Visible light catalytic sterilization polyurethane coating and preparation method thereof and electronic device

Abstract

The present invention provides a polyurethane coating capable of visible light catalytic sterilization, a preparation method thereof, and an electronic device. The raw materials for preparing the polyurethane coating include a functionalized polyol polymer and a polyisocyanate; the functionalized polyol polymer has structural units derived from (A) a photosensitive bactericide containing an unsaturated double bond and (B) a polymerizable monomer, and at least one (B) polymerizable monomer contains a hydroxyl group; the (B) polymerizable monomer includes at least a (meth)acrylate monomer, and the (meth)acrylate monomer includes at least a (meth)acrylate monomer modified with a hydrophobic substance; optionally, the (B) polymerizable monomer further includes one or more olefin monomers; the molar ratio of the (A) photosensitive bactericide containing an unsaturated double bond to the (B) polymerizable monomer is 1:8 to 1:19. The polyurethane coating of the present invention can achieve the purpose of sterilization by utilizing the visible light emitted by the electronic device itself.

Description

Technical Field

[0001] The present invention relates to a polyurethane coating capable of visible light catalytic sterilization, a preparation method thereof, and an electronic device, and in particular to a polyurethane coating capable of visible light catalytic sterilization used in electronic devices, a preparation method thereof, and an electronic device having the polyurethane coating capable of visible light catalytic sterilization, belonging to the field of functional polymer coatings. Background Art

[0002] With the continuous advancement of information technology, various electronic devices have become an integral part of daily life, yet bacterial contamination on their surfaces has received insufficient attention. Studies have shown that over 7,000 types of bacteria have been detected on mobile phone surfaces alone. Bacterial contamination rates vary among different demographics, such as 66% for middle school students, 94% for medical professionals, and 96% for university students. Today, electronic products are indispensable to daily life, and they frequently come into direct contact with our hands, cheeks, ears, mouths, and other surfaces. Bacterial contamination on these surfaces can pose serious health risks and even illness. However, there is currently no effective method to directly address bacterial contamination on electronic product surfaces.

[0003] Reference 1 discloses a non-migrating antimicrobial coating material that can be applied to the inner walls of water pipes, beer and beverage storage tanks, or medical devices. Reference 2 discloses a photodynamic bactericidal coating for implant surfaces. The coating is prepared by spraying a hyperbranched boron-phosphorus-silicon ternary polymer, prepared from boric acid, diethyl phosphate, and diethoxysilane, onto the surface of the implant. However, the preparation process for these antimicrobial coatings is complex and the material costs are high, hindering their practical application.

[0004] Reference 3 discloses a copper-based antibacterial coating containing hollow titanium dioxide spheres. The antibacterial coating comprises copper, copper oxide, and titanium dioxide. However, the preparation process of this antibacterial coating is complex and can also lead to heavy metal pollution.

[0005] Reference document 4 discloses a kind of preparation method of multifunctional waterborne polyurethane-monoquaternary ammonium salt polymer, be about to polyvalent alcohol, dibasic alcohol and polyisocyanate mixing, under the effect of quaternary ammonium salt catalyst, react for a period of time, then add a certain amount of chain extender, hydroxyl-containing unsaturated monomer and tertiary amine successively to react and make the isocyanate group-terminated polyurethane prepolymer, again prepolymer is mixed with the quaternary ammonium salt containing unsaturated group in a certain mol ratio, under the effect of redox initiator, finally obtain polyurethane-monoquaternary ammonium salt polymer.But monoquaternary ammonium salt has certain cytotoxicity, and because it has been used for a long time as the sterilant service life, causes microorganism to produce the problems such as drug resistance and sterilization efficiency reduction.

[0006] Reference 5 discloses a method for preparing a polyurethane antibacterial nanosilver coating, in which nanosilver is attached to the polyurethane surface through dopamine self-polymerization to obtain an antibacterial polyurethane. However, the surface of the polyurethane loaded with silver particles is very prone to nanosilver agglomeration, which affects the dispersion and use effect of the nanosilver.

[0007] It can be seen that although some research has been conducted on antibacterial coatings in this field, the research on antibacterial coatings that can truly be applied to the surface of smart devices to isolate bacterial contamination and will not produce drug-resistant bacteria cannot be said to be sufficient, and there is room for further research.

[0008] References:

[0009] Reference 1: CN108117831A

[0010] Reference 2: CN115737923A

[0011] Reference 3: CN115820020A

[0012] Reference 4: CN102604002A

[0013] Reference 5: CN107583112A Summary of the Invention

[0014] Problems to be solved by the invention

[0015] As mentioned above, polyurethane coatings have good biocompatibility and excellent physical and mechanical properties, but they do not have antibacterial properties themselves and are easily adhered to by microorganisms such as bacteria and fungi. In order to give them antibacterial properties, the existing technology has adopted methods such as introducing monoquaternary ammonium salts and silver particles into polyurethane. However, these methods all have certain problems.

