UV silk-screen acid and alkali resistant impact resistant tempered sintering ink and preparation method thereof

Abstract

The application discloses a kind of UV silk printing acid and alkali resistant impact tempered sintering inks and preparation method thereof, belong to ink synthesis technical field.The ink includes by mass percentage: 40-60% UV ink oil, 10-30% lead-free glass powder, 5-15% silicon powder (1-5 μm), 1-5% thioformyl-containing photoinitiator and 0.5-3% polyether modified siloxane / polycarboxylic acid ammonium salt composite additive.By gradient particle size filler synergy, light initiator ortho chlorine substitution structure and specific curing process (365 / 405nm LED, 800-1200mJ / cm 2 ), realize lead-free environmental protection and performance breakthrough.The obtained ink pencil hardness ≥6H after curing, 5% hydrochloric acid and 10% sodium hydroxide immersion for 48 hours without falling, impact strength reaches 42.5kJ / m 2 , 600 ℃ sintering after adhesion keeps 8.5MPa, and lead content <0.1ppm.Preparation method controls particle size ≤8 μm by three-roll mill, viscosity 2000-5000cps, with excellent printing suitability and high temperature stability, suitable for glass, metal products corrosion resistant protective coating.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of ink synthesis, and particularly relates to a UV screen printing acid and alkali resistant impact resistant tempered sintering ink and a preparation method thereof. BACKGROUND

[0002] UV curing ink is widely used in the field of screen printing due to its advantages of high efficiency, energy saving, low VOC emission, etc. However, the traditional UV ink has significant deficiencies in terms of resistance to strong acid and alkali corrosive media and mechanical impact resistance, especially in the tempered sintering process (usually requiring high temperature treatment of 400-600 DEG C), which is prone to problems such as adhesion loss and brittle cracking. In addition, in order to improve the sintering density and chemical resistance of the ink, lead-containing glass powder is often used as an inorganic filler in the prior art, which can improve the performance, but there is a risk of heavy metal pollution, which is difficult to meet the increasingly stringent environmental regulations (such as the EU RoHS directive).

[0003] At present, the development of lead-free glass powder is mainly focused on low temperature melting characteristics, but its compatibility with the UV resin system is poor, which easily leads to poor ink leveling and uneven dispersion, and further affects the fineness of the printed pattern and the density of the sintered coating. At the same time, the photoinitiating system of the traditional UV ink is prone to residual small molecule substances that are not completely decomposed during the high temperature sintering process, resulting in a decrease in the chemical corrosion resistance of the coating. Although the prior art attempts to improve the mechanical properties by adding silicon powder and other reinforcing fillers, it is difficult to balance the impact resistance and surface hardness due to the inaccuracy of the particle size distribution control.

[0004] Therefore, it is a technical problem to be solved in this field to develop a UV screen printing ink that is lead-free, environmentally friendly, resistant to strong acid and alkali corrosion, and high impact resistance, and is suitable for tempered sintering process. SUMMARY

[0005] The technical problem to be solved by the present application is to provide a UV screen printing ink that is lead-free, environmentally friendly, resistant to strong acid and alkali corrosion, and high impact resistance, and is suitable for tempered sintering process, and a preparation and curing method thereof, in order to overcome the significant deficiencies of the traditional UV ink in the prior art in terms of resistance to strong acid and alkali corrosive media and mechanical impact resistance, especially in the tempered sintering process, which is prone to problems such as adhesion loss and brittle cracking.

[0006] In order to solve the above technical problems, the present application adopts the following technical solutions:

[0007] A UV screen printing acid and alkali resistant impact resistant tempered sintering ink, comprising the following components by mass percentage: 40-60% of UV ink oil, 10-30% of lead-free glass powder, 5-15% of silicon powder, 1-5% of photoinitiator, and 0.5-3% of environmental protection aid.

[0008] The UV ink oil is made by mixing solid resin and UV monomer in a mass ratio of (3-1):1.

[0009] The lead-free glass powder contains 30%-50wt% of bismuth trioxide;

[0010] The environmental protection aid includes a combination of polyether modified siloxane leveling agent and polycarboxylic acid ammonium salt dispersant, both in a mass ratio of (1-2):1.

[0011] Further, the solid resin is epoxy acrylate or polyurethane acrylate.

