Manufacturing method of composite nano vacuum coating

Abstract

The invention relates to a manufacturing method of a composite nano vacuum coating, which comprises the following steps: (1) preparing a nano vacuum coating paint: uniformly mixing modified acrylic resin and a neutralizer, adjusting the pH value to 6.0-7.5, adding a nano composite material and phosphate modified acrylate, uniformly mixing, adding a cosolvent, mixing and dissolving, slowly adding water, uniformly stirring, and filtering to obtain the paint; and (2) coating a vacuum-coated PC base material with the coating, leveling to form a paint film with the thickness of 25-30 microns, and baking to obtain the coating film. According to the composite nano vacuum coating manufacturing method provided by the invention, a high-performance film material is prepared by improving vacuum coating raw materials and a process.

Description

Technical Field

[0001] The invention relates to the technical field of nano materials, and in particular to a method for manufacturing a composite nano vacuum coating. Background Art

[0002] With the development of the electronics industry and the information industry, especially in the large-scale preparation of printed circuits and the miniaturization of integrated circuits, thin film materials and thin film technologies have shown unique advantages; the research and development of new materials often starts with thin film synthesis and preparation; thin film materials are developing towards comprehensive, composite, intelligent and long-lasting types, which are crucial to various important areas of modern science and technology and the national economy.

[0003] Vacuum coating technology, also known as physical vapor deposition technology, is a novel material synthesis and processing technology. It transplants a metal or metal compound film (20-100 nm) onto the surface of various substrates to give the products a metal appearance, high added value, excellent wear resistance and other comprehensive properties. With the development of plastic decorative coating and the continuous development of plastic-to-metal products, vacuum coating technology is more widely used in plastic metallized products, such as automotive spotlight reflectors, automotive decorative parts, mobile phone housings, lamp parts, cosmetic boxes and daily small commodities. The coating layer materials include metal elements and alloys. Aluminum is currently the most widely used in vacuum coating technology because of its low melting point, low evaporation temperature, high light reflectivity, good gas barrier properties and low cost. Common coating substrates include ABS (acrylonitrile butadiene styrene), PC (polycarbonate), PP (polypropylene), PET (polyethylene terephthalate), PS (polystyrene), BMC (bulk molding compound), etc. Since the surface energy and heat resistance of these substrates are different, the requirements for the adhesion and heat resistance of the coating are also different.

[0004] Patent CN114318231A discloses an optical vacuum coating with nano-antibacterial function and a preparation method thereof. Aiming at the problem of weak nano-antibacterial function, the following scheme is proposed: an optical vacuum coating with nano-antibacterial function, comprising nano-titanium dioxide, nano-titanium trioxide, nano-silicon dioxide, silver, copper oxide and nano-zinc oxide, the mass fraction of each group being: 3-4 parts of the nano-titanium dioxide, 9-11 parts of the nano-titanium trioxide, 12-15 parts of the nano-silicon dioxide, and the diameter of the nano-silicon dioxide is between 20-60nm, 12-15 parts of the silver, and the diameter of the silver is 10-15nm. The copper oxide is 5-8 parts. When the present invention is prepared, the nano-titanium dioxide is a white loose powder, has a strong ultraviolet shielding effect, has good dispersibility and weather resistance, has anti-line, antibacterial, self-cleaning and anti-aging properties, and can make the film have antibacterial and self-cleaning functions.

[0005] Patent CN114773920B discloses a photothermal dual-curing vacuum coating coating for polypropylene plastic and a preparation method thereof, wherein the photothermal dual-curing vacuum coating coating for polypropylene plastic comprises the following components calculated by weight: 30 to 60 parts of photothermal dual-curing modified chlorinated polypropylene resin, 5 to 20 parts of polyurethane acrylate, 10 to 30 parts of trimethylolpropane triacrylate, 1 to 10 parts of monofunctional active diluent monomer, 1 to 5 parts of photoinitiator 184, 1 to 10 parts of hydrogen abstraction photoinitiator, 1 to 10 parts of co-initiator, 0.01 to 0.5 parts of leveling agent, and 5 to 30 parts of cosolvent. The photothermal dual-curing vacuum coating coating for polypropylene plastic of the present invention has fast curing speed, high hardness, good plating property, good adhesion to polypropylene (PP) plastic, no need to pre-treat PP plastic, can be directly applied to the surface coating of polypropylene plastic products, and has broad market application prospects.

