High-stability water-based nano pigment ink and preparation method thereof

Abstract

The invention belongs to the technical field of ink-jet ink, and provides high-stability water-based nano pigment ink and a preparation method thereof. The high-stability water-based nano pigment ink comprises a water-based solvent, resin, color paste, a stabilizer, a surfactant and water in specific mass fraction, wherein the structural formula of the stabilizer is shown in the specification. In the invention, the stabilizer has good compatibility and stability, the prepared water-based nano pigment ink can be stably stored for a long time and is smooth in ink jet, and the ink jet stability of the water-based nano pigment ink is improved; the stabilizer can also improve the dispersion stability of the nano pigment color paste, and has the effects of preventing blockage and stabilizing ink jet in the ink-jet printing process; by adopting the water-based nano pigment ink disclosed by the invention, the fabric does not need to be subjected to pre-treatment and post-treatment, the process is simple, no wastewater is generated in production, the production cost can be saved, and sedimentation is avoided; and compared with traditional printing, the technological process is simplified, and environment friendliness is achieved.

Description

Technical Field

[0001] This invention relates to the field of inkjet ink technology, and in particular to a highly stable water-based nano-pigment ink and its preparation method. Background Technology

[0002] Digital textile printing has become an extremely popular printing technology in the textile industry due to its advantages such as no need for plate making, simple process, rapid response to market changes, and ability to achieve small-batch, multi-variety, multi-color printing and personalized customization. Textile pigment inks, which produce no wastewater during printing, have simple printing processes, are not limited by fiber type, and have high lightfastness, are increasingly favored by users and represent the future development direction of digital textile inks.

[0003] Inkjet stability is a crucial performance characteristic of inks, directly determining whether pigment inks can be used reliably. Inkjet stability, also known as continuous inkjet performance, is related to pigment dispersion, ink viscosity, and surface tension. In high-intensity inkjet printing, excessively high ink viscosity can disrupt the ink flow, potentially causing broken lines and smaller droplets, resulting in lighter print colors. Conversely, excessively low ink viscosity can create satellite droplets during printing, also affecting print quality. Low surface tension increases ink penetration into the substrate, leading to issues like jagged edges and color bleeding. Excessively high surface tension makes it difficult for air bubbles to burst, increasing the likelihood of air blockage and causing inkjet instability.

[0004] Chinese patent CN120291385A discloses a method for preparing a highly stable self-crosslinking colloidal photonic ink for inkjet printing on textiles. It proposes a strategy combining surface-carboxylated hard-core-soft-shell nanospheres with polymer-induced bonding on the fabric surface. This effectively resists microsphere aggregation caused by high shear forces and sudden temperature changes during inkjet printing, avoiding printhead clogging. The color-fixing time is 10-20 minutes. Chinese patent CN119931416A discloses an inkjet printing water-based ink and its preparation method, as well as a composite film flexible packaging. It adds 8-12 parts of naphthalene-modified acrylic dispersant to the ink, using the naphthalene ring structure as the core framework to construct the dispersion system. The electron cloud density characteristics of the naphthalene ring structure significantly enhance the chemical adsorption stability of the dispersant on the pigment surface. Furthermore, by controlling the amount of resin and water-soluble organic solvent added, the surface tension and viscosity are adjusted, thereby improving the smoothness of inkjet printing. However, its wash fastness on textiles is not clearly defined. Chinese patent CN119866362A discloses a water-based inkjet composition for textile printing. It improves inkjet stability by adding alkali metal salts and acrylate-olefin copolymers to the ink as dispersants. However, if the amount added is too high, it will have a significant impact on inkjet stability, color and wet rubbing fastness.

[0005] Therefore, improving the inkjet stability of water-based nano-pigment inks to meet the requirements of the digital printing industry is particularly important. Summary of the Invention

[0006] The purpose of this invention is to provide a highly stable water-based nano-pigment ink and its preparation method, addressing the shortcomings of existing technologies.