[0012] Further, the solid resin has a glass transition temperature (Tg) > 120℃, a viscosity controlled at 500-2000 mPa·s (25℃), a resin that can resist 5wt% hydrochloric acid and 10wt% NaOH solution penetration after curing, a hydrophobic group ratio > 30%, and no hydrophilic ether bond residue.

[0013] Further, the UV monomer is tripropylene glycol diacrylate or 1,6-hexanediol diacrylate.

[0014] Further, the structure of the tripropylene glycol diacrylate is:

[0015] Further, the structure of the 1,6-hexanediol diacrylate is:

[0016] Further, the polyether modified siloxane leveling agent is selected from: BYK-190, TEGO Dispers 755W, EFKA-4585, Solsperse 41000; and the polycarboxylic acid ammonium salt dispersant is selected from: BYK-333, TEGO Flow 425, EFKA-3777.

[0017] Further, the lead-free glass powder includes the following components in mass percentage: 35% of SiO2, 20% of B2O3, 25% of ZnO, 5% of Al2O3, 10wt% of zinc oxide, and 5wt% of zirconium oxide.

[0018] Further, the lead-free glass powder has a softening temperature of 400-550℃, and a particle size distribution D90≤8μm.

[0019] Further, the silicon powder has a particle size of 1-5μm, and a specific surface area of 2-5m 2 / g.

[0020] Further, the photoinitiator is selected from:

[0021]

[0022]

[0023] wherein Z1 is selected from: O, S, NR1, CH2; R1 is selected from: methyl, ethyl, propyl.

[0024] Further, the photoinitiator is selected from:

[0025]

[0026]

[0027]

[0028]

[0029] A preparation method of a UV screen printing acid and alkali resistant impact resistant tempered sintering ink, comprising the following steps:

[0030] a. Dissolve the solid resin and the UV monomer at 40-60°C to form a homogeneous UV ink;

[0031] b. Add the lead-free glass powder, the silicon powder, the photoinitiator and the environmental protection auxiliary agent to the product of step a in sequence, and stir at a speed of 800-1200 r / min for 20-40 minutes;

[0032] c. Grind the mixture through a three-roll mill for 3-5 times, with a roll spacing of 10-30 μm, until the particle size is ≤8 μm;

[0033] d. Adjust the viscosity to 2000-5000 cps and the solid content to 70%-85% to obtain a UV screen printing acid and alkali resistant impact resistant tempered sintering ink,

[0034] wherein one of the UV screen printing acid and alkali resistant impact resistant tempered sintering inks is cured under ultraviolet conditions.

[0035] Further, the roll temperature of the three-roll mill in step c is 25-35°C.

[0036] Further, the curing is performed using an LED cold light source with a peak wavelength of 365 nm or 405 nm, at an irradiation energy of 800-1200 mJ / cm2, for a curing time of 1-5 seconds, at an ambient temperature of 20-30°C.

[0037] Further, the pencil hardness of the ink layer after curing is ≥4H, and the ink layer is resistant to 5wt% hydrochloric acid and 10wt% sodium hydroxide solution immersion for 48 hours without falling off.

[0038] An acid and alkali resistant and impact resistant glass or metal product, the surface of which is coated with the above-mentioned UV silk-screen printing ink and is treated by the above-mentioned curing method to form a sintered coating layer with a thickness of 10-30 μm.

[0039] The UV ink oil component (40%-60%) is the core film-forming material of the system, and the UV ink oil realizes performance balance through the synergistic effect of solid resin and UV monomer. Epoxy acrylate or polyurethane acrylate is used as a high-Tg (>120℃) solid resin to construct a rigid three-dimensional crosslinked network, and the specific hydrophobic group content (>30%) and the ether bond-free molecular design effectively block the penetration path of acid and alkali medium. The two types of UV monomers, TPGDA and HDDA, not only adjust the viscosity of the system to the suitable range for silk-screen printing (2000-5000 cps), but also form a rigid-flexible polymer network during the curing process through the complementation of long-chain flexibility and dual-functionality reactivity.

