CN113897084A

CN113897084A - Antibacterial and anti-ultraviolet formable hardening coating liquid and hardened film containing same

Info

Publication number: CN113897084A
Application number: CN202111222914.9A
Authority: CN
Inventors: 张晓良
Original assignee: Jiangsu Shangke Polymer New Mateirals Co ltd
Current assignee: Jiangsu Shangke Polymer New Mateirals Co ltd
Priority date: 2021-10-20
Filing date: 2021-10-20
Publication date: 2022-01-07

Abstract

The invention provides an antibacterial and anti-ultraviolet formable hardening coating liquid and a hardened film containing the same. The antibacterial and ultraviolet-resistant formable hardening coating liquid comprises the following raw materials: 10-20% of acrylate prepolymer, 1-2% of acrylate monomer, 5-15% of thermoplastic acrylic resin, 3-8% of hydroxyl acrylic resin, 1-3% of isocyanate curing agent, 1-3% of photoinitiator, 1-3% of nano silver ions, 1-3% of nano zinc oxide, 0.1-0.3% of flatting agent and 60-75% of solvent, wherein the sum of the mass percentages of the raw materials of the antibacterial ultraviolet-resistant formable hardening coating liquid is 100%. The coating liquid is coated on the surface of a base material, and a hardened layer is formed after the coating liquid is cured, so that the hardened layer has excellent formability, antibacterial property, ultraviolet resistance, scratch resistance, abrasion resistance, chemical resistance and weather resistance, and is suitable for occasions with high requirements on formability and physical properties in the fields of automobile interior, household appliances and the like.

Description

Antibacterial and anti-ultraviolet formable hardening coating liquid and hardened film containing same

Technical Field

The invention relates to an antibacterial and anti-ultraviolet formable hardening coating liquid and a hardening film containing the same, and belongs to the technical field of hardening films.

Background

With the development of society, the conventional hardened film is not enough to meet the decorative and functional requirements of the products of automobiles, household electrical appliances and the like. In the fields of automobiles, household appliances and the like, more decorative films are required to have high surface hardness, high wear resistance, high weather resistance and antibacterial property; and simultaneously has good tensile property to realize 3D product modeling. The conventional hardened film cannot have both good forming stretchability and surface functionality.

Disclosure of Invention

In order to solve the above-described problems, an object of the present invention is to provide a cured film having excellent formability, antibacterial properties, ultraviolet resistance, scratch resistance, abrasion resistance, chemical resistance, weather resistance, and the like.

In order to achieve the above technical object, the present invention first provides an antibacterial ultraviolet resistant formable hardening coating liquid (hardening liquid), wherein the antibacterial ultraviolet resistant formable hardening coating liquid comprises the following raw material compositions: 10-20% of acrylate prepolymer, 1-2% of acrylate monomer, 5-15% of thermoplastic acrylic resin, 3-8% of hydroxyl acrylic resin, 1-3% of isocyanate curing agent, 1-3% of photoinitiator, 1-3% of nano silver ions, 1-3% of nano zinc oxide, 0.1-0.3% of flatting agent and 60-75% of solvent, wherein the sum of the mass percentages of the raw materials of the antibacterial ultraviolet-resistant formable hardening coating liquid is 100%.

The antibacterial and ultraviolet-resistant formable and hardening coating liquid disclosed by the invention can realize excellent formability, antibacterial property and ultraviolet resistance through the synergistic effect of the raw material compositions, and can keep the color of a base material below a coating and ink from fading after long-term use. The surface of the hardened layer can be completely dried after heating and drying, the hardened layer has formability after being completely dried, and UV curing is carried out after forming and stretching, so that the hardness, scratch resistance, chemical resistance and other properties of the obtained hardened layer are further improved, and the hardened layer has the antibacterial and ultraviolet-resistant effects.

The solid content of the antibacterial and ultraviolet-resistant formable hardening coating liquid is 25-40%. The solid content of the antibacterial and ultraviolet-resistant formable hardening coating liquid is beneficial to uniformly coating a hardened layer on the surface of a base material.