[0016] To address the above-mentioned issues, the present invention provides a polyurethane coating capable of visible light catalytic sterilization. A photosensitizer is introduced into the polyurethane coating via unsaturated double bonds, achieving visible light catalytic sterilization. This polyurethane coating utilizes visible light emitted by electronic devices themselves for sterilization, and can be applied to electronic device surfaces to isolate them from bacterial contamination. Furthermore, the introduction of flexible hydrophobic groups in polysiloxane increases flexibility, thereby alleviating the increased stress and hindered film formation caused by the introduction of reactive, sterically hindered photosensitizers into the polymer chain. Furthermore, the polyurethane coating of the present invention exhibits a strong bactericidal effect without generating drug-resistant bacteria.

[0017] Furthermore, the present invention also provides a method for preparing a polyurethane coating with visible light catalytic sterilization. The preparation method adopts a solvent thermal volatilization method, which is simple to operate, has a wide source of raw materials, is easy to obtain, and is low in price. The obtained polyurethane coating can avoid the generation of drug-resistant bacteria and has practical application value.

[0018] In addition, the present invention also provides an electronic device having the above-mentioned visible light catalytic sterilization polyurethane coating, which can achieve the purpose of sterilization by utilizing the visible light generated by the electronic device itself.

[0019] Solutions for solving problems

[0020] [1] The present invention first provides a polyurethane coating capable of visible light catalytic sterilization, wherein the raw materials for preparing the polyurethane coating include functionalized polyol polymer and polyisocyanate;

[0021] The functionalized polyol polymer has structural units derived from (A) a photosensitive bactericide containing an unsaturated double bond and (B) a polymerizable monomer, and at least one of the (B) polymerizable monomers contains a hydroxyl group;

[0022] The (B) polymerizable monomers include at least (meth)acrylate monomers, and the (meth)acrylate monomers include at least (meth)acrylate monomers modified with a hydrophobic substance;

[0023] Optionally, the (B) polymerizable monomer further comprises one or more olefin monomers;

[0024] The molar ratio of the (A) photosensitive bactericide containing an unsaturated double bond to the (B) polymerizable monomer is 1:8 to 1:19.

[0025] [2] The polyurethane coating according to the present invention [1], wherein the photosensitive bactericide (A) containing an unsaturated double bond comprises a combination of one or more of porphyrin derivatives, dihydrochlorin compounds, condensed ring quinone compounds, phthalocyanine compounds, and phenothiazine compounds.

[0026] [3] The polyurethane coating according to the present invention [1] or [2], wherein the (meth)acrylate monomer further includes a (meth)acrylate monomer containing a hydroxyl group.

[0027] [4] The polyurethane coating according to any one of [1] to [3] of the present invention, wherein the olefin monomer comprises one or more of aliphatic olefins and aromatic olefins.

[0028] [5] The polyurethane coating according to the present invention [4], wherein the hydrophobic substance modified (meth)acrylate monomer comprises a combination of one or more of polysiloxane modified (meth)acrylate monomers or fluoropolyether alcohol modified (meth)acrylate monomers; preferably, the polysiloxane modified (meth)acrylate monomer is selected from polydimethylsiloxane-(meth)acrylate, and the fluoropolyether alcohol modified (meth)acrylate monomer is selected from perfluoropolyether alcohol-(meth)acrylate.

[0029] [6] The polyurethane coating according to [4] or [5] of the present invention, wherein the content of the polysiloxane-modified (meth)acrylate monomer in the polymerizable monomer (B) is 5 mol% to 12 mol%.

[0030] [7] The polyurethane coating according to any one of [1] to [6] of the present invention is formed in the presence of an initiator (C), and the molar ratio of the photosensitive bactericidal agent (A) containing an unsaturated double bond to the initiator is 1:1 to 5:1.

[0031] [8] The polyurethane coating according to any one of [1] to [7] of the present invention, wherein the molar ratio of the functionalized polyol polymer to the polyisocyanate is 2:1 to 1:2.

[0032] [9] The polyurethane coating according to any one of [1] to [8] of the present invention, wherein the polyisocyanate comprises one or more of an aliphatic polyisocyanate, an alicyclic polyisocyanate and an aromatic polyisocyanate.

[0033]

[10] Furthermore, the present invention also provides a method for preparing the polyurethane coating according to any one of [1] to [9] of the present invention, which comprises the following steps:

[0034] The (A) photosensitive bactericide containing an unsaturated double bond and the (B) polymerizable monomer are polymerized under the action of the (C) initiator to obtain the functionalized polyol polymer;

[0035] The functionalized polyol polymer, polyisocyanate and organic solvent are mixed and subjected to solvent thermal volatilization to obtain a polyurethane coating.

[0036]

[11] According to the preparation method described in

[10] of the present invention, the polymerization reaction temperature is 70-90°C and the time is 3-24 hours.

[0037]

[12] According to the preparation method described in

[10] or

[11] of the present invention, the temperature of the solvent thermal volatilization is 60-100°C and the time is 6-12 hours.

[0038]

[13] In addition, the present invention also provides an electronic device, which includes a display device, wherein the surface of the display element of the display device has the polyurethane coating according to any one of [1] to [9] of the present invention.