[0040] The lead-free glass powder (10%-30%) realizes the dual breakthrough of environmental protection and performance through the unique SiO2-B2O3-ZnO-Al2O3-ZrO2 five-element system. The introduction of B2O3 precisely controls the softening point in the range of 400-550℃, which is highly matched with the tempering process temperature window. The phase change toughening-crystal boundary strengthening synergistic effect of ZrO2 (5%) and ZnO (25%) makes the impact strength of the coating reach 42kJ / m 2 (ASTM D256). The design of particle size D90≤8 μm forms a gradient filling structure with silicon powder, and SEM observation shows that the porosity is <0.3%, which is 67% lower than that of the conventional formula.

[0041] The silicon powder (5%-15%) selected 1-5 μm spherical silicon powder plays a dual function of nano-enhancement and interface optimization in the system. Its 2-5 m 2 / g specific surface area forms strong physical adsorption with the resin matrix, and finite element simulation shows that it can disperse more than 60% of the stress concentration. The Si-O-Al chemical bond generated by the reaction between the Al2O3 component in the lead-free glass powder and the silicon powder makes the adhesion of the coating to the metal substrate reach 8.5 MPa.

[0042] The photoinitiator system (1%-5%) has a molar extinction coefficient of 520 L / (mol·cm) for thioformyl at 365 nm wavelength when Z1 is S atom, which is 3.8 times higher than that of the conventional TPO initiator, and realizes 800 mJ / cm 2 irradiation to complete 90% curing in 0.5 seconds. The steric hindrance effect caused by the chlorine substitution at the ortho position of the benzene ring makes the thermal decomposition temperature of the initiator reach 280℃, avoiding the residue of small molecules in the sintering process. HPLC detection shows that the amount of residual monomer after curing is <0.3 ppm, which fully meets the food contact material standard.

[0043] The environmental protection assistant agent (0.5%-3%) is compatible with the polyether modified siloxane leveling agent and the polycarboxylic acid ammonium salt dispersant to form a "surface-phase" double regulation mechanism. The polyether segment (EO / PO=3:1) in the leveling agent is matched with the polarity of the UV monomer, so that the surface tension of the ink is reduced to 28 mN / m, and the hole blocking phenomenon of the screen printing plate is eliminated. The dispersant is chelated with the carboxylic acid group and the surface hydroxyl group of ZnO, and the charge neutralization effect of the ammonium ion is combined, so that the Zeta potential of the filler is stabilized at ±30 mV, and there is no sedimentation and stratification after centrifugal test (3000 rpm / 30 min). Dynamic rheological test shows that the assistant agent combination makes the ink thixotropic index reach 6.8, perfectly balancing the printing suitability and leveling performance.

[0044] The system realizes performance leap through three dimensions: in the aspect of thermodynamics, the thermal expansion coefficients of the glass powder (CTE 7.5×10 -6 / ℃) and the resin matrix (CTE 8.2×10 -6 / ℃) are matched, so that the residual stress is less than 15 MPa after 600℃ sintering and cooling; in the aspect of chemical stability, the SiO2-Al2O3 network (acid-resistant Knoop hardness 820) and the ZnO-B2O3 phase (alkali-resistant mass loss rate 0.8%) form an acid-alkali double barrier structure; in the aspect of mechanical performance, the nano-reinforcement of the silicon powder and the ZrO2 phase transformation toughening produce a multiplier effect, so that the coating has a pencil hardness of 6H and still maintains an elongation at break of 8%.

[0045] Compared with the prior art, the beneficial effects of the present application are:

[0046] 1. Lead-free environmental protection and high-temperature sintering performance synergy breakthrough: through the innovative SiO2-B2O3-ZnO-Al2O3-ZrO2 five-component lead-free glass system, the precise matching of the softening point and the tempering process is realized at 400-550℃ while completely eliminating heavy metal pollution (lead content <0.1 ppm). The synergistic effect of ZrO2 phase transformation toughening and ZnO grain boundary strengthening makes the impact strength of the coating reach 42.5kJ / m 2 (26.5% higher than Comparative Example 2), and still maintains a substrate adhesion of 8.5 MPa after 600℃ sintering, breaking the technical bottleneck that lead-free and high-temperature performance cannot be achieved at the same time.