[0007] To achieve the above-mentioned objectives, the present invention provides the following technical solution: This invention provides a highly stable water-based nano-pigment ink, which comprises the following raw materials by mass fraction: The composition is as follows: 10-15% aqueous solvent, 15-32% resin, 20-40% color paste, 5-10% stabilizer, 0.1-1% surfactant, and the balance is water. The structural formula of the stabilizer is: , Among them, R1 to R4 independently contain H, C1 to C6 alkyl, C1 to C6 alkoxy, C1 to C6 alkenyl or C1 to C6 alkynyl; R5 contains a carbonyl group, a thiocarbonyl group, or -CNH-; Q1~Q4 contain H, -OH or -NH2 independently.

[0008] Preferably, the aqueous solvent comprises one or more of anhydrous ethanol, n-propanol, isopropanol, n-butanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, polyethylene glycol, glycerol, pentaerythritol, 2-pyrrolidone, and N-methylpyrrolidone.

[0009] Preferably, the resin comprises one or more of polyurethane resin, acrylic resin, polyolefin resin, epoxy resin, formaldehyde resin, urea-formaldehyde resin, and fluorocarbon resin.

[0010] Preferably, the pigment paste is a nano-pigment pigment paste, and the D of the nano-pigment pigment paste is... 50 The wavelength is 100~130nm.

[0011] Preferably, the surfactant comprises one or more of the following: acetylenic diol surfactants, polyether siloxane surfactants, acrylic surfactants, and organofluorine surfactants.

[0012] The present invention also provides a method for preparing the high-stability water-based nano-pigment ink, wherein an aqueous solvent, resin, pigment, stabilizer, surfactant and water are mixed and filtered to obtain the high-stability water-based nano-pigment ink.

[0013] Preferably, the mixing process involves stirring at a speed of 200-500 r / min for a duration of 0.5-5 h.

[0014] The beneficial effects of this invention are: 1) In this invention, the stabilizer has good compatibility and stability, and the prepared water-based nano pigment ink can be stored stably for a long time with smooth inkjet printing, thus improving the inkjet printing stability of the water-based nano pigment ink; the stabilizer can also improve the dispersion stability of the nano pigment paste, and play a role in preventing clogging and stabilizing inkjet printing during the inkjet printing process.

[0015] 2) The water-based nano pigment ink of the present invention does not require pre- or post-treatment of the fabric, the process is simple, no wastewater is generated during production, which can save production costs and will not cause sedimentation; compared with traditional printing, it simplifies the process and is environmentally friendly. Detailed Implementation

[0016] This invention provides a highly stable water-based nano-pigment ink, which comprises the following raw materials by mass fraction: The composition is as follows: 10-15% aqueous solvent, 15-32% resin, 20-40% color paste, 5-10% stabilizer, 0.1-1% surfactant, and the balance is water. The structural formula of the stabilizer is: , Among them, R1 to R4 independently contain H, C1 to C6 alkyl, C1 to C6 alkoxy, C1 to C6 alkenyl or C1 to C6 alkynyl; R5 contains a carbonyl group, a thiocarbonyl group, or -CNH-; Q1~Q4 contain H, -OH or -NH2 independently.

[0017] In this invention, the highly stable water-based nano-pigment ink comprises the following raw materials by mass fraction: The aqueous solvent comprises 10-15%, preferably 11-14%, more preferably 12-13%; the resin comprises 15-32%, preferably 18-28%, more preferably 20-25%; the color paste comprises 20-40%, preferably 25-35%, more preferably 30%; the stabilizer comprises 5-10%, preferably 6-9%, more preferably 7-8%; the surfactant comprises 0.1-1%, preferably 0.3-0.8%, more preferably 0.5%; and the balance is water.

[0018] In this invention, the aqueous solvent preferably comprises one or more of anhydrous ethanol, n-propanol, isopropanol, n-butanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, polyethylene glycol, glycerol, pentaerythritol, 2-pyrrolidone, and N-methylpyrrolidone.

[0019] In this invention, the polyethylene glycol preferably comprises one or more of polyethylene glycol 200, polyethylene glycol 400 and polyethylene glycol 600.

[0020] In this invention, the resin preferably comprises one or more of polyurethane resin, acrylic resin, polyolefin resin, epoxy resin, formaldehyde resin, urea-formaldehyde resin and fluorocarbon resin.