In one embodiment of the present invention, the acrylate prepolymer used is a multifunctional acrylate prepolymer; wherein, the functional group in the multifunctional acrylate prepolymer is selected from one or a combination of more of hydroxyl (-OH) or carboxyl (-COOH). The functional group in the multifunctional acrylate prepolymer can provide the surface polymerization degree of the hardened layer, and ensures the excellent wear resistance of the hardened layer.

In a further embodiment of the present invention, the acrylate prepolymer is an acrylic resin oligomer; specifically, the acrylate prepolymer is selected from acrylate prepolymers with a functional group less than or equal to 6; more specifically, the acrylate prepolymer is selected from one or a combination of at least two of a hexafunctional acrylate prepolymer or a trifunctional acrylate prepolymer. Wherein, the urethane acrylate, the epoxy acrylic resin, the polyester acrylic resin and the polyether acrylic resin are light-cured resins.

In one embodiment of the present invention, the acrylate monomer is also referred to as an acrylic monomer. The adopted acrylate monomer is selected from difunctional acrylate monomers; preferably, the acrylate monomer used is selected from one or a combination of at least two of urethane acrylate monomer, epoxy acrylate monomer, ether acrylate monomer and ester acrylate monomer.

In the antibacterial and anti-ultraviolet formable hardening coating liquid, the hardness, the wear resistance and the adhesive force of a hardened layer can be regulated and controlled through the synergistic effect of the acrylate monomer and the acrylic resin prepolymer.

In one embodiment of the invention, the thermoplastic acrylates used have a glass transition temperature of from 80 ℃ to 105 ℃; the molecular weight of the thermoplastic acrylate used is 80000-220000. Specifically, the adjustment of the type and the addition amount of the thermoplastic acrylic resin can realize the adjustment and control of the thermal elongation, the surface drying property and the wear resistance of the hardened layer.

In one embodiment of the present invention, the hydroxy acrylate used is selected from the group consisting of high hydroxyl number hydroxy acrylic resins having a hydroxyl number of 80 to 150. Specifically, the adjustment of the kind and the addition amount of the hydroxyacrylic resin can realize the regulation of the thermal elongation and the chemical resistance of the hardened layer.

In one embodiment of the present invention, the isocyanate curing agent is an HDI trimer.

In one embodiment of the present invention, the photoinitiator used is a cleavage type photoinitiator or/and a photosensitive type photoinitiator. Specifically, the photoinitiator is one or a combination of more of 2-hydroxy-methylphenylpropane-1-one (1173), 1-hydroxycyclohexyl phenyl ketone (184), 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-propanone (907), benzoin dimethyl ether (651), 2,4,6 (trimethylbenzoyl) diphenyl phosphine oxide (TPO), Benzophenone (BP) and 2-Isopropyl Thioxanthone (ITX); more specifically, the photoinitiators used are 1-hydroxycyclohexyl phenyl ketone (184) from basf and 2,4,6 (trimethylbenzoyl) diphenylphosphine oxide (TPO).

In one embodiment of the present invention, the nano silver ions used are nano silver ion dispersion formed by dispersing nano silver ions in an organic solvent, wherein the concentration of the nano silver ions in the nano silver ion dispersion is 1-1000 ppm. Specifically, the particle size of the adopted nano silver ions is 10-100 nm; more specifically, the particle size of the nano silver ions is 30nm-70 nm; the nano silver ion particle size is preferably 30 nm. The antibacterial property of the hardened layer can be adjusted by adjusting the addition amount and the particle size of the nano silver ions.

In one embodiment of the invention, the particle size of the nano zinc oxide is 20nm-60 nm; specifically, the passage of the nano zinc oxide used was 30 nm. The uvioresistant property of the hardened layer, namely the ultraviolet shielding property of the hardened layer can be adjusted by adjusting the addition amount and the particle size of the nano zinc oxide.

In one embodiment of the present invention, the leveling agent used is an acrylic or organosiloxane compound; specifically, the adopted leveling agent is one or a combination of more of BYK-307, BYK-377, BYK-333, BYK-254, BYK-306, EFKA (EFKA) EFKA3239, EFKA3772 and EFKA3299 of Netherlands Effia assistant; specifically, the leveling agent used is BYK-333.