[0047] 2. Construction of acid-alkali double barrier protection system: through the hierarchical design of the SiO2-Al2O3 rigid network (acid-resistant hardness 820 HK) and the B2O3-ZnO buffer layer (alkali-resistant mass loss rate 0.8%), a double physical and chemical barrier to acid and alkali medium penetration is formed. After 48 hours of immersion test in 5wt% hydrochloric acid and 10wt% sodium hydroxide, the coating has no swelling and falling off (Comparative Example 1 has stratification), and the adhesion by the crosshatch method remains 0 level, which is more than 5 times longer than the acid and alkali life of the traditional formula.

[0048] 3. High efficiency and low residue of photoinitiating system: the molar extinction coefficient of the specific structure of thiocarbonyl photoinitiator (such as Example 1-A) reaches 520 L / (mol·cm) at 365 nm, achieving 820 mJ / cm 2 0.68 seconds under irradiation to complete 90% curing (43% energy saving compared with TPO system of Comparative Example 1). The chloro substitution at the ortho position of the benzene ring increases the thermal decomposition temperature to 280℃, and the HPLC detection of the cured residual monomer is <0.3 ppm, and the mass residual rate after sintering at 600℃ reaches 94.2%, completely solving the problem of small molecule emission in high temperature process.

[0049] 4. Gradient enhancement and interface synergistic effect: 1-5 μm silica powder and D90≤8 μm glass powder form a sub-micron-micron gradient filling, and the stress concentration dispersion efficiency is improved by 60% through finite element simulation. Combined with polyether modified siloxane / polycarboxylic acid ammonium salt auxiliary system (thixotropic index 6.8), the ink maintains 6H pencil hardness while the elongation at break reaches 8%, achieving rigid-flexible balance (Comparative Example 3 hardness is only 2H), and the printing suitability and mechanical performance indicators are more than 30% higher than the industry standard. BRIEF DESCRIPTION OF DRAWINGS

[0050] Figure 1 The structure of the UV screen printing acid and alkali resistant impact resistant sintering ink photoinitiator is one of the UV screen printing acid and alkali resistant impact resistant sintering ink photoinitiators of the present application. DETAILED DESCRIPTION

[0051] The technical solutions of the present application will be described clearly and completely below in combination with the drawings in the present application. Obviously, the described embodiments are only part of the embodiments of the present application, not all. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0052] Example 1-A

[0053]

[0054] Step 1 : Compound 1-1 (20 g, 1 eq) and AlCl3(2 eq) were added to 200 g of dichloromethane, a solution of furan formyl chloride (compound 1-2) (1.2 eq) in 75 ml of dichloromethane was slowly added dropwise at -20 to 10 °C, the reaction was carried out at room temperature, after the reaction was completed, the reaction solution was slowly poured into 500 ml of 0.1 mol / L HC1 at 0 °C, stirred for 30 min, static liquid separation, the organic phase was retained, the aqueous phase was washed with 50 ml of dichloromethane for 2-3 times, the organic phase was combined, 100 ml of 0.1 mol / L sodium bicarbonate solution was added, stirred and shaken, the pH was adjusted to neutral, the organic phase was retained, dried with 20 g of anhydrous magnesium sulfate, filtered, rotary evaporated, 200 ml of n-heptane was added, stirred for 1-3 h, filtered, and dried to obtain the reaction compound 1-3;

[0055] Step 2: The product of step 1, compound 1-1 (1.0 eq), AlCl3(22.08 g, 2.0 eq) were added to 200 g of dichloromethane, acetyl chloride (7.80 g, 1.2 eq) was slowly added dropwise at 0 °C, the reaction was carried out at room temperature, after the reaction was completed, the reaction solution was slowly poured into 500 ml of 0.1 mol / L HC1 at 0 °C, stirred for 30 min, static liquid separation, the organic phase was retained, the aqueous phase was washed with 50 ml of dichloromethane for 2-3 times, the organic phase was combined, 100 ml of 0.1 mol / L sodium bicarbonate solution was added, stirred and shaken, the pH was adjusted to neutral, the organic phase was retained, dried with 20 g of anhydrous magnesium sulfate, filtered, rotary evaporated, and dried to obtain compound 1-4;

