CN113549357A - UV-curable hardening resin with antibacterial function and synthetic method thereof - Google Patents
UV-curable hardening resin with antibacterial function and synthetic method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
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Abstract
The invention discloses a UV-curable hardening resin with an antibacterial function and a synthesis method thereof, wherein the UV-curable hardening resin comprises the following raw materials: the anti-fouling paint comprises terminal triacryloxy pentaerythritol metal phthalocyanine ester, urethane acrylate, a photoinitiator, MIBK, MEK, a leveling agent, a slipping agent and an AF surface anti-fouling assistant. The coating prepared from the UV-cured sterilization anti-static anti-fingerprint resin material has the advantages of rapid and super-strong sterilization capability and anti-static capability, permanence and good wear resistance, can be well applied to coating treatment of the surface of a display window or screen glass, and is also suitable for surface coating treatment of stainless steel for medical use, kitchen marble and the like.
Description
Technical Field
The invention relates to the technical field of resin, in particular to UV-curable hardening resin with an antibacterial function and a synthetic method thereof.
Background
The coating is a liquid or solid material which is coated on the surface of an object and forms a film with protection, decoration or other special functions under certain conditions. There are many methods for classifying paints, and they can be classified into architectural paints, industrial paints, household paints, auxiliary paints, and the like according to their functions and uses. With the progress of science and technology and the development of urbanization, medical and living appliances are more and more emphasized by people. The UV coating is a common medical and living appliance coating and is mainly used for protecting the surface of a building. The UV coating can be coated by methods such as dip coating, curtain coating, paint coating, spin coating, even vacuum coating and the like, and then is cured into a film by ultraviolet photon irradiation, and the UV coating has the advantages of high curing speed, production efficiency improvement, energy conservation, no environmental pollution, wide application range and the like in use.
Although the existing UV light-cured coating has strong practicability, the defects still exist in the using process of the surface of stainless steel for medical treatment and marble in a kitchen, because the UV coating is organic liquid coating and the internal structures of various stainless steel and marble are different, after the UV coating is condensed into solid materials for a period of time, microorganisms are easily attached to the coating, substances secreted by various microorganisms can decompose the UV light-cured coating after curing, the service life of the UV light-cured building coating is influenced, and the generation of the microorganisms influences the antibacterial protection of products needing to be protected by the coating. Therefore, how to provide a UV curable hardening resin with antibacterial function and a synthetic method thereof are problems that need to be solved by those skilled in the art.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, the invention aims to provide UV-curable hardening resin with an antibacterial function and a synthesis method thereof, and the coating made of the UV-curable sterilization anti-static anti-fingerprint resin material has fast and super-strong sterilization capability and anti-static capability, has permanence and good wear resistance, can be well applied to the coating treatment of the surface of a display window or screen glass, and is also suitable for the surface coating treatment of medical stainless steel, kitchen marble and the like.
The UV-curable hardening resin with the antibacterial function, provided by the embodiment of the invention, is composed of the following raw materials: the anti-fouling paint comprises terminal triacryloxy pentaerythritol metal phthalocyanine ester, urethane acrylate, a photoinitiator, MIBK, MEK, a leveling agent, a slipping agent and an AF surface anti-fouling assistant.
Preferably, the raw materials comprise the following components in percentage by weight: 5-20% of terminal triacryloyloxy pentaerythritol metal phthalocyanine ester, 30-35% of polyurethane acrylate, 4-6% of photoinitiator, 0.1-0.3% of MIBK 30-35%, 0.2-0.5% of MEK 10%, 0.5-1% of leveling agent, 0.2-0.5% of slipping agent and 0.5-1% of AF surface oil stain-proofing auxiliary agent.
Preferably, the terminal triacryloyloxypentaerythritol metal phthalocyanine ester is prepared by reacting tetracarboxyl metal zinc phthalocyanine and pentaerythritol triacrylate.
Preferably, the zinc tetracarboxyl metal phthalocyanine is prepared by reacting trimellitic anhydride, urea, zinc chloride and ammonium molybdate.
