A hydrophobic ink and its preparation process

Abstract

The present invention discloses a kind of hydrophobic ink and preparation process thereof, specifically related to the field of novel ink technology.A kind of hydrophobic ink, including the component composition of the following mass ratio: 20 35 parts of fluorocarbon resin, 15 30 parts of hydrophobic filler, 40 60 parts of organic solvent, 0.1 2 parts of leveling agent, 1 5 parts of dispersant, 0.5 1 parts of defoamer, 1 3 parts of ultraviolet absorption stabilizer.By introducing the ultraviolet absorption stabilizer of specific structure, C H photolysis is reduced by deuterium substitution, and ultraviolet photons of UVB and UVA bands can be efficiently captured, converted into harmless energy, and polymer chain rupture and pigment fading are prevented in ink; Fluorocarbon resin cooperates with hydrophobic filler to block photooxidation chain reaction, suppress filler light agglomeration, and then significantly extend the anti-UV aging life of ink, so that it can still maintain performance under long-term sunlight irradiation.

Description

Technical Field

[0001] This invention relates to the field of novel ink technology, specifically to a hydrophobic ink and its preparation process. Background Technology

[0002] With the continuous advancement of technology and people's increasing demands for quality of life, ink technology is also constantly developing and innovating. However, existing inks still have some problems in practical applications. Traditional inks perform poorly in terms of hydrophobic properties, easily affected by water, leading to blurred prints, fading, and other phenomena, thus affecting the aesthetics and durability of printed materials. This problem is particularly prominent in printing scenarios that require long-term clarity and vibrancy, such as outdoor advertising and packaging materials.

[0003] Furthermore, existing inks also have shortcomings in terms of weather resistance. Prolonged exposure to sunlight and ultraviolet rays accelerate the aging process of the ink, causing its color to fade and its performance to decline. This not only shortens the lifespan of printed materials but also increases the cost of replacement and maintenance. The ink preparation process also faces several challenges. The dispersibility and stability of the ink are difficult to control, and problems such as sedimentation and stratification can easily occur, affecting the uniformity and consistency of the printing effect. At the same time, to meet environmental protection requirements, higher demands are placed on the solvent composition of inks, necessitating the search for more environmentally friendly and biodegradable organic solvents to replace traditional solvents.

[0004] To address the aforementioned problems, this invention proposes a hydrophobic ink and its preparation process, aiming to improve the hydrophobic properties, weather resistance, and stability of the ink, while employing more environmentally friendly materials and processes to meet market demands. Summary of the Invention

[0005] The purpose of this invention is to address the problems of poor hydrophobic properties, insufficient weather resistance, and poor stability in existing inks, and to provide a hydrophobic ink with excellent hydrophobic properties, good weather resistance, and strong stability to meet the market demands of ink application fields.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is: a hydrophobic ink, comprising the following components in the indicated mass ratios: 20-35 parts fluorocarbon resin, 15-30 parts hydrophobic filler, 40-60 parts organic solvent, 0.1-2 parts leveling agent, 1-5 parts dispersant, 0.5-1 part defoamer, and 1-3 parts ultraviolet absorption stabilizer.

[0007] The ultraviolet absorption stabilizer has the structure shown in Formula 1:

[0008] Formula 1;

[0009] In Formula 1, R1 is a substituent, specifically selected from: methyl, tert-butyl, phenyl, cyano;

[0010] In Equation 1, D represents deuterium.

[0011] Furthermore, the fluorocarbon resin is polytetrafluoroethylene.

[0012] Furthermore, the hydrophobic filler is silicon dioxide with a particle size of 50-200 nm.

[0013] Furthermore, the organic solvent is at least one of ethyl acetate, propylene glycol methyl ether, or methyl isobutyl ketone.

[0014] Furthermore, the leveling agent is BYK-346.

[0015] Furthermore, the dispersant is polyethylene glycol.

[0016] Furthermore, the defoamer is mineral oil TEGO Foamex 810.

[0017] Furthermore, the ultraviolet absorption stabilizer is any one of the compounds shown in the following structures:

[0018]

[0019] .

[0020] A method for preparing a hydrophobic ink includes the following steps:

[0021] S1. Mix the organic solvent, dispersant and 1 / 2 part by mass of fluorocarbon resin, and stir at 800-1200 rpm for 10 min to obtain material A;

[0022] S2. Add the hydrophobic filler to material A in 3 batches, with an interval of 5 minutes between each batch. Stir at 1500-2000 rpm for 30-60 minutes to obtain material B.