[0056] Step 3: The product of step 2, compound 1-4 (1.0 eq), hydroxylamine hydrochloride (8.27 g, 1.5 eq), sodium acetate (7.00 g, 1.5 eq) were added to 200 g of tetrahydrofuran, the reaction was carried out for 6-12 h, after the reaction was completed, the reaction solution was added to 1000 ml of water at 0 °C overnight, filtered, and a powdery solid was obtained, the powdery solid was dissolved in 100 ml of ethyl acetate, dried with 20 g of anhydrous magnesium sulfate, filtered, rotary evaporated, and dried to obtain compound 1-5;

[0057] Step 4: The product of step 3, compound 1-5 (1.0 eq), compound 1-6 (5.06 g, 1.2 eq) were added to 200 ml of dichloromethane, triethylamine (8.16 g, 1.5 eq) was slowly added dropwise at 0 °C, the reaction was carried out at room temperature for 4-6 h, after the reaction was completed, 0 °C

[0058] 500ml water, stirring 1h, static layering, retaining the organic phase, the organic phase is then 0.1 mol / L of dilute hydrochloric acid to adjust the pH to neutral, water washing 1 time, retaining the organic phase, adding 30g of anhydrous magnesium sulfate to the organic phase to dry, filtering, rotary evaporation of the solvent, obtaining a viscous liquid, the purity is greater than 93%. The viscous liquid is dissolved in 100ml of ethanol, then the ethanol solution is added dropwise to a large amount of water under high speed stirring, and the white solid product is precipitated, filtered and dried to obtain the product compound 1-7.

[0059] MS (MS+1) of compound 1-7: 871.

[0060] The synthesis steps of examples 1-B to 1-R are different from the compound 1-2 of step 1 and the compound 1-6 of step 3 in example 1-A, and other target compounds in the above formula are prepared in the same way as in example 1-A (the same reaction molar ratio and reaction conditions). The specific example structure is shown in Table 1.

[0061] Table 1.

[0062]

[0063]

[0064]

[0065] Example 1

[0066] The quality ratio of a UV silk-screen acid and alkali resistant impact resistant tempered sintered ink is: UV ink oil: 55% (epoxy acrylate: TPGDA = 2:1); lead-free glass powder: 25%; silicon powder: 10% (particle size 3μm, specific surface area 3.5m 2 g); photoinitiator: 4% (example 1-A compound); environmental protection auxiliary agent: 1.5% (BYK-190: BYK-333 = 1.5:1).

[0067] Preparation of a UV silk-screen acid and alkali resistant impact resistant tempered sintered ink: epoxy acrylate solid resin and tripropylene glycol dipropylene acrylate (TPGDA) are mixed in a mass ratio of 2:1, stirred at 500r / min under constant temperature conditions of 50℃ for 40 minutes to form a homogeneous UV ink oil; then lead-free glass powder (D 90 =6.5μm, softening point 480℃), silicon powder (particle size 3μm, specific surface area 3.5m 2Example 1-A photoinitiator and environmentally friendly additives (BYK-190 and BYK-333 mass ratio 1.5:1), high-speed dispersion at 1000 r / min for 35 minutes; transfer the mixture to a three-roll mill (roller temperature 30℃, roll gap 20μm) and cycle grinding 4 times until the particle size D 90 ≤8μm; finally add UV monomer to adjust the system viscosity to 3500±200cps, and control the solid content to 78% by vacuum degassing, to obtain the UV screen-printing acid and alkali resistant impact tempered sintering ink.

[0068] The UV screen-printing acid and alkali resistant impact tempered sintering ink is cured by irradiation with a LED cold light source with a peak wavelength of 365nm until curing.

[0069] BYK-190 is purchased from Guangzhou Haoyi New Material Technology Co., Ltd., and BYK-333 is purchased from BYK, Germany.

[0070] Examples 2-18

[0071] The formulation and preparation method are the same as Example 1, except that the photoinitiator is replaced by the corresponding compound of Examples 1-B to 1-R.

[0072] Comparative Example 1 (conventional photoinitiator)

[0073] The formulation is the same as Example 1, but the photoinitiator is replaced by conventional TPO (2,4,6-trimethylbenzoyl diphenyl phosphine oxide).

[0074] Comparative Example 2 (glass powder containing lead)

[0075] The formulation is the same as Example 1, but the lead-free glass powder is replaced by a glass powder containing 15% PbO.

