 nm, R2 at 540–590 nm, R3 at 568 nm, R4 at 550 nm, R5 at 510 nm, and R6 at 500–565 nm (Fig. 11).

[0164] After dyeing, all dyes exhibited broad peaks, but the color of the dye molecules did not change significantly between the solution and after dyeing. This implies that these molecules are highly effective for fabric dyeing. Noticeable color changes were observed during dyeing even with small substitution changes in the electron donor function, and since the intensity of the dye within the fabric varies depending on the substitution of the electron donor group, the color of the fabric can be easily controlled by changing the substitution of the electron donor unit. The reflectance spectrum of the dyed fabric was also measured. The reflectance curve was formed around R1, a broad peak at 530–588 nm, R2 at 540–590 nm, R3 at 568 nm, R4 at 550 nm, R5 at 510 nm, and R6 at 500–565 nm.

[0165] depletion rate

[0166] The dye depletion rates for dyes R1 through R6 were calculated from the UV-Visible spectrum data, and the results are shown in Figure 12. In this experiment, dye dispersions were used before and after dyeing. 200 mL of dye solution was dissolved in 2 mL of water and uniformly mixed for all dyes to obtain UV-Visible spectra. The UV-Visible spectra showed dye depletion rates of approximately 50.2% for R1, 45% for R2, 72.9% for R3, 50.9% for R4, 9.7% for R5, and 62.7% for R6. The carbazole-fused dye molecule R5 exhibited very weak interaction with the fiber compared to other dye molecules studied in this research.

[0167] Inkjet printing on paper and fabric

[0168] The synthesized molecules R1-R6 were printed on A4 paper and fabric surfaces using digital printing materials. For this purpose, a Canon printer model MG2590 and a Canon color cartridge CL-946 were used.

[0169] The above cartridge was purchased from a local market and the ink in the cartridge was completely removed by washing it with water and ethanol. Approximately 0.5 g of dye R1 was mixed with 10 ml of ethanol, 0.25 ml of glycerol, and 3 ml of water to make a homogeneous solution, and the remaining dye solutions R2-R6 were prepared in a similar manner. The prepared dyes are highly suitable for use as digital printing inks, and a schematic representation of the process performed in inkjet printing after injecting the ink into the cartridge is shown in Fig. 13. Images were printed on both paper and fabric, as shown in Figs. 14A and 14B. The color intensity of the image printed on paper is very vivid and visible compared to the image printed on fabric.

[0170] Therefore, the development of this material can be very convenient and advantageous for printing on substrates such as paper and fabric. When comparing the dyed fabric and the printed image, dyes with phenyl (R3, R4) and carbazole (R5) substituted in the electron donor unit did not bind much in the dyed fabric. In the printed image, only the cyan dye substituted with carbazole (R5) showed poor results when compared to other dyes.

[0171] Frontier Molecular Orbital Analysis

[0172] The color (λmax) and substitution effects of molecules R1-R6 were determined using DFT calculations. The HOMO and LUMO energy gaps of molecules R1-R6 were measured using the Gaussian 09 program along with the B3LYP (321G) base set. The results of these calculations confirm information regarding the energy gaps and electron distributions (Fig. 15). Through these calculations, a correlation between the dye color and the substitution effects could be established. The HOMO was found primarily in the phenyl ring (electron donor unit) substituted with an amine, whereas the LUMO was clearly present in the indolium ring (electron acceptor unit) substituted with a carboxyl group. The energy gap of molecules R1-R6 ranges from 2.4 to 2.7 eV. The distinct electron distributions of the electron donor and electron acceptor units indicate strong charge transfer between them. R1 = 2.515 eV (λmax = 559 nm), R2 = 2.481 eV (λmax = 562 nm), R3 = 2.626 eV (λmax = 547 nm), R4 = 2.554 eV (λmax = 550 nm), R5 = 2.753 eV (λmax = 513 nm), and R6 = 2.553 eV (λmax = 553 nm). The energy gap was lower for molecule R2, which is substituted with N-ethyl, and higher for dye R5, which is substituted with carbazole. Therefore, dye molecule R2 exhibited a greater color variation compared to dye R5. The energy gaps and λmax obtained from DFT calculations and the UV-visible spectrum show that as E increases, λmax decreases, and vice versa.

[0173] In conclusion, six cyanine dyes with different electron-donating unit substituents could be easily synthesized using readily available starting materials. The prepared dye molecules were spectroscopically characterized. The molecules were highly soluble in almost all solvents. The λmax values ​​for the dyes were R1: 559 nm, R2: 562 nm, R3: 547 nm, R4: 550 nm, R5: 513 nm, and R6: 553 nm. Since modacrylic fabrics are used for various purposes, such as worker warning cloths, dye dispersions were prepared for appropriate dyeing. The dye molecules exhibited similar colors in the solution and the dispersant, and no color variation was observed depending on the dispersant used. The dyed fabrics showed excellent color intensity K / S for molecules R1 (9.89), R2 (9.55), and R6 (9.11), while exhibiting very weak color intensity for R3 (1.24), R4 (2.57), and R5 (2.75). These dyes can also be used to print on substrates such as paper and fabric using inkjet printing. Images obtained from the prepared ink showed better coloring for all dyes except dye R5. Therefore, compared to fabric dyeing, these molecules can be used exclusively for printing on various substrates. As a result of performing theoretical calculations on these six dye molecules, it was observed that λmax decreases as △E increases; thus, customized molecules with various colors could be obtained through theoretical design and synthesis.

[0174] Although preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements by those skilled in the art using the basic concept of the present invention as defined in the following claims also fall within the scope of the present invention.

Claims

Claim 1 Compound represented by the following chemical formula 3: [Chemical Formula 3] [Chemical Formula 4] [Chemical Formula 5] [Chemical Formula 6] Here, * is the bonding portion, n is 1, m is an integer from 0 to 5, p and q are identical or different from each other and are each independently integers from 0 to 4, Ar1 is selected from the group consisting of substituents represented by the above chemical formulas 4 to 6, and X1 is N + (R3) and X3 is N(R 14 ) and X4 is C(R 12 )(R 13 ) and X5 is N + (R 16 ) and, R1 is a carboxyl group, and R3, R7, R8, R 12 , R 13 , R 14 and R 16 is identical or different from one another and is each independently a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, R9 is selected from the group consisting of a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, and a substituted or unsubstituted aralkylamino group having 7 to 30 carbon atoms, and R 10 and R 11 It is hydrogen. Claim 2 delete Claim 3 delete Claim 4 delete Claim 5 A cationic dye composition comprising a compound according to claim 1. Claim 6 An inkjet printing method comprising a cationic dye composition according to claim 5, and printing through an inkjet printer filled with said cationic dye composition. Claim 7 In claim 6, the inkjet printing method is an inkjet printing method that prints a desired shape on paper or fabric. Claim 8 A method for dyeing a fabric in a dyeing device using a cationic dye composition according to paragraph 5. Claim 9 In paragraph 8, the above fabric is a hydrophobic fabric, and the dyeing method of the fabric. Claim 10 In claim 9, the above hydrophobic fabric is a dyeing method for a fabric selected from the group consisting of acrylic fibers, polyester fibers, nylon fibers, and modacrylic fibers.

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