In a specific embodiment of the present invention, the solvent used is one or a combination of several of butanol, isopropanol, ethyl acetate, butyl acetate, butanone and propylene glycol monomethyl ether.

In a specific embodiment of the present invention, the raw material composition of the antibacterial ultraviolet-resistant formable hardening coating liquid includes 10% to 20% of acrylate prepolymer, 1% to 2% of acrylate monomer, 5% to 15% of thermoplastic acrylic resin, 3% to 8% of hydroxyl acrylic resin, 1% to 3% of isocyanate curing agent, 1% to 3% of photoinitiator, 1% to 3% of nano silver ions, 1% to 3% of nano zinc oxide, 0.1% to 0.3% of leveling agent, and 60% to 75% of solvent. The thickness of the coating is 3-10 mu m; wherein, the acrylate prepolymer is selected from one or a combination of a hexafunctional acrylate prepolymer or a trifunctional acrylate prepolymer; the acrylic resin monomer is a difunctional acrylate monomer; the glass transition temperature point of the thermoplastic acrylate is preferably 80-120 ℃, and the molecular weight is 80000-220000; the hydroxy acrylic ester is preferably a high hydroxyl value hydroxy acrylic resin having a hydroxyl value of 80 to 150.

In a specific embodiment of the present invention, the raw material composition of the antibacterial ultraviolet-resistant formable hardening coating liquid includes 10% to 20% of acrylate prepolymer, 1% to 2% of acrylate monomer, 5% to 15% of thermoplastic acrylic resin, 3% to 8% of hydroxyl acrylic resin, 1% to 3% of isocyanate curing agent, 1% to 3% of photoinitiator, 1% to 3% of nano silver ions, 1% to 3% of nano zinc oxide, 0.1% to 0.3% of leveling agent, and 60% to 75% of solvent. The thickness of the coating is 6-10 μm. Further, the acrylate prepolymer comprises 5-10% of hexafunctional polyurethane acrylic resin oligomer and 10-15% of trifunctional polyurethane acrylic resin oligomer. Wherein, the acrylic resin monomer is a difunctional acrylate monomer; the glass transition temperature point of the thermoplastic acrylate is preferably 100-110 ℃, and the molecular weight is 100000-180000; the hydroxyl acrylate is preferably a high hydroxyl value hydroxyl acrylic resin with a hydroxyl value of 120-140.

The antibacterial and anti-ultraviolet formable hardening coating liquid with the specific composition can ensure excellent formability and surface dryness of a hardened layer, and can also ensure the performances of wear resistance, chemical resistance, antibacterial property, ultraviolet resistance and the like.

In order to achieve the above technical object, the present invention also provides a formable hardening film, which includes a base film, a hardening layer, a protective film; the hardened layer comprises an acrylate prepolymer, an acrylate monomer, thermoplastic acrylic resin, hydroxyl acrylic resin, an isocyanate curing agent, a photoinitiator, nano silver ions, nano zinc oxide, a leveling agent, a solvent and the like. Specifically, the hardened layer is formed by curing the antibacterial ultraviolet-resistant formable hardening coating liquid of the present invention.

In a specific embodiment of the present invention, the base film comprises a PC (polycarbonate) film, a PMMA (polymethyl methacrylate) film, or a blended base film of PC and PMMA. The protective film is a PE or PP co-extrusion protective film.

In a further embodiment of the invention, the thickness of the hardened layer is 6 μm to 10 μm (preferably 8 μm to 10 μm); the thickness of the base film is 50 μm to 500 μm (preferably 100 μm to 250 μm, most preferably 250 μm).

The formable hardening film of the present invention can be used for a decorative film for automotive interiors or home appliances. The preparation method of the hardened film comprises the following steps:

an antibacterial and ultraviolet-resistant formable hardening coating liquid is coated on the surface of a base material (a base film) and is placed in a circulating oven for drying to form a hardened layer.

Specifically, the temperature of the circulating oven drying was 120 ℃ for 2 minutes. Specifically, the substrate is a polycarbonate substrate provided by kosta, also known as a PC substrate.

The coating process and the drying process can be set according to the prior art.