[0076] Comparative Example 3 (additive mismatch)

[0077] The formulation is the same as Example 1, but the environmentally friendly additives are replaced by BYK-306 (silicone leveling agent) and BYK-111 (non-ionic dispersant) with a mass ratio of 1.5:1.

[0078] Comparative Example 4 (glass powder particle size exceeds the standard)

[0079] The formulation is the same as Example 1, but the lead-free glass powder D 90 =12μm.

[0080] Performance testing:

[0081] 1. Pencil hardness test:

[0082] The cured ink coating (thickness 20±2 μm) was fixed on a water platform; the hardness grade was selected from 6H to 6B pencil, and the coating surface was drawn at a 45° angle with a 1 kg load; the highest hardness value without permanent scratches was taken as the test result.

[0083] 2. Acid and alkali resistance test:

[0084] Solution: 5wt% HC1 (25℃), 10wt% NaOH (25℃);

[0085] Soaking time: 48 hours;

[0086] The sample (50mm x 50mm (glass substrate, coating thickness 20±2 μm)) was completely immersed in the solution and kept at constant temperature; after taking out, it was rinsed with water and dried at room temperature for 24 hours; whether the coating appeared blistering, peeling or discoloration was observed, and the adhesion was evaluated by the crosshatch method, and the peeling area <5% was qualified.

[0087] 3. Impact resistance test:

[0088] The coating sample (substrate: 304 stainless steel plate, size 80mm x 10mm x 2mm, coating thickness 20±2 μm) was prepared; the pendulum energy was set to 5J, and the impact blade curvature radius was 0.8mm; the impact energy value (kJ / m 2 ) was recorded when the sample broke, and the average value of three tests was taken.

[0089] 4. Adhesion test:

[0090] A 6x6 grid was cut on the coating surface to the substrate; after pressing with 3M tape for 10 seconds, it was quickly peeled off; according to the area ratio of coating peeling in the grid area, it was graded (0 grade: no peeling; 5 grade: >65% peeling).

[0091] 5. Lead content detection:

[0092] 0.5g of ink sample was treated by microwave digestion (nitric acid + hydrofluoric acid, 180℃); it was diluted to 50mL, filtered and analyzed; the lead content was calculated according to the standard curve, and the detection limit was 0.1ppm.

[0093] 6. Curing speed test:

[0094] 365nm LED cold light source (irradiation intensity 1200mW / cm 2 ), temperature: 25.0±0.5℃ (constant temperature laboratory), humidity: 50±3% RH (dehumidification system control).

[0095] The ink was evenly coated on a KBr salt sheet, and placed in a 25°C incubator for 5 minutes; an LED light source (wavelength 365±2nm) was started, and the FTIR real-time monitoring was also started; the 810cm -1 area of the C=C double bond characteristic peak; when the double bond conversion rate reached 90%, the cumulative irradiation energy was recorded (energy meter model: Thorlabs PM100D); the curing time = cumulative irradiation energy / irradiation intensity (1200mW / cm 2 =1.2W / cm 2 ).

[0096] Double bond conversion rate (%) = [1-(A_t / A_0)]×100; A_0: C=C peak area before curing; A_t: C=C peak area at time t.

[0097] 7. High temperature residue test:

[0098] Conditions: nitrogen atmosphere, heating rate 10°C / min, temperature range 30-600°C;

[0099] 10mg of the cured ink sample was placed in a crucible; the mass loss rate at 600°C was recorded, and the residue ratio (%) was calculated.

[0100] 8. Viscosity and solid content determination:

[0101] Solid content: 2g of the ink sample was taken and placed in a 25°C incubator for 1 hour, and then loaded into the rotor; the viscometer was started, and the rotational viscosity (unit: centipoise, cps) was recorded when the torque was stable within 10%-90% range;

[0102] The ink was evenly coated on an aluminum foil weighing pan, and placed in a heating chamber to heat to 150°C; the program was started until the mass change

[0103] <0.1mg / 30s, calculation formula:

[0104] 9. Dispersion stability of environmental protection additives:

[0105] 30mL of the ink sample was taken and loaded into a centrifuge tube, and left to stand for 10 minutes to eliminate bubbles; after centrifugation (3000rpm, 30min, 25±0.5°C), the upper clear liquid was separated, and the solid content was determined to calculate the centrifugal stability:

[0106]

[0107] The ink was diluted to 0.1% solid content (to avoid multiple scattering), and injected into a sample cell (temperature: 25±0.1°C, electric field strength: 40V / cm, dispersion medium: ultrapure water (conductivity <0.1μS / cm)); after 5 minutes of equilibrium, the average value of three automatic measurements was taken.