Preferably, the synthesis method comprises the following steps:
step 1, adding triacryloyloxy pentaerythritol metal phthalocyanine ester into a flask, sequentially adding urethane acrylate, MIBK and MEK, heating to 75-80 ℃, starting stirring reaction at the stirring speed of 180-;
step 2, sequentially adding a photoinitiator, a leveling agent, a slipping agent and an AF surface oil stain prevention auxiliary agent into the flask reacted in the step 1, stirring at the normal temperature for 5-7h at the stirring speed of 170-;
and 3, step 2, coating the photocuring coating liquid on the surface of the transparent substrate layer of the PET substrate film, horizontally drawing the film on the surface of the coating layer in the coating film at a constant speed by using a wire rod according to the solid content and the coating thickness, heating the film coated with the antibacterial coating in an oven at the temperature of 130-140 ℃ for 90-100s, and then placing the film under a UV lamp for photocuring for 8-10s to obtain the UV-curable hardened resin layer with the antibacterial function.
Preferably, in step 1, the method for synthesizing the terminal triacryloyloxy pentaerythritol metal phthalocyanine ester comprises the following steps:
step 1.1, adding tetracarboxyl metal zinc phthalocyanine and a fluorocarbon solvent into a flask, adding pyridine, heating to 70-75 ℃, and stirring for 25-35 min;
and step 1.2, dropwise adding thionyl chloride into the flask heated and stirred in the step 1.1, stirring and reacting for 6-10h, removing excessive thionyl chloride through reduced pressure distillation, finally adding pentaerythritol triacrylate, and reacting for 22-24h at the temperature of 50-55 ℃ to obtain a product.
Preferably, the terminal triacryloyloxypentaerythritol metal phthalocyanine ester is terminal triacryloyloxypentaerythritol zinc phthalocyanine ester.
Preferably, in step 1, the synthesis method of the tetracarboxyl metal phthalocyanine complex comprises the following steps:
step 1.1.1, adding trimellitic anhydride, urea, zinc chloride and ammonium molybdate into a mixing device, mixing, grinding uniformly in a mortar, transferring into a beaker, covering the beaker with a cover, and covering the mouth of the beaker with a watch glass;
step 1.1.2, placing the step 1.1.1 in an oven, heating to the temperature of 120-;
step 1.1.3, taking out the gray black solid obtained in the step 1.1.2, crushing, adding the gray black solid into a saturated solution of sodium chloride, slightly boiling, cooling, filtering and drying;
and step 1.1.4, adding the product obtained in the step 1.1.3 into a sodium hydroxide solution, adding salt crystals at the same time, heating to 85-90 ℃ until no ammonia gas is discharged, cooling the solution, pouring the cooled solution into distilled water, filtering out insoluble substances, adjusting the solution to pH 2 with a hydrochloric acid solution, standing for 12-16h, completely precipitating, performing centrifugal separation, collecting and drying to obtain the product.
Preferably, the dissolving and precipitating processes in the step 1.1.4 are repeated for 2 to 3 times.
Preferably, the use of the UV curable hardening resin with antibacterial function according to claim 1 for surface coating of medical stainless steel and kitchen marble.
Compared with the prior art, the invention has the beneficial effects that:
the coating prepared from the UV-cured sterilization anti-static anti-fingerprint resin material has the advantages of rapid and super-strong sterilization capability and anti-static capability, permanence and good wear resistance, can be well applied to coating treatment of the surface of a display window or screen glass, and is also suitable for surface coating treatment of stainless steel for medical use, kitchen marble and the like.