[0023] S3. Add the remaining fluorocarbon resin, leveling agent, dispersant, defoamer, and UV absorber to the material B, and stir at 800-1200 rpm for 20 minutes to obtain material C;

[0024] S4. Transfer the material C to a sand mill and grind it to a fineness of ≤10μm, then vacuum defoam and filter to obtain the finished product.

[0025] Furthermore, S2 is operated at 25-40°C.

[0026] Furthermore, the grinding media in the sand mill is zirconia beads, and the grinding time is 2-3 hours.

[0027] Furthermore, the S4 filter uses a 20-50 mesh filter.

[0028] The R1 substituent and D in the UV absorption stabilizer of this invention enhance the photostability of the molecule. The introduction of deuterium improves the molecule's resistance to photodegradation because it reduces the photosensitivity of hydrogen atoms; while the R1 group modulates the polarity and UV absorption range of the molecule, making it more effective at capturing UVB and / or UVA bands. When the ink is exposed to sunlight, the molecule absorbs UV photons and converts them into heat energy or harmless vibrational energy, preventing UV-induced polymer chain breakage or pigment fading in the ink. The UV absorption stabilizer of this invention works synergistically with fluorocarbon resin. The fluorocarbon resin provides low surface tension and hydrophobic groups, forming a "waterproof layer." The UV absorption stabilizer protects the resin from UV degradation, preventing a decrease in hydrophobicity. The molecular interaction involves physical adsorption and / or hydrogen bonding. The stabilizer adheres to the resin surface, blocking the photo-oxidation chain reaction. The synergistic effect of the UV absorption stabilizer and hydrophobic filler described in this invention enhances the hydrophobic effect by increasing the surface roughness of the hydrophobic filler. The UV absorption mechanism of the UV absorption stabilizer prevents the filler from agglomerating and / or failing due to light exposure, ensuring long-term hydrophobicity. At the molecular level, the stabilizer may interact with the filler surface through van der Waals forces to maintain dispersion stability.

[0029] The hydrophobic ink component described in this invention solves three major technical problems—insufficient hydrophobicity, poor weather resistance, and poor stability—through a synergistic effect.

[0030] 1) Synergistic hydrophobicity: The core component, fluorocarbon resin (which provides low surface energy hydrophobic groups), is combined with hydrophobic nano-silica fillers with specific particle sizes (50-200nm). The resin continuous phase encapsulates the fillers to form a micro-nano composite structure, which significantly improves surface roughness and enhances the hydrophobic effect.

[0031] 2) Synergistic effect on weather resistance: UV absorption stabilizer (UV absorption 280-400nm, deuterium substitution reduces CH photolysis) is adsorbed on the surface of resin and filler through van der Waals forces or hydrogen bonds, simultaneously blocking the UV oxidation and breakage of resin chains and inhibiting filler photoaggregation, thus extending the UV aging resistance life.

[0032] 3) Stability Synergy: Dispersants (to prevent sedimentation), defoamers (to eliminate bubbles), leveling agents (to optimize film formation) and environmentally friendly solvents (such as ethyl acetate) are combined at the process end, along with a step-by-step addition strategy and high-speed grinding, to ensure that the filler is uniformly dispersed and free from sedimentation, resulting in a long shelf life;

[0033] Ultimately, through the deep integration of component functional design and process innovation, an environmentally friendly ink with high hydrophobicity, long weather resistance, and strong stability is achieved, meeting the demanding requirements of outdoor applications.

[0034] Compared with the prior art, the beneficial effects of the present invention are:

[0035] 1. Significantly improved hydrophobic properties: This invention utilizes the synergistic effect of fluorocarbon resin and hydrophobic nano-silica fillers of specific particle size to construct a micro-nano composite structure, enhancing surface roughness and thus significantly improving the hydrophobicity of the ink. This effectively prevents the ink from becoming blurred or fading due to water, making it more suitable for complex environments such as outdoor settings.