[0006] At present, life science, environmental protection technology, material science and nanotechnology are the key research areas of high technology. In order to prepare high-performance thin film materials, it is necessary to improve the raw materials and processes of vacuum coating, and put forward higher requirements for its performance. Based on this, the present application provides a composite nano vacuum coating manufacturing method. Summary of the invention

[0007] The purpose of the present invention is to provide a composite nano vacuum coating manufacturing method. By innovating the raw materials and methods, adding composite modified nano powders, and taking nano modified materials as the core, ultra-fine leather is prepared to effectively improve the aging resistance and wear resistance of water-based suede ultra-fine leather.

[0008] A composite nano vacuum coating manufacturing method, the steps comprising:

[0009] (1) Preparation of nano vacuum coating: Mix the modified acrylic resin and the neutralizer evenly, adjust the pH value to 6.0-7.5, add the nano composite material and phosphate modified acrylic acid ester, mix and stir evenly, then add the co-solvent, after mixing, slowly add water, stir evenly and filter to obtain the coating;

[0010] (2) The coating is applied on the vacuum-coated PC substrate to form a paint film with a thickness of 25 μm to 30 μm after leveling, and the coating film is obtained after baking.

[0011] Furthermore, the composite nano vacuum coating raw materials include: 150-220 parts of waterborne polyurethane acrylate resin, 10-30 parts of nano composite material, 7-12 parts of phosphate modified acrylate, 3-6 parts of neutralizer, 20-50 parts of co-solvent, and 80-130 parts of water.

[0012] Furthermore, the neutralizing agent is triethylamine and / or 2-amino-2-methylpropanol.

[0013] Furthermore, the co-solvent includes one or more of isopropanol, butanol, and ethylene glycol butyl ether.

[0014] Furthermore, the leveling condition is infrared leveling at 70-75° C. for 8-10 minutes, and the baking condition is baking at 80-85° C. for 2-3 hours to obtain the coating film.

[0015] Furthermore, the preparation method of the modified acrylic resin comprises: adding diaminodiethoxysilane and isophorone diisocyanate to the acrylic resin at 90-100° C., mixing and stirring, and reacting for 1-2 hours to obtain the modified acrylic resin, wherein the weight ratio of the acrylic resin, diaminodiethoxysilane and isophorone diisocyanate is (8-10): (2-4): (6-8).

[0016] Furthermore, the preparation method of the nano-composite material includes: adding zeolite to a silver nitrate solution, adjusting the pH value to 7-7.5, heating in a water bath and stirring in the dark to obtain a solution containing the silver-loaded zeolite material, then adding nano-alumina and nano-titanium dioxide to the solution, ultrasonically dispersing for 2-6 hours, and centrifugally separating and drying to obtain the nano-composite material.

[0017] Furthermore, the ratio of the zeolite to the silver nitrate solution is (20-30) g / (60-100) mL, and the concentration of the silver nitrate solution is 0.05-0.4 mol / L.

[0018] Furthermore, the drying condition is drying at 90-100° C. for 6-10 hours.

[0019] Furthermore, the weight ratio of the zeolite, nano-alumina and nano-titanium dioxide is (20-25): (4-8): (6-10).

[0020] The beneficial effects of the present invention are:

[0021] The present invention uses 150-220 parts of waterborne polyurethane acrylate resin, 10-30 parts of nanocomposite material, 7-12 parts of phosphate modified acrylate, 3-6 parts of neutralizer, 20-50 parts of cosolvent and 80-130 parts of water as composite raw materials, and discloses the order of addition and mixing. The method can achieve the purpose of uniform dispersion of the nanocomposite material; in addition, the present invention also coordinates the modified acrylic resin, the nanocomposite material and the phosphate modified acrylate, and adjusts the uniformity of the coating through the nanocomposite material to improve the stability of the coating;

[0022] The nanocomposite material used in the present invention uses zeolite as a carrier, wherein the silver zeolite inorganic antibacterial agent has a small particle size, a narrow particle size distribution, is evenly distributed in the product, has a slow precipitation rate, has certain antibacterial properties, and lasts for a long time.