[0021] In this invention, the color paste is preferably a nano-pigment color paste, and the D of the nano-pigment color paste is... 50 Preferably, it is 100~130nm, more preferably 105~125nm, and even more preferably 110~120nm.

[0022] In this invention, the nano pigment paste is preferably a nano pigment paste with good dispersion stability.

[0023] In this invention, the surfactant preferably comprises one or more of the following: acetylenic diol surfactants, polyether siloxane surfactants, acrylic surfactants, and organofluorine surfactants.

[0024] The present invention also provides a method for preparing the high-stability water-based nano-pigment ink, wherein an aqueous solvent, resin, pigment, stabilizer, surfactant and water are mixed and filtered to obtain the high-stability water-based nano-pigment ink.

[0025] In this invention, stirring is preferably performed during the mixing process, and the stirring speed is preferably 200~500 r / min, more preferably 250~400 r / min, and even more preferably 300~350 r / min; the stirring time is preferably 0.5~5 h, more preferably 1~4 h, and even more preferably 2~3 h.

[0026] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0027] The resin used in the embodiments and comparative examples of this invention is polyurethane resin (Mitsui W-6110), the surfactant is acetylenol surfactant (surfynol 465), and the color paste is self-dispersing color paste PD-2401 (D). 50 (110nm, purchased from Shenyang Sinochem New Materials Technology Co., Ltd.)

[0028] Example 1

[0029] 10g of urea, 10g of deionized water, and 22.37g of 1-ethanolamine were mixed and stirred, heated to 120℃, and maintained at 120℃ for 2 hours. After the reaction was completed, the temperature was lowered to 60℃, methanol (the crystallization solvent) was added, and the mixture was stirred at 300 rpm for 1 hour before being cooled to 40℃ to obtain crude stabilizer. The product was centrifuged and vacuum dried at 120℃ for 4 hours to obtain the stabilizer N,N-dihydroxyethylurea.

[0030] In this embodiment, the structural formula of the stabilizer N,N-dihydroxyethylurea is: It is labeled as mN,N-bis(hydroxyethyl)urea.

[0031] The preparation method of highly stable water-based nano-pigment ink is as follows: 15 parts by weight of glycerol, 30 parts by weight of W-6110, 30 parts by weight of pigment, 5 parts by weight of mN,N-dihydroxyethyl urea, 1 part by weight of Surfynol 465, and 19 parts by weight of deionized water are mixed and stirred at 300 rpm for 2 hours. After stirring, the mixture is filtered through a 0.45 μm PP filter membrane to obtain the highly stable water-based nano-pigment ink.

[0032] Example 2

[0033] The stabilizer obtained by replacing the crystallization solvent methanol in Example 1 with anhydrous ethanol is labeled as eN,N-bishydroxyethylurea.

[0034] The preparation method of the high-stability water-based nano pigment ink differs from that in Example 1 in that mN,N-bishydroxyethylurea is replaced with eN,N-bishydroxyethylurea.

[0035] Example 3

[0036] The stabilizer obtained by replacing the crystallization solvent methanol in Example 1 with isopropanol is labeled as IPA-N,N-bishydroxyethylurea.

[0037] The preparation method of the high-stability water-based nano pigment ink differs from that in Example 1 in that mN,N-bishydroxyethylurea is replaced with IPA-N,N-bishydroxyethylurea.

[0038] Example 4

[0039] The stabilizer obtained by replacing the crystallization solvent methanol in Example 1 with n-butanol is labeled as bN,N-bishydroxyethylurea.

[0040] The preparation method of the high-stability water-based nano pigment ink differs from that in Example 1 in that mN,N-bishydroxyethylurea is replaced with bN,N-bishydroxyethylurea.

[0041] Example 5

[0042] The stabilizer obtained by replacing the crystallization solvent methanol in Example 1 with acetone is labeled as aN,N-bishydroxyethylurea.

[0043] The preparation method of the high-stability water-based nano pigment ink differs from that in Example 1 in that mN,N-bishydroxyethylurea is replaced with aN,N-bishydroxyethylurea.

[0044] Example 6

[0045] The stabilizer obtained by replacing the crystallization solvent methanol in Example 1 with pyridine is labeled as pN,N-bishydroxyethylurea.