[0036] 2. Significantly enhanced weather resistance: On the one hand, the UV absorption stabilizer reduces CH photolysis through deuterium substitution, and the R1 group can adjust the polarity and UV absorption range, which can efficiently capture ultraviolet photons in the UVB and UVA bands and convert them into harmless energy, preventing polymer chain breakage and pigment fading in the ink; on the other hand, the fluorocarbon resin and hydrophobic filler work together to block the photo-oxidation chain reaction and inhibit filler photoaggregation, thereby significantly extending the UV aging resistance life of the ink, allowing it to maintain its performance under long-term sunlight exposure.

[0037] 3. Significantly improved stability: Dispersants prevent filler sedimentation, defoamers eliminate bubbles, and leveling agents help optimize film formation. At the same time, environmentally friendly organic solvents, combined with a step-by-step addition strategy and high-speed grinding process, ensure that the filler is evenly dispersed and does not settle, greatly extending the ink's shelf life and guaranteeing the uniformity and consistency of printing results. Attached Figure Description

[0038] Figure 1 The UV absorption stabilizer 1 described in this invention 1 HNMR image. Detailed Implementation

[0039] The technical solution of the present invention will now be clearly and completely described with reference to the accompanying drawings. Obviously, the described embodiments are merely some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0040] Synthesis example 1

[0041] Synthesis of UV absorption stabilizer 1:

[0042] ;

[0043] Step 1: Under a nitrogen atmosphere, add 20g of raw material 1, 12.65g of raw material 2, 14.13g of anhydrous potassium carbonate, 1.77g of tetra(triphenylphosphine)palladium, and 230g of a mixture of toluene, ethanol, and aqueous solution in a volume ratio of 2:1:1 to the reaction system. Heat to 95°C and reflux for 10 hours. Turn off the heating, cool to room temperature, allow to stand, and separate the liquid phases. Extract the aqueous phase twice with ethyl acetate, combine the organic phases, dry the organic phase with anhydrous magnesium sulfate, filter, evaporate to dryness, and perform silica gel column chromatography using a mixture of petroleum ether and ethyl acetate as eluent. Evaporate to dryness to obtain 21.01g of intermediate 1.

[0044] Step 2: Under a nitrogen atmosphere, 21.01 g of intermediate 1, 9.35 g of raw material 3, 0.4 g of tri-tert-butylphosphine, 0.05 g of palladium on carbon, 11.81 g of anhydrous potassium carbonate, and 250 g of toluene were added to the reaction system. The mixture was heated to 120 °C and refluxed for 12 hours. After the reaction was completed, the temperature was slightly lowered, and the mixture was filtered using diatomaceous earth. After the filtrate was cooled to room temperature, it was washed three times with water, and the organic phase was retained. The aqueous phase was then extracted with ethyl acetate. The organic phases were combined, dried over anhydrous magnesium sulfate, filtered, and evaporated to dryness. The mixture was then subjected to silica gel column chromatography using a mixture of petroleum ether and ethyl acetate as the eluent. After evaporation, 19.59 g of UV absorber stabilizer 1 was obtained.

[0045] Structural assessment:

[0046] MS(m / z) of intermediate 1: [M+H] + =492;

[0047] MS (m / z) of UV absorber stabilizer 1: [M+H] + =610;

[0048] The 1H NMR (Chloroform-d) values ​​of UV absorber stabilizer 1 are as follows: δ 8.86–8.80 (m, 1H), 8.07–7.83 (m, 5H), 7.71–7.45 (m, 5H), 7.26–7.17 (m, 1H), 7.11 (dd, 1H), 5.25–5.18 (m, 1H), 5.03 (d, 1H), 4.34–4.24 (m, 1H), 4.17–3.97 (m, 2H), 3.93–3.77 (m, 1H), 2.53 (s, 3H).

[0049] Synthesis Example 2-Synthesis Example 4

[0050] In Synthesis Examples 2-4, UV absorption stabilizer 2-UV absorption stabilizer 4 were synthesized sequentially, following the same synthesis method as in Synthesis Example 1, except that raw material 2 was replaced; the rest remained the same as in Synthesis Example 1. Specific structures of raw material 2, UV absorption stabilizer 2-UV absorption stabilizer 4, and MS (m / z): [M+H] are detailed below.+ The data is shown in Table 1.

[0051] Table 1. Structures of raw material 2, UV absorber stabilizer 2-UV absorber stabilizer 4, and MS (m / z): [M+H] involved in Synthesis Examples 2-4 + data.