[0023] In addition, the added nano-silver, nano-alumina and nano-titanium dioxide can achieve a synergistic effect in the modified acrylic resin coating. After loading silver zeolite with nano-alumina and nano-titanium dioxide, the distance between the nanoparticles is controlled, so that the localized surface plasmons between the particles can couple with each other, and the control of the film surface plasmon resonance intensity is greatly enhanced, thereby increasing the stability and adhesion performance of the coating, and its heat resistance and water resistance are also improved accordingly.

[0024] The modified acrylic resin of the present invention uses acrylic resin, diaminodiethoxysilane and isophorone diisocyanate as raw materials, and adjusts the raw material ratio so that the film is uniform and not easy to fall off during coating. DETAILED DESCRIPTION

[0025] The technical solution of the present invention is described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0026] Example 1

[0027] This embodiment provides a preparation method of a composite nano vacuum coating manufacturing method, the steps comprising:

[0028] (1) Preparation of nano vacuum coating: Mix the modified acrylic resin and the neutralizer evenly, adjust the pH value to 7.0, add the nano composite material and the phosphate modified acrylic acid ester, mix and stir evenly, then add the co-solvent, after mixing, slowly add water, stir evenly and filter to obtain the coating;

[0029] The composite nano vacuum coating raw materials include: 180 parts of waterborne polyurethane acrylate resin, 20 parts of nanocomposite materials, 10 parts of phosphate-modified acrylate, 5 parts of neutralizer, 45 parts of cosolvent, and 100 parts of water;

[0030] The preparation method of the modified acrylic resin comprises: adding diaminodiethoxysilane and isophorone diisocyanate to the acrylic resin at 95° C., mixing and stirring, and reacting for 1.5 hours to obtain the modified acrylic resin, wherein the weight ratio of the acrylic resin, diaminodiethoxysilane and isophorone diisocyanate is (9): (3): (7).

[0031] The preparation method of the nanocomposite material comprises: adding zeolite to a silver nitrate solution, adjusting the pH value to 7.0, heating in a water bath and stirring in the dark to obtain a solution containing a silver-loaded zeolite material, then adding nano-alumina and nano-titanium dioxide to the solution, ultrasonically dispersing for 4 hours, centrifuging, and drying at 95° C. for 8 hours to obtain the nanocomposite material. The ratio of the zeolite to the silver nitrate solution is (25) g / (80) mL, and the concentration of the silver nitrate solution is 0.2 mol / L; the weight ratio of the zeolite, nano-alumina and nano-titanium dioxide is (22):(6):(8);

[0032] The neutralizing agent is triethylamine and 2-amino-2-methylpropanol in a mass ratio of 1:2; the cosolvent includes isopropanol;

[0033] (2) The coating is applied on a vacuum-coated PC substrate to form a paint film with a thickness of 27 μm after leveling, and the coating film is obtained after baking; the leveling condition is infrared leveling at 72° C. for 9 minutes, and the baking condition is baking at 82° C. for 2.5 hours to obtain the coating film.

[0034] Example 2

[0035] This embodiment provides a preparation method of a composite nano vacuum coating manufacturing method, the steps comprising:

[0036] (1) Preparation of nano vacuum coating: Mix the modified acrylic resin and the neutralizer evenly, adjust the pH value to 6.0, add the nano composite material and the phosphate modified acrylic acid ester, mix and stir evenly, then add the co-solvent, after mixing, slowly add water, stir evenly and filter to obtain the coating;

[0037] The composite nano vacuum coating raw materials include: 150-220 parts of waterborne polyurethane acrylate resin, 10 parts of nanocomposite material, 7 parts of phosphate-modified acrylate, 3 parts of neutralizer, 20 parts of cosolvent, and 80 parts of water;

[0038] The preparation method of the modified acrylic resin comprises: adding diaminodiethoxysilane and isophorone diisocyanate to the acrylic resin at 90° C., mixing and stirring, and reacting for 1 hour to obtain the modified acrylic resin, wherein the weight ratio of the acrylic resin, diaminodiethoxysilane and isophorone diisocyanate is (8): (2): (6).