Specifically, the protective film is arranged on the post-UV curing molding hardened layer, and the glue layer of the protective film is contacted with the completely dried post-UV curing molding hardened layer;

the above-mentioned production method further includes a step of configuring the hardened layer as an antibacterial ultraviolet resistant formable hardening coating liquid before applying the antibacterial ultraviolet resistant formable hardening coating liquid on the surface of the base material.

The control of the quantity and the content of the functional groups in the acrylic resin prepolymer in the antibacterial and ultraviolet-resistant formable hardening coating liquid has an important influence on the hardness of the surface of a hardened layer in a hardened film, and further influences the wear-resisting property of the hardened film; the type and the addition amount of the thermoplastic acrylic resin can be adjusted to control the thermal elongation, the surface drying property and the wear resistance of the hardened layer. The control of the thermal elongation and chemical resistance of the cured layer can be achieved by adjusting the type and the addition amount of the hydroxy acrylic resin. The antibacterial property and the ultraviolet resistance can be adjusted by adjusting the dosage and the particle size of the nano silver ions and the nano zinc oxide.

The antibacterial and ultraviolet-resistant formable and hardening coating liquid is coated on the surface of a transparent film (base material) and forms a hardened layer after being cured, and the hardened coating has excellent formability, antibacterial property, ultraviolet resistance, scratch resistance, wear resistance, chemical resistance and weather resistance, and is suitable for occasions with high requirements on formability and physical properties in the fields of automobile interior trim, household appliances and the like.

Drawings

Fig. 1 is a schematic structural view of a cured film in embodiment 1 of the present invention.

The main reference symbols denote:

10. a base film; 20. a hardened layer; 30. and (5) protecting the film.

Detailed Description

The hardened film provided by the invention was subjected to the following tests:

pencil hardness: the pencil hardness of the hardened layer was measured in accordance with the standard of JISK5400-1990 "measurement of adhesion of powder coating film".

Adhesion test between coating and base film: experimental tests were carried out according to GB/T9286-1998 (Baige method);

drug resistance test: carrying out a sunscreen cream resistance test according to the popular PV3964 standard;

scratch resistance (abrasion resistance): scratch testing was performed on the coating using an instrumented tacit 318 hardness pen; (Nib diameter 0.75mm load 10N)

Forming and stretching ratio: testing by using a universal tensile machine;

xenon lamp aging test (uv resistance): coating yellow ink on the other side of the substrate, and testing the delta E value after irradiation according to the popular PV1303 test standard, wherein the smaller the delta E value is, the better the uvioresistant property is;

and (3) antibacterial property: the antibacterial activity value test method is characterized in that cultured corresponding strains are placed on a tested surface, the survival rate of the tested strains is tested after the same time, the higher the antibacterial activity value is, the higher the antibacterial efficiency is, the antibacterial test standard refers to the method for testing the antibacterial performance of the plastic surface of GB/T314022015, and the specific experimental strains are as follows: e.coli ATCC 8739; staphylococcus aureus ATCC 6538P.

Example 1

The preparation method of the hardening liquid provided by the embodiment comprises the following steps:

3 percent of hexa-functional polyurethane acrylic resin oligomer, 7 percent of trifunctional polyurethane acrylic resin oligomer, 2 percent of difunctional acrylate monomer and 5 percent of thermoplastic acrylic resin are mixed, the glass transition temperature is 105 ℃, and the molecular weight is 180000; 5% of hydroxy acrylic resin; 1% of a photoinitiator 184; 2% of nano silver ions, wherein the concentration of the nano silver ions is 500ppm, and the particle size is 30 nm; 2 percent of nano zinc oxide with the particle size of 30 nm; 0.2 percent of flatting agent with the model number of BYK-333; 71.8% of solvent, wherein the solvent comprises butanone, butyl acetate and isopropanol; fully mixing until the resin is completely dissolved; finally adding 1% of isocyanate curing agent; the coating was coated on a 250 μm PC base film to form a hardened layer having a thickness of 10 μm.

The structure of the cured film of the present embodiment is shown in fig. 1, and includes a base film 10, a cured layer 20, and a protective film 30. The coating liquid of the present example was applied to the surface of a substrate, and the substrate was dried in a circulating oven at a temperature of 120 ℃ for 2 minutes to form a hardened layer. The substrate is a polycarbonate substrate provided by Costa, also known as a PC substrate.