[0052]

[0053] Example 1

[0054] Preparation of a hydrophobic ink:

[0055] 1. Raw material mass ratio:

[0056] Fluorocarbon resin: 30 parts, which is polytetrafluoroethylene;

[0057] Hydrophobic filler: 25 parts, made of silica, with a particle size of 50-200 nm;

[0058] Organic solvent: 50 parts, ethyl acetate;

[0059] Leveling agent: 1 part, BYK-346 (purchased from Guangdong Wengjiang Chemical Reagent Co., Ltd., product number PB21308).

[0060] Dispersant: 2.5 parts, polyethylene glycol;

[0061] Defoamer: 0.7 parts, which is mineral oil TEGO Foamex 810 (purchased from Guangdong Yunxing Biotechnology Co., Ltd.);

[0062] UV absorption stabilizer: 2 parts, which is UV absorption stabilizer 1 synthesized in Synthesis Example 1.

[0063] 2. Preparation method:

[0064] S1. Add organic solvent (ethyl acetate), dispersant (polyethylene glycol) and 1 / 2 part by weight (15 parts) of fluorocarbon resin to a stainless steel reactor and stir at 1000 rpm for 10 minutes to obtain a uniform and transparent material A.

[0065] S2. Heat material A to 30°C, add hydrophobic filler (silica) in 3 batches with an interval of 5 minutes between each batch, increase the stirring speed to 1800 rpm, and continue stirring for 45 minutes to obtain highly dispersible material B;

[0066] S3. Add the remaining fluorocarbon resin (15 parts), leveling agent (BYK-346), defoamer (TEGO Foamex810) and UV absorption stabilizer 1 to material B, and stir at 1000 rpm for 20 minutes to form a uniform material C.

[0067] S4. Transfer material C to a sand mill and grind for 2.5 hours until the fineness is ≤10μm. Then defoam under a vacuum of -0.09MPa for 30 minutes, and finally filter through a 30-mesh filter to obtain the finished hydrophobic ink.

[0068] Examples 2-4

[0069] The preparation of a hydrophobic ink is carried out by referring to the preparation method of Example 1, except that the ultraviolet absorption stabilizer is replaced sequentially with ultraviolet absorption stabilizer 2-ultraviolet absorption stabilizer 4 synthesized in Synthesis Examples 2-4, and the rest is the same as in Example 1.

[0070] Comparative Example 1

[0071] A hydrophobic ink was prepared according to the preparation method of Example 1, except that the ultraviolet absorption stabilizer was not added, and the rest remained the same as in Example 1.

[0072] Comparative Example 2

[0073] A hydrophobic ink was prepared by referring to the preparation method of Example 1, except that the ultraviolet absorption stabilizer was replaced with comparative compound 1, and the rest remained the same as in Example 1.

[0074] Comparative compound 1: .

[0075] Comparative Example 3

[0076] A hydrophobic ink was prepared by referring to the preparation method of Example 1, except that the ultraviolet absorption stabilizer was replaced with comparative compound 2, and the rest remained the same as in Example 1.

[0077] Comparative compound 2: .

[0078] Comparative Example 4

[0079] A hydrophobic ink was prepared by referring to the preparation method of Example 1, except that the mass fraction of fluorocarbon resin was replaced with 45 parts, while the rest remained the same as in Example 1.

[0080] Comparative Example 5

[0081] A hydrophobic ink was prepared by referring to the preparation method of Example 1, except that the mass fraction of the hydrophobic filler was replaced with 40 parts, while the rest remained the same as in Example 1.

[0082] Comparative Example 6

[0083] A hydrophobic ink was prepared by referring to the preparation method of Example 1, except that the ultraviolet absorption stabilizer was replaced with ultraviolet absorber UV-326 (CAS: 3896-11-5), and the rest remained the same as in Example 1.

[0084] Performance testing:

[0085] 1. Adhesion test: The hydrophobic ink prepared in the examples and comparative examples was tested according to GB / T9286, and the data are shown in Table 2.

[0086] 2. Water resistance test: The hydrophobic ink prepared in the examples and comparative examples was tested according to GB / T1733, and the data are shown in Table 2.

[0087] 3. Acid resistance test: A hydrophobic ink prepared in the examples and comparative examples was taken as a sample, and a 5% concentrated sulfuric acid solution was applied to the sample surface for 48 hours. The changes in the sample were observed and the data are shown in Table 2.