Detailed Description
Example 1:
step 1, adding 5g of triacrylate pentaerythritol metal phthalocyanine into a flask, adding 34g of urethane acrylate, MIBK35g and MEK15g, heating to 75 ℃, starting stirring for reaction at the stirring speed of 180r/min for 5 hours, and cooling to normal temperature after stirring;
step 1.1, adding 30g of tetracarboxyl metal zinc phthalocyanine and 30ml of fluorocarbon solvent into a flask, adding 30g of pyridine, heating to 70 ℃, and stirring for 25 min;
step 1.1.1, mixing 8.45g of trimellitic anhydride, 15g of urea, 2.1g of zinc chloride and 0.113g of ammonium molybdate, grinding the mixture uniformly in a mortar, and transferring the mixture into a 500ml beaker (a 2000ml beaker is sleeved outside, and the mouth of the beaker is covered by a watch glass);
step 1.1.2, placing the step 1.1.1 in an oven, heating to 120 ℃, keeping the temperature constant for 5min, raising the temperature of the system to 180 ℃ after the foaming phenomenon stops, and reacting at constant temperature for 3.5h to obtain a gray black solid;
step 1.1.3, taking out the gray black solid obtained in the step 1.1.2, crushing, adding the gray black solid into a saturated solution of sodium chloride, slightly boiling, cooling, filtering and drying;
and step 1.1.4, adding the product obtained in the step 1.1.3 into a sodium hydroxide solution, adding salt crystals at the same time, heating to 85 ℃ until no ammonia gas is discharged, cooling the solution, pouring the cooled solution into distilled water, filtering out insoluble substances, adjusting the solution to pH 2 by using a hydrochloric acid solution, standing for 12 hours, completely precipitating, performing centrifugal separation, collecting and drying to obtain the product.
And step 1.2, dropwise adding 20ml of thionyl chloride into the flask heated and stirred in the step 1.1, stirring and reacting for 6 hours, removing excessive thionyl chloride through reduced pressure distillation, finally adding 2g of pentaerythritol triacrylate, and reacting for 22 hours at the temperature of 50 ℃ to obtain a product.
Step 2, sequentially adding 184-5g of photoinitiator, 0.2g of flatting agent, 0.3g of slipping agent and 0.5g of AF surface oil stain-proofing auxiliary agent into the flask reacted in the step 1, stirring at normal temperature for 5 hours at the stirring speed of 170r/min, standing for defoaming after stirring is stopped, and obtaining photocuring coating liquid;
and 3, step 2, coating the photocuring coating liquid on the surface of a transparent substrate layer of the PET substrate film, horizontally drawing the film on the surface of the coating layer in the coating film at a constant speed by using a wire rod according to the solid content and the coating thickness, heating the film coated with the antibacterial coating in a 130-DEG C oven for 90s, and then placing the film under a UV lamp for photocuring for 8s to obtain the UV-curable hardened resin layer with the antibacterial function.
Example 2:
step 1, adding 5g of triacrylate pentaerythritol metal phthalocyanine into a flask, adding 34g of urethane acrylate, MIBK35g and MEK15g, heating to 77 ℃, starting stirring for reaction at the stirring speed of 190r/min for 6 hours, and cooling to normal temperature after stirring;
step 1.1, adding 30g of tetracarboxyl metal zinc phthalocyanine and 30ml of fluorocarbon solvent into a flask, adding 30g of pyridine, heating to 73 ℃, and stirring for 30 min;
step 1.1.1, mixing 8.45g of trimellitic anhydride, 15g of urea, 2.1g of zinc chloride and 0.113g of ammonium molybdate, grinding the mixture uniformly in a mortar, and transferring the mixture into a 500ml beaker (a 2000ml beaker is sleeved outside, and the mouth of the beaker is covered by a watch glass);
step 1.1.2, placing the step 1.1.1 in an oven, heating to 130 ℃, keeping the temperature constant for 5-10min, raising the temperature of the system to 183 ℃ after the foaming phenomenon stops, and reacting at constant temperature for 4h to obtain a gray black solid;
step 1.1.3, taking out the gray black solid obtained in the step 1.1.2, crushing, adding the gray black solid into a saturated solution of sodium chloride, slightly boiling, cooling, filtering and drying;
and step 1.1.4, adding the product obtained in the step 1.1.3 into a sodium hydroxide solution, adding salt crystals, heating to 87 ℃ until no ammonia gas is discharged, cooling the solution, pouring the solution into distilled water, filtering out insoluble substances, adjusting the solution to pH 2 by using a hydrochloric acid solution, standing for 14h, completely precipitating, performing centrifugal separation, collecting and drying to obtain the product.
And step 1.2, dropwise adding 20ml of thionyl chloride into the flask heated and stirred in the step 1.1, stirring and reacting for 8 hours, removing excessive thionyl chloride through reduced pressure distillation, finally adding 2g of pentaerythritol triacrylate, and reacting for 23 hours at the temperature of 53 ℃ to obtain a product.