[0108] Rheometer temperature setting at 25 ± 0.1 °C, setting program: 0.1 s -1 (simulated rest state) -> 100 s -1 (simulated printing shear) -> 0.1 s -1 (recovery), each stage lasting 60 seconds,

[0109] Centrifuge stability > 95%: indicates that the adjuvant achieves super strong anti-settling ability;

[0110] Zeta potential > +24 mV: high positive potential ensures electrostatic repulsion between particles, preventing flocculation;

[0111] Thixotropic index > 5.8: excellent shear thinning properties, balancing printing suitability and storage stability.

[0112] Performance test data are shown in Tables 2 and 5.

[0113] Pencil hardness test, acid and alkali resistance test, impact resistance test and adhesion test data of Example 1-Example 18, Comparative Example 1-Comparative Example 4 are shown in Table 2.

[0114]

[0115]

[0116] Lead content test and curing speed test of Example 1-Example 18, Comparative Example 1-Comparative Example 4 are shown in Table 3.

[0117]

[0118] High temperature residue test, viscosity and solid content determination of Example 1-Example 18, Comparative Example 1-Comparative Example 4 are shown in Table 4.

[0119]

[0120]

[0121] Dispersing stability determination of environmentally friendly adjuvant of Example 1-Example 18, Comparative Example 1-Comparative Example 4 are shown in Table 5.

[0122] Sample No. Centrifuge stability (%) Zeta potential (mV) Thixotropic index Example 1 98.2 28.5 6.8 Example 2 97.8 27.9 6.5 Example 3 96.5 26.3 6.2 Example 4 95.4 25.1 6 Example 5 98 28.1 6.7 Example 6 97.5 27.2 6.4 Example 7 97.3 26.8 6.3 Example 8 96.8 25.9 6.1 Example 9 98.1 28.3 6.7 Example 10 95.7 24.6 5.9 Example 11 97.6 27.5 6.5 Example 12 96.9 26.1 6.2 Example 13 98.4 29 6.9 Example 14 97.2 26.7 6.4 Example 15 96.3 25.8 6 Example 16 95.1 24 5.8 Example 17 97 26.5 6.3 Example 18 97.4 27.1 6.5 Comparative Example 1 72.5 -15.3 2.1 Comparative Example 2 84.3 12.6 3.7 Comparative Example 3 68.9 -18.7 1.9 Comparative Example 4 85.4 14.2 3.5

[0123] The data of examples 1-18 show that the ink using the new photoinitiator (such as examples 1-A to 1-R) is significantly better than the traditional formula in comprehensive performance. In terms of chemical resistance, all examples have no peeling after 5% hydrochloric acid and 10% sodium hydroxide immersion for 48 hours (only individual slight yellowing or fogging occurs), and the pencil hardness is stable at 4H-6H, indicating that it forms a dense acid-base double barrier structure by gradient filling of lead-free glass powder (SiO2-B2O3-ZnO-Al2O3-ZrO2 system) and silicon powder. The impact strength reaches 35.6-43.1kJ / m 2 , far exceeding the 22.3kJ / m 2 of comparative example 1, which benefits from the synergistic effect of nano-reinforcement of silicon powder (1-5μm) and phase change toughening of ZrO2. In terms of curing performance, the new photoinitiator makes the double bond conversion rate reach 87.6%-94.2%, and the curing energy only needs 785-980mJ / cm 2 (0.65-0.82 seconds), which is more than 30% more efficient than comparative example 1 (TPO initiator), while the lead content is <0.1ppm, fully meeting environmental regulations.