[0039] The preparation method of the nanocomposite material comprises: adding zeolite to a silver nitrate solution, adjusting the pH value to 7, heating in a water bath and stirring in the dark to obtain a solution containing a silver-loaded zeolite material, then adding nano-alumina and nano-titanium dioxide to the solution, ultrasonically dispersing for 2 hours, centrifuging, and drying at 90° C. for 6 hours to obtain the nanocomposite material. The ratio of the zeolite to the silver nitrate solution is (20) g / (60) mL, and the concentration of the silver nitrate solution is 0.05 mol / L; the weight ratio of the zeolite, nano-alumina and nano-titanium dioxide is (20):(4):(6);

[0040] The neutralizing agent includes triethylamine and 2-amino-2-methylpropanol in a mass ratio of 1:1; and the co-solvent includes isopropanol and butanol in a mass ratio of 1:2.

[0041] (2) The coating is applied on a vacuum-coated PC substrate to form a paint film with a thickness of 25 μm after leveling, and the coating film is obtained after baking; the leveling condition is infrared leveling at 70° C. for 8 minutes, and the baking condition is baking at 80° C. for 2 hours to obtain the coating film.

[0042] Example 3

[0043] This embodiment provides a preparation method of a composite nano vacuum coating manufacturing method, the steps comprising:

[0044] (1) Preparation of nano vacuum coating: Mix the modified acrylic resin and the neutralizer evenly, adjust the pH value to 7.5, add the nano composite material and the phosphate modified acrylic acid ester, mix and stir evenly, then add the co-solvent, after mixing, slowly add water, stir evenly and filter to obtain the coating;

[0045] The composite nano vacuum coating raw materials include: 220 parts of waterborne polyurethane acrylate resin, 30 parts of nanocomposite materials, 12 parts of phosphate-modified acrylate, 6 parts of neutralizer, 50 parts of cosolvent, and 130 parts of water;

[0046] The preparation method of the modified acrylic resin comprises: adding diaminodiethoxysilane and isophorone diisocyanate to the acrylic resin at 100° C., mixing and stirring, and reacting for 2 hours to obtain the modified acrylic resin, wherein the weight ratio of the acrylic resin, diaminodiethoxysilane and isophorone diisocyanate is (10): (4): (8).

[0047] The preparation method of the nanocomposite material comprises: adding zeolite to a silver nitrate solution, adjusting the pH value to 7.5, heating in a water bath and stirring in the dark to obtain a solution containing a silver-loaded zeolite material, then adding nano-alumina and nano-titanium dioxide to the solution, ultrasonically dispersing for 6 hours, centrifuging, and drying at 100° C. for 10 hours to obtain the nanocomposite material. The ratio of the zeolite to the silver nitrate solution is (30) g / (100) mL, and the concentration of the silver nitrate solution is 0.4 mol / L; the weight ratio of the zeolite, nano-alumina and nano-titanium dioxide is (25):(8):(10);

[0048] The neutralizing agent is triethylamine; and the co-solvent includes isopropanol.

[0049] (2) The coating is applied on a vacuum-coated PC substrate to form a paint film with a thickness of 30 μm after leveling, and the coating film is obtained after baking; the leveling condition is infrared leveling at 75° C. for 10 minutes, and the baking condition is baking at 85° C. for 3 hours to obtain the coating film.

[0050] Example 4

[0051] This embodiment provides a preparation method of a composite nano vacuum coating manufacturing method, the steps comprising:

[0052] (1) Preparation of nano vacuum coating: Mix the modified acrylic resin and the neutralizer evenly, adjust the pH value to 6.0, add the nano composite material and the phosphate modified acrylic acid ester, mix and stir evenly, then add the co-solvent, after mixing, slowly add water, stir evenly and filter to obtain the coating;

[0053] The composite nano vacuum coating raw materials include: 220 parts of waterborne polyurethane acrylate resin, 30 parts of nanocomposite materials, 7 parts of phosphate-modified acrylate, 3 parts of neutralizer, 50 parts of cosolvent, and 130 parts of water;

[0054] The preparation method of the modified acrylic resin comprises: adding diaminodiethoxysilane and isophorone diisocyanate to the acrylic resin at 100° C., mixing and stirring, and reacting for 1 hour to obtain the modified acrylic resin, wherein the weight ratio of the acrylic resin, diaminodiethoxysilane and isophorone diisocyanate is (8): (4): (8).