The results of the property test of the obtained hardened film are shown in Table 1.

Example 2

5 percent of hexa-functional polyurethane acrylic resin oligomer, 5 percent of trifunctional polyurethane acrylic resin oligomer, 2 percent of difunctional acrylate monomer and 5 percent of thermoplastic acrylic resin are mixed, the glass transition temperature is 95 ℃, and the molecular weight is 200000; 5% of hydroxy acrylic resin; 1% of photoinitiator BP; 2% of nano silver ions, wherein the concentration of the nano silver ions is 300ppm, and the particle size is 50 nm; 2% of nano zinc oxide with the particle size of 50 nm; 0.2 percent of flatting agent with the model of BYK-307; 71.8% of a solvent comprising ethyl acetate, butyl acetate, propylene glycol monomethyl ether; fully mixing until the resin is completely dissolved; finally adding 1% of isocyanate curing agent; the coating was coated on a 250 μm PC based film. The thickness of the hardened layer formed was 10 μm.

Example 3

3 percent of hexa-functional polyurethane acrylic resin oligomer, 7 percent of trifunctional polyurethane acrylic resin oligomer, 2 percent of difunctional acrylate monomer and 8 percent of thermoplastic acrylic resin are mixed, the glass transition temperature is 110 ℃, and the molecular weight is 220000; 5% of hydroxyl acrylic resin and 1% of photoinitiator, wherein the photoinitiator 184 accounts for 0.5%, and the photoinitiator TPO accounts for 0.5%; 2% of nano silver ions, wherein the concentration of the nano silver ions is 300ppm, and the particle size is 30 nm; 2 percent of nano zinc oxide with the particle size of 40 nm; 0.2 percent of flatting agent with the model of BYK-254; 68.8% of a solvent comprising ethyl acetate, butyl acetate, isopropanol; fully mixing until the resin is completely dissolved; finally adding 1% of isocyanate curing agent; the coating was coated on a 250 μm PC based film.

The thickness of the hardened layer formed was 10 μm.

Example 4

3 percent of hexa-functional polyurethane acrylic resin oligomer, 7 percent of trifunctional polyurethane acrylic resin oligomer and 2 percent of difunctional acrylate monomer; 8% of thermoplastic acrylic resin, the glass transition temperature of which is 800 ℃ and the molecular weight of which is 140000; 8% of hydroxy acrylic resin; 1% of photoinitiator, wherein the photoinitiator BP accounts for 0.5% and the photoinitiator TPO accounts for 0.5%; 2% of nano silver ions, wherein the concentration of the nano silver ions is 600ppm, and the particle size is 70 nm; 2% of nano zinc oxide with the particle size of 60 nm; 0.2% of a leveling agent with the model of EFKA 3239; 64.8% of solvent, including butanone, butyl acetate and butanol; fully mixing until the resin is completely dissolved; finally adding 2% of isocyanate curing agent; the coating was coated on a 250 μm PC based film. The thickness of the hardened layer formed was 10 μm.

Comparative example 1

3% of hexa-functional polyurethane acrylic resin oligomer, 7% of tri-functional polyurethane acrylic resin oligomer, 2% of di-functional acrylate monomer, 5% of thermoplastic acrylic resin, 5% of hydroxy acrylic resin, 1% of photoinitiator, 2% of nano silver ions, 2% of nano zinc oxide, 0.2% of flatting agent and 71.8% of solvent; fully mixing until the resin is completely dissolved; finally adding 1% of isocyanate curing agent; the coating was coated on a 250 μm PC based film. The thickness of the hardened layer formed was 3 μm.

Comparative example 2

3 percent of hexa-functional polyurethane acrylic resin oligomer, 7 percent of trifunctional polyurethane acrylic resin oligomer, 2 percent of difunctional acrylate monomer, 5 percent of thermoplastic acrylic resin, 5 percent of hydroxy acrylic resin, 1 percent of photoinitiator, 2 percent of nano zinc oxide, 0.2 percent of flatting agent and 73.8 percent of solvent; fully mixing until the resin is completely dissolved; finally adding 1% of isocyanate curing agent; the coating was coated on a 250 μm PC based film. The thickness of the hardened layer formed was 10 μm.