[0046] The preparation method of the high-stability water-based nano pigment ink differs from that in Example 1 in that mN,N-bishydroxyethylurea is replaced with pN,N-bishydroxyethylurea.

[0047] Example 7

[0048] 10g of thiourea, 10g of deionized water, and 17.65g of 1-ethanolamine were mixed and stirred, heated to 120℃, and maintained at 120℃ for 2 hours. After the reaction was completed, the temperature was lowered to 60℃, methanol (the crystallization solvent) was added, and the mixture was stirred at 300 rpm for 1 hour before being cooled to 40℃ to obtain crude stabilizer. The product was centrifuged and vacuum dried at 120℃ for 4 hours to obtain the stabilizer N,N-bishydroxyethylthiourea.

[0049] In this embodiment, the structural formula of the stabilizer N,N-dihydroxyethylthiourea is: It is labeled as mN,N-bis(hydroxyethyl)thiourea.

[0050] The preparation method of highly stable water-based nano-pigment ink is as follows: 14 parts by weight of glycerol, 32 parts by weight of W-6110, 32 parts by weight of pigment, 7 parts by weight of mN,N-dihydroxyethylthiourea, 1 part by weight of Surfynol 465, and 14 parts by weight of deionized water are mixed and stirred at 300 rpm for 2 hours. After stirring, the mixture is filtered through a 0.45 μm PP filter membrane to obtain the highly stable water-based nano-pigment ink.

[0051] Example 8

[0052] The stabilizer obtained by replacing the crystallization solvent methanol in Example 7 with anhydrous ethanol is labeled as eN,N-bishydroxyethylthiourea.

[0053] The preparation method of the high-stability water-based nano pigment ink differs from that in Example 7 in that mN,N-bishydroxyethylthiourea is replaced with eN,N-bishydroxyethylthiourea.

[0054] Example 9

[0055] The stabilizer obtained by replacing the crystallization solvent methanol in Example 7 with isopropanol is labeled as IPA-N,N-bishydroxyethylthiourea.

[0056] The preparation method of the high-stability water-based nano pigment ink differs from that in Example 7 in that mN,N-bishydroxyethylthiourea is replaced with IPA-N,N-bishydroxyethylthiourea.

[0057] Example 10

[0058] The stabilizer obtained by replacing the crystallization solvent methanol in Example 7 with n-butanol is labeled as bN,N-bishydroxyethylthiourea.

[0059] The preparation method of the high-stability water-based nano pigment ink differs from that in Example 7 in that mN,N-bishydroxyethylthiourea is replaced with bN,N-bishydroxyethylthiourea.

[0060] Example 11

[0061] The stabilizer obtained by replacing the crystallization solvent methanol in Example 7 with acetone is labeled as aN,N-bishydroxyethylthiourea.

[0062] The preparation method of the high-stability water-based nano pigment ink differs from that in Example 7 in that mN,N-bishydroxyethylthiourea is replaced with aN,N-bishydroxyethylthiourea.

[0063] Example 12

[0064] The stabilizer obtained by replacing the crystallization solvent methanol in Example 7 with pyridine is labeled as pN,N-bishydroxyethylthiourea.

[0065] The preparation method of the high-stability water-based nano pigment ink differs from that in Example 7 in that mN,N-bishydroxyethylthiourea is replaced with pN,N-bishydroxyethylthiourea.

[0066] Example 13

[0067] 10g of imine urea, 10g of deionized water, and 22.38g of ethylenediamine were mixed and stirred, heated to 120℃, and maintained at 120℃ for 2 hours. After the reaction was completed, the temperature was lowered to 60℃, and methanol, the crystallization solvent, was added. The mixture was stirred at 300 rpm for 1 hour, and then cooled to 40℃ to obtain crude stabilizer. The product was centrifuged and vacuum dried at 120℃ for 4 hours to obtain the stabilizer N,N-bisethylenediamineimine urea.

[0068] In this embodiment, the structural formula of the stabilizer N,N-bis(ethylenediamineiminourea) is: It is labeled as mN,N-bis(ethylenediamine)iminourea.