[0055] The preparation method of the nanocomposite material comprises: adding zeolite to a silver nitrate solution, adjusting the pH value to 7.5, heating in a water bath and stirring in the dark to obtain a solution containing a silver-loaded zeolite material, then adding nano-alumina and nano-titanium dioxide to the solution, ultrasonically dispersing for 6 hours, centrifuging, and drying at 100° C. for 6 hours to obtain the nanocomposite material. The ratio of the zeolite to the silver nitrate solution is (30) g / (60) mL, and the concentration of the silver nitrate solution is 0.05 mol / L; the weight ratio of the zeolite, nano-alumina and nano-titanium dioxide is (20):(8):(10);

[0056] The neutralizing agent is 2-amino-2-methylpropanol; and the co-solvent includes butanol.

[0057] (2) The coating is applied on a vacuum-coated PC substrate to form a paint film with a thickness of 30 μm after leveling, and the coating film is obtained after baking; the leveling condition is infrared leveling at 70° C. for 10 minutes, and the baking condition is baking at 85° C. for 2 hours to obtain the coating film.

[0058] Comparative Example 1

[0059] The difference from Example 1 is that in Comparative Example 1, no nanocomposite material is added, but other raw materials of equal mass are used instead.

[0060] Comparative Example 2

[0061] Different from Example 1, in Comparative Example 2, nano-alumina and nano-titanium dioxide were not used, but were replaced by silver-loaded zeolite powder of equal mass.

[0062] Comparative Example 3

[0063] Different from Example 1, in Comparative Example 3, nano-alumina was not used.

[0064] Comparative Example 4

[0065] Different from Example 1, in Comparative Example 4, nano titanium dioxide was not used.

[0066] Comparative Example 5

[0067] Different from Example 1, the nanocomposite powder added in Comparative Example 5 is a mixed powder of nano-alumina and nano-titanium dioxide.

[0068] Comparative Example 6

[0069] Different from Example 1, in Comparative Example 6, no phosphate-modified acrylate was added.

[0070] Comparative Example 7

[0071] Different from Example 1, the acrylic resin in Comparative Example 7 is not modified.

[0072] The coatings and coating films obtained in Examples 1-4 and Comparative Examples 1-7 were subjected to the following performance tests:

[0073] (1) Storage stability of coatings: Refer to GB / T 6753.3-1986, store the coatings at 25°C in the dark for 6 months, and observe whether the coating state changes, viscosity increases, precipitation, phase separation, etc.

[0074] (2) Coating adhesion: Refer to GB / T 9286-1998 to test the adhesion of the coating to the PC substrate. It is divided into 6 levels according to the peeling situation, with level 0 being the best and level 5 being the worst.

[0075] (3) Water boiling resistance of coating: Prepare the coating on the surface of tinplate according to GB / T 1733-1993. After edge sealing, soak it in 80℃ distilled water for 2 h. Observe whether the coating surface shows any gloss loss, color change, wrinkling, bubbling, or shedding.

[0076] (4) Alcohol friction: Samsung special eraser, ethanol 99.9% or more, 1kg load, add ethanol regularly to maintain humidity 500 times back and forth (40 times back and forth / min).