[0088] 4. Alkali resistance test: A hydrophobic ink prepared in the examples and comparative examples was taken as a sample, and a 5% sodium hydroxide solution was applied to the sample surface for 48 hours. The changes in the sample were observed and the data are shown in Table 2.

[0089] 5. Weather Resistance Test: The hydrophobic inks prepared in the examples and comparative examples were exposed to a xenon lamp aging test chamber for 2400 hours to simulate natural aging conditions such as light exposure, condensation, and humidity changes. The exposure conditions were: radiation intensity 0.35 W / m². 2 (340nm wavelength) Temperature cycling was performed at 60℃ (light exposure stage) and 40℃ (condensation stage), and humidity cycling was performed at 50%±5% (light exposure stage) and 95%±5% (condensation stage). The light exposure stage lasted for 8 hours, and the condensation stage (simulated rain) lasted for 4 hours. After exposure, the water resistance of the ink was tested according to GB / T9286 standard, and the results are shown in Table 2.

[0090] Table 2. Performance test data of a hydrophobic ink prepared in the examples and comparative examples.

[0091]

[0092] Compared to the comparative examples, the hydrophobic ink prepared in the embodiments of this invention significantly outperforms the comparative examples overall. The embodiments exhibit superior performance in all test indicators: overall adhesion is stronger, while the comparative examples show varying degrees of decline; in terms of water resistance, the embodiments demonstrate significantly higher water resistance, while the comparative examples show relatively shorter resistance duration; in acid and alkali resistance tests, the embodiments remain stable without any abnormalities, while the comparative examples generally show signs of degradation such as discoloration or peeling. These trends fully highlight the advantages of the formulation and process of this invention in improving the overall performance of the ink.

[0093] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A hydrophobic ink, characterized in that, It comprises the following components in the indicated mass ratios: 20-35 parts fluorocarbon resin, 15-30 parts hydrophobic filler, 40-60 parts organic solvent, 0.1-2 parts leveling agent, 1-5 parts dispersant, 0.5-1 part defoamer, and 1-3 parts ultraviolet absorption stabilizer. The ultraviolet absorption stabilizer has the structure shown in Formula 1: Formula 1; In Formula 1, R1 is a substituent, specifically selected from: methyl, tert-butyl, phenyl, cyano; In Equation 1, D represents deuterium.

2. The hydrophobic ink according to claim 1, characterized in that, The fluorocarbon resin is polytetrafluoroethylene.

3. The hydrophobic ink according to claim 1, characterized in that, The hydrophobic filler is silicon dioxide with a particle size of 50-200 nm.

4. The hydrophobic ink according to claim 1, characterized in that, The organic solvent is at least one of ethyl acetate, propylene glycol methyl ether, or methyl isobutyl ketone.

5. The hydrophobic ink according to claim 1, characterized in that, The leveling agent is BYK-346, the dispersant is polyethylene glycol, and the defoamer is mineral oil TEGO Foamex 810.

6. The hydrophobic ink according to claim 1, characterized in that, The ultraviolet absorption stabilizer is any one of the compounds shown in the following structures: 。 7. A method for preparing a hydrophobic ink according to any one of claims 1-6, characterized in that, Includes the following steps: S1. Mix the organic solvent, dispersant and 1 / 2 part by mass of fluorocarbon resin, and stir at 800-1200 rpm for 10 min to obtain material A; S2. Add the hydrophobic filler to material A in 3 batches, with an interval of 5 minutes between each batch. Stir at 1500-2000 rpm for 30-60 minutes to obtain material B. S3. Add the remaining fluorocarbon resin, leveling agent, dispersant, defoamer, and UV absorber to the material B, and stir at 800-1200 rpm for 20 minutes to obtain material C; S4. Transfer the material C to a sand mill and grind it to a fineness of ≤10μm, then vacuum defoam and filter to obtain the finished product.

8. The method for preparing a hydrophobic ink according to claim 7, characterized in that, The S2 is operated at 25-40°C.

9. The method for preparing a hydrophobic ink according to claim 7, characterized in that, The grinding media in the sand mill is zirconia beads, and the grinding time is 2-3 hours.

10. The method for preparing a hydrophobic ink according to claim 7, characterized in that, The S4 filter uses a 20-50 mesh filter.

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