[0069] The preparation method of highly stable water-based nano-pigment ink is as follows: 12 parts by weight of glycerol, 31 parts by weight of W-6110, 28 parts by weight of pigment, 9 parts by weight of mN,N-diethylenediamineimine urea, 1 part by weight of Surfynol 465, and 19 parts by weight of deionized water are mixed and stirred at 300 rpm for 2 hours. After stirring, the mixture is filtered through a 0.45 μm PP filter membrane to obtain the highly stable water-based nano-pigment ink.

[0070] Example 14

[0071] The stabilizer obtained by replacing the crystallization solvent methanol in Example 13 with anhydrous ethanol is labeled as eN,N-bis(ethylenediamine)iminourea.

[0072] The preparation method of the high-stability water-based nano pigment ink differs from that in Example 13 in that mN,N-bisethylenediamineimide urea is replaced with eN,N-bisethylenediamineimide urea.

[0073] Example 15

[0074] The stabilizer obtained by replacing the crystallization solvent methanol in Example 13 with isopropanol is labeled as IPA-N,N-bis(ethylenediamine)iminourea.

[0075] The preparation method of the high-stability water-based nano pigment ink differs from that in Example 13 in that mN,N-bisethylenediamineimide urea is replaced with IPA-N,N-bisethylenediamineimide urea.

[0076] Example 16

[0077] The stabilizer obtained by replacing the crystallization solvent methanol in Example 13 with n-butanol is labeled as bN,N-bis(ethylenediamine)iminourea.

[0078] The preparation method of the high-stability water-based nano pigment ink differs from that in Example 13 in that mN,N-bisethylenediamineimide urea is replaced with bN,N-bisethylenediamineimide urea.

[0079] Example 17

[0080] The stabilizer obtained by replacing the crystallization solvent methanol in Example 13 with acetone is labeled as aN,N-bis(ethylenediamine)imineurea.

[0081] The preparation method of the high-stability water-based nano pigment ink differs from that in Example 13 in that mN,N-bisethylenediamineimide urea is replaced with aN,N-bisethylenediamineimide urea.

[0082] Example 18

[0083] The stabilizer obtained by replacing the crystallization solvent methanol in Example 13 with pyridine is labeled as pN,N-bis(ethylenediamine)imineurea.

[0084] The preparation method of the high-stability water-based nano pigment ink differs from that in Example 13 in that mN,N-bisethylenediamineimine urea is replaced with pN,N-bisethylenediamineimine urea.

[0085] Comparative Example 1

[0086] By weight, 15 parts glycerol, 30 parts W-6110, 30 parts pigment, 5 parts Dispers 710, 1 part surfynol 465, and 19 parts deionized water were mixed and stirred at 300 rpm for 2 hours. After stirring, the mixture was filtered through a 0.45 μm PP filter membrane to obtain water-based nano-pigment ink.

[0087] Comparative Example 2

[0088] By weight, 14 parts glycerol, 32 parts W-6110, 32 parts pigment, 7 parts Dispers 710, 1 part surfynol 465, and 14 parts deionized water were mixed and stirred at 300 rpm for 2 hours. After stirring, the mixture was filtered through a 0.45 μm PP filter membrane to obtain water-based nano-pigment ink.

[0089] Comparative Example 3

[0090] By weight, 12 parts glycerol, 31 parts W-6110, 28 parts pigment, 9 parts Dispers 710, 1 part surfynol 465, and 19 parts deionized water were mixed and stirred at 300 rpm for 2 hours. After stirring, the mixture was filtered through a 0.45 μm PP filter membrane to obtain a highly stable water-based nano-pigment ink.

[0091] Comparative Example 4

[0092] The difference from Comparative Example 1 is that Dispers 710 was omitted and 24 parts of deionized water were used.

[0093] Comparative Example 5

[0094] The difference from Comparative Example 2 is that Dispers 710 was omitted and 21 parts of deionized water were used.

[0095] Comparative Example 6

[0096] The difference from Comparative Example 3 is that Dispers 710 was omitted and 28 parts of deionized water were used.