Comparative example 3

3 percent of hexa-functional polyurethane acrylic resin oligomer, 7 percent of trifunctional polyurethane acrylic resin oligomer and 2 percent of difunctional acrylate monomer; 5% of a thermoplastic acrylic resin; 5% of hydroxy acrylic resin, 1% of photoinitiator, 2% of nano silver ions, 0.2% of flatting agent and 73.8% of solvent; fully mixing until the resin is completely dissolved; finally adding 1% of isocyanate curing agent; the coating was coated on a 250 μm PC based film. The thickness of the hardened layer formed was 10 μm.

Comparative example 4

3 percent of hexa-functional polyurethane acrylic resin oligomer, 7 percent of trifunctional polyurethane acrylic resin oligomer, 2 percent of difunctional acrylate monomer, 5 percent of thermoplastic acrylic resin, 5 percent of hydroxy acrylic resin, 1 percent of photoinitiator, 0.2 percent of flatting agent and 75.8 percent of solvent; fully mixing until the resin is completely dissolved; finally adding 1% of isocyanate curing agent; the coating was coated on a 250 μm PC based film. The thickness of the hardened layer formed was 10 μm.

Comparative example 5

This comparative example is essentially the same as example 2, except that:

15 percent of hexa-functional polyurethane acrylic resin oligomer, 15 percent of trifunctional polyurethane acrylic resin oligomer, 3 percent of difunctional acrylate monomer, 3 percent of thermoplastic acrylic resin, 2 percent of hydroxy acrylic resin, 1 percent of photoinitiator, 2 percent of nano silver ions, 2 percent of nano zinc oxide, 0.2 percent of flatting agent and 55.8 percent of solvent; fully mixing until the resin is completely dissolved; finally adding 1% of isocyanate curing agent; the coating was coated on a 250 μm PC based film. The thickness of the hardened layer formed was 10 μm.

Table 1 results of performance test of the hardened films provided in examples 1 to 4 and comparative examples 1 to 4

Note: the forming elongations in table 1 were tested just before UV curing of the hardened layer; the other properties are tested after UV curing;

as can be seen from table 1, when the coating thickness of comparative example 1 was too thin, uv resistance and scratch resistance were poor although the addition amounts of nano-nano silver ions and nano-zinc oxide were consistent with those of example 1. In contrast, comparative example 2, in which no nano silver ion was added, had far less antibacterial activity than example 1 to example 4; in comparative example 3, the color difference of the ink under the hardened film is larger, the fading is serious, and the antibacterial activity is reduced to some extent after xenon lamp aging test without adding nano zinc oxide, which shows that nano zinc oxide also has certain antibacterial ability; in the comparative example 5, the high proportion of the hexa-functional polyurethane acrylic resin oligomer and the trifunctional polyurethane acrylic resin oligomer can cause the coating to have obvious finger touch sticky feeling after being dried, which can cause the marks and sticky roll adhesion in the winding process, and the mass production is not realized; from examples 1 to 4, it can be seen that, as the ratio of the amount of the hexafunctional urethane acrylate to the amount of the trifunctional urethane acrylate is larger, the hardness of the hardened layer is higher, the molding elongation is lower, and the sunscreen properties are more excellent; when the thermoplastic acrylic resin component is more, the stretching ratio of the hardened layer is larger, but the sun cream performance is reduced; the addition of the hydroxyl acrylic resin and the isocyanate curing agent can improve the sun cream resistance of the hardened layer;

the antibacterial and ultraviolet-resistant formable hardening coating liquid provided by the invention is coated on the surface of a transparent film (base material), a hardening layer is formed after heating and drying, the hardening coating has excellent formability, and the hardening coating is cured by UV after forming to form the hardening layer.

The antibacterial property and the ultraviolet resistance of the examples 1 to 4 are excellent, wherein the comprehensive performance of the hardened films provided by the examples 2 and 4 is better, but the forming stretching ratios of the two examples are slightly different; of these, examples 1 and 3 can provide greater tensile rates, but are less resistant to sunscreen testing.