Step 2, sequentially adding 184-5g of photoinitiator, 0.2g of flatting agent, 0.3g of slipping agent and 0.5g of AF surface oil stain-proofing auxiliary agent into the flask reacted in the step 1, stirring at normal temperature for 6 hours at the stirring speed of 200r/min, standing for defoaming after stirring is stopped, and obtaining photocuring coating liquid;
and 3, coating the photocuring coating liquid on the surface of the transparent substrate layer of the PET substrate film, horizontally drawing the film on the surface of the coating layer in the coating film at a constant speed by using a wire rod according to the solid content and the coating thickness, heating the film coated with the antibacterial coating in a 135 ℃ oven for 95s, and then placing the film under a UV lamp for photocuring for 9s to obtain the UV-curable hardened resin layer with the antibacterial function.
Example 3:
step 1, adding 5g of triacrylate pentaerythritol metal phthalocyanine into a flask, adding 34g of urethane acrylate, MIBK35g and MEK15g, heating to 80 ℃, starting stirring for reaction at a stirring speed of 200r/min for 5-7h, and cooling to normal temperature after stirring;
step 1.1, adding 30g of tetracarboxyl metal zinc phthalocyanine and 30ml of fluorocarbon solvent into a flask, adding 30g of pyridine, heating to 75 ℃, and stirring for 25-35 min;
step 1.1.1, mixing 8.45g of trimellitic anhydride, 15g of urea, 2.1g of zinc chloride and 0.113g of ammonium molybdate, grinding the mixture uniformly in a mortar, and transferring the mixture into a 500ml beaker (a 2000ml beaker is sleeved outside, and the mouth of the beaker is covered by a watch glass);
step 1.1.2, placing the step 1.1.1 in an oven, heating to 135 ℃, keeping the temperature constant for 10min, raising the temperature of the system to 185 ℃ after the bubbling phenomenon stops, and reacting at constant temperature for 4.5h to obtain a gray black solid;
step 1.1.3, taking out the gray black solid obtained in the step 1.1.2, crushing, adding the gray black solid into a saturated solution of sodium chloride, slightly boiling, cooling, filtering and drying;
and step 1.1.4, adding the product obtained in the step 1.1.3 into a sodium hydroxide solution, adding salt crystals at the same time, heating to 90 ℃ until no ammonia gas is discharged, cooling the solution, pouring the solution into distilled water, filtering out insoluble substances, adjusting the solution to pH 2 by using a hydrochloric acid solution, standing for 16 hours, completely precipitating, performing centrifugal separation, collecting and drying to obtain the product.
And step 1.2, dropwise adding 20ml of thionyl chloride into the flask heated and stirred in the step 1.1, stirring and reacting for 10 hours, removing excessive thionyl chloride through reduced pressure distillation, finally adding 2g of pentaerythritol triacrylate, and reacting for 24 hours at the temperature of 55 ℃ to obtain a product.
Step 2, sequentially adding 184-5g of photoinitiator, 0.2g of flatting agent, 0.3g of slipping agent and 0.5g of AF surface oil stain prevention auxiliary agent into the flask reacted in the step 1, stirring at normal temperature for 7 hours at the stirring speed of 210r/min, standing for defoaming after stirring is stopped, and obtaining photocuring coating liquid;
and 3, coating the photocuring coating liquid on the surface of the transparent substrate layer of the PET substrate film, horizontally drawing the film on the surface of the coating layer in the coating film at a constant speed by using a wire rod according to the solid content and the coating thickness, heating the film coated with the antibacterial coating in a drying oven at 140 ℃ for 100s, and then placing the film under a UV lamp for photocuring for 10s to obtain the UV-curable hardened resin layer with the antibacterial function.
Example 4:
the carboxyl metal phthalocyanine complex is synthesized by trimellitic anhydride, metal chloride, urea and other materials to obtain the tetracarboxyl metal phthalocyanine complex.