[0097] The water-based nano-pigment inks of Examples 1 to 18 and Comparative Examples 1 to 6 were respectively loaded into the ink cartridges of a digital printing machine. The digital printing machine was equipped with a Kyocera KJ4B-0300 print head, and digital printing was carried out on pure cotton fabric in an environment of 25°C and RH50%. The pattern was a solid color block of 300mm × 400mm. The fabric products after digital printing were placed in a color fixing machine and heat-fixed at 160°C for 2 minutes to obtain digital printed fabrics. The rubbing fastness of the digital printed fabrics was tested according to GB / T3920-2008, and the soaping fastness was tested according to GB / T3921-2008 (tested at 60°C for 30 minutes).

[0098] The thermal storage stability of the water-based nano-pigment ink was tested according to QB / T 5489-2020. The test condition was to stand still in an environment of 60°C for 7 days. If the change of each physical and chemical index was within 10%, it was qualified.

[0099] The machine cleaning test method for the water-based nano-pigment ink was as follows: smooth ink feeding at the first time, and no ink breakage, skew spraying, etc. after 2 consecutive cleanings was qualified.

[0100] The inkjet stability test method for the water-based nano-pigment ink was as follows: the digital printing machine was set to 3-pass printing mode, with a precision of 360 × 1800dpi. A solid color block with 100% ink volume was continuously printed for 100 meters, and the integrity of the lines at 100 meters was observed. The number of broken line grids per color ≤ 3 needles was qualified.

[0101] Table 1 Performance test results of water-based nano-pigment ink

[0102] As can be seen from Table 1, the water-based nano-pigment inks prepared in Examples 1 to 18 can be stored stably for a long time, have smooth inkjet, and excellent inkjet stability.

[0103] As can be seen from the above examples, the present invention provides a water-based nano-pigment ink with high stability and its preparation method. By adding a stabilizer with the structural formula , the water-based nano-pigment ink has excellent inkjet stability, which can play a role in preventing blockage and stabilizing inkjet; the digital printed fabric printed with the high-stability water-based nano-pigment ink of the present invention has excellent rubbing fastness and soaping fastness, and there is no need to perform pre-treatment and post-treatment on the fabric. The process flow is simple, no wastewater is generated during the printing process, the cost is saved, and it is environmentally friendly.

[0104] The above are only the preferred embodiments of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and retouches can be made, and these improvements and retouches should also be regarded as the protection scope of the present invention.

Claims

1. A highly stable water-based nano-pigment ink, characterized in that, By mass fraction, it contains the following raw materials: The composition is as follows: 10-15% aqueous solvent, 15-32% resin, 20-40% color paste, 5-10% stabilizer, 0.1-1% surfactant, and the balance is water. The structural formula of the stabilizer is: , Among them, R1 to R4 independently contain H, C1 to C6 alkyl, C1 to C6 alkoxy, C1 to C6 alkenyl or C1 to C6 alkynyl; R5 contains a carbonyl group, a thiocarbonyl group, or -CNH-; Q1~Q4 contain H, -OH or -NH2 independently.

2. The high-stability water-based nano-pigment ink according to claim 1, characterized in that, The aqueous solvent comprises one or more of anhydrous ethanol, n-propanol, isopropanol, n-butanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, polyethylene glycol, glycerol, pentaerythritol, 2-pyrrolidone, and N-methylpyrrolidone.

3. The high-stability water-based nano-pigment ink according to claim 1 or 2, characterized in that, The resin comprises one or more of polyurethane resin, acrylic resin, polyolefin resin, epoxy resin, formaldehyde resin, urea-formaldehyde resin, and fluorocarbon resin.

4. The high-stability water-based nano-pigment ink according to claim 3, characterized in that, The color paste is a nano-pigment color paste, and the D of the nano-pigment color paste is... 50 The wavelength is 100~130nm.

5. The high-stability water-based nano-pigment ink according to claim 4, characterized in that, The surfactant comprises one or more of the following: acetylenic diol surfactants, polyether siloxane surfactants, acrylic surfactants, and organofluorine surfactants.

6. The method for preparing the highly stable aqueous nano-pigment ink according to any one of claims 1 to 5, characterized in that, A highly stable water-based nano-pigment ink is obtained by mixing water-based solvent, resin, pigment, stabilizer, surfactant and water, and then filtering.

7. The preparation method according to claim 6, characterized in that, During the mixing process, stirring is carried out at a speed of 200~500 r / min for a duration of 0.5~5 h.

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