The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

Claims

1. An antibacterial ultraviolet-resistant formable hardening coating liquid, wherein the raw material composition of the antibacterial ultraviolet-resistant formable hardening coating liquid comprises: 10-20% of acrylate prepolymer, 1-2% of acrylate monomer, 5-15% of thermoplastic acrylic resin, 3-8% of hydroxyl acrylic resin, 1-3% of isocyanate curing agent, 1-3% of photoinitiator, 1-3% of nano silver ions, 1-3% of nano zinc oxide, 0.1-0.3% of flatting agent and 60-75% of solvent, wherein the sum of the mass percentages of the raw materials of the antibacterial ultraviolet-resistant formable hardening coating liquid is 100%.

2. The antibacterial ultraviolet-resistant formable hardening coating liquid according to claim 1, wherein the acrylate prepolymer is selected from acrylate prepolymers having a functional group of 6 or less;

preferably, the acrylate prepolymer is selected from one or more of a hexafunctional acrylate prepolymer or a trifunctional acrylate prepolymer;

more preferably, the functional groups of the acrylate prepolymer are selected from hydroxyl and/or carboxyl;

more preferably, the acrylate prepolymer is selected from one or a combination of at least two of polyurethane acrylic resin, epoxy acrylic resin, polyester acrylic resin and polyether acrylic resin.

3. The antibacterial ultraviolet-resistant formable hardening coating liquid according to claim 1, wherein the acrylate monomer is selected from difunctional acrylate monomers;

preferably, the acrylate monomer is selected from one or a combination of at least two of a urethane acrylate monomer, an epoxy acrylate monomer, an ether acrylate monomer and an ester acrylate monomer.

4. The antibacterial ultraviolet-resistant formable hardening coating liquid as claimed in claim 1, wherein the glass transition temperature point of the thermoplastic acrylate is 80 ℃ to 105 ℃;

preferably, the molecular weight of the thermoplastic acrylate is 80000-220000.

5. The antibacterial ultraviolet-resistant formable hardening coating liquid as claimed in claim 1, wherein the hydroxy acrylate is selected from a high hydroxyl value hydroxy acrylic resin having a hydroxyl value of 80 to 150.

6. The antibacterial ultraviolet resistant formable hardening coating liquid according to claim 1, wherein the isocyanate curing agent is HDI trimer.

7. The antibacterial ultraviolet-resistant formable hardening coating liquid according to claim 1, wherein the photoinitiator is one or a combination of several of 2-hydroxy-methylphenylpropane-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-propanone, benzoin bis methyl ether, 2,4,6 (trimethylbenzoyl) diphenylphosphine oxide, benzophenone, 2-isopropylthioxanthone;

preferably, the photoinitiator is 1-hydroxycyclohexyl phenyl ketone and 2,4,6 (trimethylbenzoyl) diphenyl phosphine oxide.

8. The antibacterial ultraviolet resistant formable hardening coating liquid according to claim 1, wherein the nano silver ions are a nano silver ion dispersion formed by dispersing nano silver ions in an organic solvent, the concentration of the nano silver ions in the nano silver ion dispersion is 1 to 1000ppm, and the particle size of the nano silver ions used is 10 to 100 nm;

preferably, the particle size of the nano zinc oxide is 20nm-60 nm;

preferably, the leveling agent is an acrylic or organosiloxane compound;

more preferably, the leveling agent is one or a combination of more of BYK-307, BYK-377, BYK-333, BYK-254, BYK-306, EFKA3239, EFKA3772 and EFKA3299 of Netherlands Effia assistant in Germany Bick chemistry;

preferably, the solvent is one or a combination of more of butanol, isopropanol, ethyl acetate, butyl acetate, butanone and propylene glycol monomethyl ether.

9. A formable hardened film includes a base film, a hardened layer, a protective film; wherein the hardened layer is formed by curing the antibacterial ultraviolet resistant formable hardening coating liquid described in any one of claims 1 to 8.

10. The formable hardening film of claim 9, wherein the base film comprises a PC film, a PMMA film, or a blended base film of PC and PMMA;

preferably, the protective film is a co-extruded protective film of PE or PP.