The specific synthetic route is as follows: 8.45g of trimellitic anhydride, 15g of urea, 2.1g of zinc chloride and 0.113g of ammonium molybdate are mixed, ground uniformly in a mortar, transferred into a 500ml beaker (a 2000ml beaker is sleeved outside, and the mouth part of the beaker is covered by a watch glass), placed in an oven and heated to 130 ℃ for a constant number of minutes, after the bubbling phenomenon stops, the temperature of the system is raised to 185 ℃, and a gray black solid is obtained after a constant temperature reaction for 4 hours. Taking out the product, crushing, adding the product into 250ml of 1mol/L hydrochloric acid/sodium chloride saturated solution, slightly boiling, cooling, filtering and drying. The product was then added to 500ml of 2.0mol/L sodium hydroxide solution, while adding 200g of salt crystals and heating to 90 ℃ at which temperature the reaction was carried out until no ammonia gas evolved. The solution was cooled and poured into 1000ml of distilled water, the insoluble material was filtered off, the solution was adjusted to PH 2 with hydrochloric acid solution (6.0mol/L), allowed to stand overnight, after complete precipitation of the product, centrifuged, collected and dried. This dissolution-precipitation process was repeated 2-3 times. The product was vacuum dried to constant weight to give 4.49g with a yield of 52.1%. The reaction equation is as follows:
then the product tetracarboxyl metal zinc phthalocyanine reacts with pentaerythritol triacrylate to prepare the terminal triacryloyloxy pentaerythritol metal phthalocyanine ester.
The acrylate resin can be hydroxy acrylic acid, hydroxy vinyl resin, hydroxy vinyl organosilicon with carbon-carbon double bond, or modified epoxy, polyester, or polyimide materials with carbon-carbon double bond.
Monomers which can provide hardness in the acrylic resin in the present invention are hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate and the like, with hydroxyethyl methacrylate being preferred in the present invention. Monomers that can provide flexibility are hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, pentaerythritol triacrylate, and the like, with pentaerythritol triacrylate being preferred in the present invention.
The specific synthetic route is as follows:
adding 30g of metal phthalocyanine carboxylic acid and 30ml of fluorocarbon solvent into a three-neck flask, adding 30g of pyridine, heating to 72 ℃, stirring for 30 minutes, then dropwise adding 20ml of thionyl chloride, stirring and reacting for 6-10 hours, removing excessive thionyl chloride through reduced pressure evaporation, finally adding 2g of pentaerythritol triacrylate, and reacting for 24 hours at the temperature of 50 ℃ to obtain the terminal triacryloxy pentaerythritol metal phthalocyanine. The terminal triacryloxy pentaerythritol metal phthalocyanine is preferably terminal triacryloxy pentaerythritol zinc phthalocyanine, and the material can be applied to a UV light curing glue solution formula, and the specific formula is as follows:
5 percent of terminal triacryloyloxy pentaerythritol metal phthalocyanine, 10 percent of terminal triacryloyloxy pentaerythritol metal phthalocyanine, 15 percent of terminal triacryloyloxy pentaerythritol metal phthalocyanine, 20 percent of polyurethane acrylate, 5 percent of photoinitiator 184, 35 percent of MIBK, 15 percent of MEK, 0.2 percent of flatting agent, 0.3 percent of slipping agent and 0.5 percent of AF surface anti-oil stain additive.
Wherein 5 percent of terminal triacryloyloxy pentaerythritol metal phthalocyanine ester is synthesized as follows:
5g of triacrylate pentaerythritol metal phthalocyanine ester is added into a three-neck flask, 34g of urethane acrylate, 35 MIBK35g and MEK15g are added, the temperature is raised to 80 ℃, stirring reaction is started, the stirring speed is 200r/min, stirring is carried out for 6h, cooling is carried out to the normal temperature, 184-5g of photoinitiator, 0.2g of flatting agent, 0.3g of slipping agent and 0.5g of AF surface oil stain resistant auxiliary agent are sequentially added, stirring is carried out for 6h again at the normal temperature, the stirring speed is 200r/min, after stirring is stopped, standing and defoaming are carried out, and the viscosity of the UV photocuring antibacterial hardening liquid is measured to be 45 cps.
The preparation steps of different addition amounts of the terminal triacrylate pentaerythritol metallophthalocyanine ester with the equal ratio of 10g/15g/20g are the same as above.