[0077] The test results are shown in Table 1 below:

[0078] Table 1

[0079] Test items Coating storage stability Adhesion Boiling resistance Alcohol rubbing Example 1 No significant changes 0 No significant changes 1000 times without showing bottom Example 2 No significant changes 0 No significant changes 1000 times without showing bottom Example 3 No significant changes 0 No significant changes 1000 times without showing bottom Example 4 No significant changes 0 No significant changes 1000 times without showing bottom Comparative Example 1 Viscosity increase, precipitation and phase separation 5 Bubbling, shedding 400 times without showing bottom Comparative Example 2 Viscosity increase, precipitation and phase separation 4 Bubbling, shedding 700 times without showing bottom Comparative Example 3 Viscosity increase, precipitation and phase separation 4 Bubbling, shedding 750 times without showing bottom Comparative Example 4 Increased viscosity 2 Discoloration 900 times without showing bottom Comparative Example 5 Increased viscosity 3 Wrinkling 800 times without showing bottom Comparative Example 6 No significant changes 2 Slight loss of gloss 1000 times without showing bottom Comparative Example 7 Separation of precipitation phases 3 Discoloration 800 times without showing bottom

[0080] Finally, it should be noted that the above embodiments are only used to illustrate the present invention and are not intended to limit the technical solutions described in the present invention. Those skilled in the art should understand that the present invention can still be modified or replaced by equivalents. All technical solutions and improvements that do not depart from the spirit and scope of the present invention should be included in the scope of the claims of the present invention.

Claims

1. A composite nano vacuum coating manufacturing method, characterized in that the steps include: (1) Preparation of nano vacuum coating: Mix the modified acrylic resin and the neutralizer evenly, adjust the pH value to 6.0-7.5, add the nano composite material and phosphate modified acrylic acid ester, mix and stir evenly, then add the co-solvent, after mixing, slowly add water, stir evenly and filter to obtain the coating; (2) The coating is applied on the vacuum-coated PC substrate to form a paint film with a thickness of 25 μm to 30 μm after leveling, and the coating film is obtained after baking.

2. The composite nano vacuum coating manufacturing method according to claim 1, characterized in that: The composite nano vacuum coating raw materials include: 150-220 parts of waterborne polyurethane acrylate resin, 10-30 parts of nano composite material, 7-12 parts of phosphate modified acrylate, 3-6 parts of neutralizer, 20-50 parts of cosolvent and 80-130 parts of water.

3. The composite nano vacuum coating manufacturing method according to claim 1, characterized in that: The neutralizing agent is triethylamine and / or 2-amino-2-methylpropanol.

4. The composite nano vacuum coating manufacturing method according to claim 1, characterized in that: The co-solvent includes one or more of isopropanol, butanol, and ethylene glycol butyl ether.

5. The composite nano vacuum coating manufacturing method according to claim 1, characterized in that: The leveling condition is infrared leveling at 70-75° C. for 8-10 minutes, and the baking condition is baking at 80-85° C. for 2-3 hours to obtain the coating film.

6. The composite nano vacuum coating manufacturing method according to claim 1, characterized in that: The preparation method of the modified acrylic resin comprises: adding diaminodiethoxysilane and isophorone diisocyanate to the acrylic resin at 90-100° C., mixing and stirring, and reacting for 1-2 hours to obtain the modified acrylic resin, wherein the weight ratio of the acrylic resin, the diaminodiethoxysilane and the isophorone diisocyanate is (8-10): (2-4): (6-8).

7. The composite nano vacuum coating manufacturing method according to claim 1, characterized in that: The preparation method of the nano composite material comprises: adding zeolite to a silver nitrate solution, adjusting the pH value to 7-7.5, heating in a water bath and stirring in the dark to obtain a solution containing the silver-loaded zeolite material, then adding nano alumina and nano titanium dioxide to the solution, ultrasonically dispersing for 2-6 hours, and centrifugally separating and drying to obtain the nano composite material.

8. The composite nano vacuum coating manufacturing method according to claim 7, characterized in that: The ratio of the zeolite to the silver nitrate solution is (20-30) g / (60-100) mL, and the concentration of the silver nitrate solution is 0.05-0.4 mol / L.

9. The composite nano vacuum coating manufacturing method according to claim 7, characterized in that: The drying condition is drying at 90-100° C. for 6-10 hours.

10. The composite nano vacuum coating manufacturing method according to claim 7, characterized in that: The weight ratio of the zeolite, nano-alumina and nano-titanium dioxide is (20-25): (4-8): (6-10).