[0124] Comparative examples 1-4 highlight the defects of traditional technology: using TPO initiator (comparative example 1) leads to serious deterioration of acid and alkali resistance (coating dissolution and peeling), and higher curing energy requirement (1200mJ / cm 2 ); lead-containing glass powder (comparative example 2) improves impact resistance (33.6kJ / m 2 ), but there is a risk of heavy metal pollution; improper compatibility of additives (comparative example 3) causes dispersion failure, resulting in 5-level adhesion (>65% peeling) and a sharp drop in impact resistance (18.7kJ / m 2 ); and the particle size of lead-free glass powder exceeds the standard (comparative example 4, D90=12μm), leading to increased porosity and local peeling in acid resistance. This confirms the core innovation of the present application - the "surface-bulk" regulation mechanism of specific photoinitiator structure, environmentally friendly additives (polyether-modified siloxane / polyammonium carboxylate), and precise control of glass powder particle size (D90≤8μm) and softening point (400-550℃), which is the key to balancing lead-free environmental protection, corrosion resistance and mechanical properties.

[0125] Although embodiments of the present application have been shown and described, it will be understood by those having ordinary skill in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the present application, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A UV screen printing acid and alkali resistant impact resistant tempered sintered ink, characterized by, The following components are included by mass percentage: 40%-60% UV ink, 10%-30% lead-free glass powder, 5%-15% silicon powder, 1%-5% photoinitiator, 0.5%-3% environmentally friendly auxiliary agent; The UV ink is made by mixing solid resin and UV monomer at a mass ratio of (3-1):1; The lead-free glass powder includes the following components by mass percentage: 35% SiO2, 20% B2O3, 25% ZnO, 5% Al2O3, and 5wt% zirconium oxide; The environmentally friendly auxiliary agent includes a combination of polyether-modified siloxane leveling agent and polycarboxylic acid ammonium salt dispersant at a mass ratio of (1-2):1; The solid resin is epoxy acrylate or polyurethane acrylate; The UV monomer is tripropylene glycol diacrylate or 1,6-hexanediol diacrylate; The photoinitiator is selected from: ； ； ； ； Z1 is selected from O, S, NR1, and CH2; R1 is selected from methyl, ethyl, and propyl; The softening temperature of the lead-free glass powder is 400-550 DEG C, and the particle size distribution D90 is less than or equal to 8 microns; the particle size of the silicon micropowder is 1-5 microns, and the specific surface area is 2-5 m 2 / g.

2. A UV screen printing acid and alkali resistant impact resistant tempered sintering ink according to claim 1, characterized in that, The polyether-modified siloxane leveling agent is selected from BYK-190, TEGO Dispers 755W, EFKA-4585, and Solsperse 41000; The polycarboxylic acid ammonium salt dispersant is selected from BYK-333, TEGO Flow 425, and EFKA-3777.

3. A method of preparing a UV screen-printing acid and alkali resistant impact resistant tempered sintered ink according to any one of claims 1-2, characterized in that, The following steps are included: a. Dissolve the solid resin and the UV monomer at 40-60°C to form a homogeneous UV ink; b. Add the lead-free glass powder, the silicon powder, the photoinitiator, and the environmentally friendly auxiliary agent to the product of step a in sequence, and stir at a speed of 800-1200 r / min for 20-40 minutes; c. Grind the mixture through a three-roll mill for 3-5 times with a roller spacing of 10-30μm until the particle size is ≤8μm; d. Adjust the viscosity to 2000-5000cps and the solid content to 70%-85% to obtain UV screen printing acid and alkali resistant impact-resistant sintering ink; The UV screen printing acid and alkali resistant impact-resistant sintering ink is cured under UV conditions.

4. The preparation method of the UV silk printing acid and alkali resistant impact resistant tempered sintering ink according to claim 3, characterized in that, The roller temperature of the three-roll mill in step c is 25-35°C.

5. The method for preparing a UV silk printing acid and alkali resistant impact resistant tempered sintering ink according to claim 3, characterized in that, The curing is carried out using LED cold light sources with a peak wavelength of 365 nm or 405 nm at an irradiation energy of 800-1200 mJ / cm 2 Curing is carried out for 1-5 seconds at an ambient temperature of 20-30°C.

6. The method for preparing a UV silk printing acid and alkali resistant impact resistant tempered sintering ink according to claim 3, characterized in that, The pencil hardness of the cured ink layer is ≥4H, and it does not fall off after being soaked in 5wt% hydrochloric acid and 10wt% sodium hydroxide solution for 48 hours.

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