The solid content of the UV photocuring antibacterial hardening formula glue solution is 50%, the photocuring coating solution is coated on the surface of a transparent base material layer of a PET base material film, and a No. 23 rod is selected according to the solid content and the coating thickness (4-5 microns). And (3) horizontally drawing the film on the inner coating surface of the coating film at a constant speed by using a wire rod, wherein the size of the film material is 19 x 28 cm. And (3) heating the film coated with the antibacterial coating in a drying oven at 140 ℃ for 100s, and then placing the film under a UV lamp for photocuring for 10s to obtain the UV-curable hardened resin layer with the antibacterial function.
Meanwhile, the coating prepared from the UV-cured sterilization anti-static anti-fingerprint resin material obtained in the embodiment is tested for the antibacterial performance of the product according to the international standard GB4789.2-2016, and the testing method comprises the following steps:
A. taking a sample of the example protective film with the size of 2cm multiplied by 3cm and a control sample;
B. weighing 3.3g agar, dissolving in 100ml water, pouring into conical flask, placing into autoclave, and sterilizing at 120 deg.C under 103kPa for 15 min;
C. dipping a small amount of escherichia coli by using an inoculating loop into a test tube containing 25mL of PBS, and shaking up;
D. respectively transferring 0.12mL of the bacterial liquid from the bacterial liquid into a plurality of test tubes containing 25mL of PBS, simultaneously putting the corresponding protective film sample and the corresponding control sample of the embodiment into the test tubes, shaking up, and standing for 20 min;
E. respectively sucking the 0.12mL of bacterial liquid, placing the bacterial liquid in a flat culture dish, pouring 10mL of nutrient agar culture medium cooled to 40-45 ℃, rotating the flat dish to ensure that the bacterial liquid is fully and uniformly mixed, turning over the flat plate after agar is solidified, culturing for 48 hours at 35 +/-2 ℃, and counting viable bacteria colonies.
The data are obtained as follows:
meanwhile, the coating prepared from the UV-cured sterilization anti-static anti-fingerprint resin material produced in the embodiment is subjected to surface water drop angle, resistance value, anti-static (friction voltage) and wear resistance value detection at the humidity of 55% and the temperature of 25 ℃, so that the following data are obtained;
specific test data for this coating:
the coating prepared from the UV-cured sterilization anti-static anti-fingerprint resin material has the advantages of rapid and super-strong sterilization capability and anti-static capability, permanence and good wear resistance, can be well applied to coating treatment of the surface of a display window or screen glass, and is also suitable for surface coating treatment of stainless steel for medical use, kitchen marble and the like.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. The UV-curable hardening resin with the antibacterial function is characterized by comprising the following raw materials: the anti-fouling paint comprises terminal triacryloxy pentaerythritol metal phthalocyanine ester, urethane acrylate, a photoinitiator, MIBK, MEK, a leveling agent, a slipping agent and an AF surface anti-fouling assistant.
2. The UV-curable hardening resin with antibacterial function according to claim 1, wherein the raw materials comprise, by weight: 5-20% of terminal triacryloyloxy pentaerythritol metal phthalocyanine ester, 30-35% of polyurethane acrylate, 4-6% of photoinitiator, 0.1-0.3% of MIBK 30-35%, 0.2-0.5% of MEK 10%, 0.5-1% of leveling agent, 0.2-0.5% of slipping agent and 0.5-1% of AF surface oil stain-proofing auxiliary agent.
3. The UV-curable hardening resin with antibacterial function according to claim 1, wherein the terminal triacryloyloxypentaerythritol metal phthalocyanine is prepared by reacting tetracarboxyl metal zinc phthalocyanine with pentaerythritol triacrylate.
4. The UV-curable hardening resin with antibacterial function according to claim 2, wherein the zinc tetracarboxyl metal phthalocyanine is obtained by reacting trimellitic anhydride, urea, zinc chloride and ammonium molybdate.
5. The method for synthesizing an antibacterial UV-curable hardening resin according to any one of claims 1 to 4, comprising the steps of:
step 1, adding triacryloyloxy pentaerythritol metal phthalocyanine into a flask, sequentially adding urethane acrylate, MIBK and MEK, heating to 75-80 ℃, starting stirring for reaction at the stirring speed of 180-200r/min for 5-7h, and cooling to normal temperature after stirring;
step 2, sequentially adding a photoinitiator, a leveling agent, a slipping agent and an AF surface oil stain prevention auxiliary agent into the flask reacted in the step 1, stirring at the normal temperature for 5-7h at the stirring speed of 170-;
and 3, step 2, coating the photocuring coating liquid on the surface of the transparent substrate layer of the PET substrate film, horizontally drawing the film on the surface of the coating layer in the coating film at a constant speed by using a wire rod according to the solid content and the coating thickness, heating the film coated with the antibacterial coating in an oven at the temperature of 130-140 ℃ for 90-100s, and then placing the film under a UV lamp for photocuring for 8-10s to obtain the UV-curable hardened resin layer with the antibacterial function.
6. The method of synthesizing UV curable hardening resin with antibacterial function according to claim 5, wherein the method for synthesizing terminally triacryloyloxypentaerythritol metal phthalocyanine ester in step 1 comprises the following steps:
step 1.1, adding tetracarboxyl metal zinc phthalocyanine and a fluorocarbon solvent into a flask, adding pyridine, heating to 70-75 ℃, and stirring for 25-35 min;
and step 1.2, dropwise adding thionyl chloride into the flask heated and stirred in the step 1.1, stirring and reacting for 6-10h, removing excessive thionyl chloride through reduced pressure distillation, finally adding pentaerythritol triacrylate, and reacting for 22-24h at the temperature of 50-55 ℃ to obtain a product.
7. The method of claim 6, wherein the terminal triacryloyloxypentaerythritol metal phthalocyanine ester is terminal triacryloyloxypentaerythritol zinc phthalocyanine ester.
8. The method for synthesizing a UV-curable hardening resin with antibacterial function according to claim 6, wherein in step 1, the method for synthesizing the tetracarboxyl-based metal phthalocyanine complex comprises the steps of:
step 1.1.1, adding trimellitic anhydride, urea, zinc chloride and ammonium molybdate into a mixing device, mixing, grinding uniformly in a mortar, transferring into a beaker, covering the beaker with a cover, and covering the mouth of the beaker with a watch glass;
step 1.1.2, placing the step 1.1.1 in an oven, heating to the temperature of 120-;
step 1.1.3, taking out the gray black solid obtained in the step 1.1.2, crushing, adding the gray black solid into a saturated solution of sodium chloride, slightly boiling, cooling, filtering and drying;
and step 1.1.4, adding the product obtained in the step 1.1.3 into a sodium hydroxide solution, adding salt crystals at the same time, heating to 85-90 ℃ until no ammonia gas is discharged, cooling the solution, pouring the cooled solution into distilled water, filtering out insoluble substances, adjusting the solution to pH 2 with a hydrochloric acid solution, standing for 12-16h, completely precipitating, performing centrifugal separation, collecting and drying to obtain the product.
9. The method for synthesizing UV curable hardening resin with antibacterial function according to claim 8, wherein the dissolving and precipitating processes in step 1.1.4 are repeated 2-3 times.
10. Use of the UV curable hardening resin with antibacterial function according to claim 1 for surface coating of medical stainless steel and kitchen marble.
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|---|---|---|---|---|
| US4522755A (en) * | 1982-09-08 | 1985-06-11 | The United States Of America As Represented By The United States National Aeronautics And Space Administration | Metal phthalocyanine intermediates for the preparation of polymers |
| CN102675625A (en) * | 2012-04-27 | 2012-09-19 | 东华大学 | Preparation method for water-solubility metal phthalocyanine derivative |
| CN102799069A (en) * | 2011-05-25 | 2012-11-28 | 乐凯华光印刷科技有限公司 | Photo-polymerization type lithographic printing plate body |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4522755A (en) * | 1982-09-08 | 1985-06-11 | The United States Of America As Represented By The United States National Aeronautics And Space Administration | Metal phthalocyanine intermediates for the preparation of polymers |
| CN102799069A (en) * | 2011-05-25 | 2012-11-28 | 乐凯华光印刷科技有限公司 | Photo-polymerization type lithographic printing plate body |
| CN102675625A (en) * | 2012-04-27 | 2012-09-19 | 东华大学 | Preparation method for water-solubility metal phthalocyanine derivative |
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