[0039] Effects of the Invention

[0040] By implementing the above technical solution, the present invention can achieve the following technical effects:

[0041] 1) The present invention introduces a photosensitive bactericide into the polyurethane coating via an unsaturated double bond, thereby achieving visible light catalytic sterilization of the polyurethane coating. The visible light emitted by the electronic device itself can be used to achieve the purpose of sterilization, and can be applied to the surface of electronic equipment to isolate bacterial contamination.

[0042] 2) The photosensitizer of the present invention generates reactive oxygen species (ROS) after being irradiated with visible light. These ROS can generate oxygen-containing free radicals such as superoxide anions (O2· - ), hydroxyl radicals (·OH), or by transferring energy to surrounding oxygen molecules to form singlet oxygen molecules ( 1 O2), this sterilization method based on various visible light-excited π-conjugated photosensitizers is easy to implement and operate. Furthermore, ROS kills bacteria by damaging the bacterial cell membrane, leaking cytoplasmic components and destroying DNA in the cell matrix. The polyurethane coating of the present invention, which can photocatalytically sterilize, has a strong bactericidal effect while preventing the development of drug-resistant bacteria.

[0043] 3) The raw materials for preparing the polyurethane coating of the present invention also contain a flexible hydrophobic substance, a polysiloxane-modified (meth)acrylate monomer. The hydrophobic substance is introduced into the coating through an unsaturated double bond, so that the polyurethane coating has good hydrophobic properties and flexibility while having bactericidal properties, which is further conducive to deposition and film formation and prevents bacterial growth.

[0044] 4) The present invention prepares a polyurethane coating with visible light catalytic sterilization through a solvent thermal volatilization method. The preparation method is simple, the raw materials are widely available, easy to obtain, and low in price. The obtained polyurethane coating can avoid the generation of drug-resistant bacteria and has practical application value. BRIEF DESCRIPTION OF THE DRAWINGS

[0045] Figure 1 This is the synthetic route of the functionalized polyol polymer of Example 1;

[0046] Figure 2 The surface morphology of bacteria on the surface of the polyurethane coating for visible light catalytic sterilization prepared in Example 1 and the blank group;

[0047] Figure 3Live / dead staining of bacteria on the surface of the polyurethane coating with visible light catalytic sterilization prepared in Example 1 and the blank group;

[0048] Figure 4 The polyurethane material with visible light catalytic sterilization prepared in Example 1 was used for skin wound repair in SD rats and compared with the blank group. DETAILED DESCRIPTION

[0049] The following is a detailed description of the present invention. The following description of the technical features is based on representative embodiments and specific examples of the present invention, but the present invention is not limited to these embodiments and specific examples. It should be noted that:

[0050] In this specification, the numerical range expressed using "a numerical value A to a numerical value B" means a range including the endpoints A and B.

[0051] In this specification, the numerical range expressed using "above" or "below" means a numerical range including the number.

[0052] In this specification, the use of "may" includes both the meaning of performing a certain process and the meaning of not performing a certain process.

[0053] In this specification, the use of "optional" or "optional" indicates that certain substances, components, execution steps, application conditions and other factors are used or not used.

[0054] In this specification, the “normal temperature” or “room temperature” used refers to an indoor ambient temperature of “23±2° C.”, and unless otherwise specified, the “viscosity” of the present invention refers to the viscosity at this temperature.

[0055] In this specification, the unit names used are all international standard unit names, and unless otherwise stated, the "%" used means weight or mass percentage.

[0056] In this specification, the use of "substantially" means that the standard deviation from a theoretical model or theoretical data is within a numerical range of 5%, preferably 3%, and more preferably 1%.

[0057] When the terms “include” and / or “comprising” are used in this specification, they indicate the presence of features, steps, operations, devices, components and / or their combinations.

[0058] In this specification, references to "some specific / preferred embodiments," "other specific / preferred embodiments," "embodiments," etc., mean that the specific elements (e.g., features, structures, properties, and / or characteristics) described in connection with the embodiments are included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it should be understood that the elements may be combined in various embodiments in any suitable manner.

[0059] The present invention provides a polyurethane coating capable of visible light catalytic sterilization and a preparation method thereof. The polyurethane coating incorporates a photosensitizer via unsaturated double bonds, achieving visible light catalytic sterilization. This polyurethane coating utilizes visible light emitted by electronic devices to achieve sterilization, and can be applied to electronic device surfaces to isolate them from bacterial contamination. Furthermore, while exhibiting a strong bactericidal effect, the polyurethane coating does not promote the development of drug-resistant bacteria.

[0060] The present invention is based on the following insights:

[0061] It is known that polyurethane coating has good biocompatibility and mechanical properties, but it does not have antibacterial properties. In order to improve its antibacterial properties, the existing technology is introduced into methods such as monoquaternary ammonium salts and silver particles, but these methods all have certain problems. Photodynamic antibacterial is a new technology that utilizes light irradiation of a specific wavelength of photosensitizer to promote it to produce reactive oxygen to destroy the cytoplasmic membrane and nucleus of bacteria to achieve antibacterial purposes. The antibacterial mode of this oxidative stress will not weaken the bactericidal effect due to the evolution of bacteria, so it does not develop drug resistance and is one of the main means to solve the problem of bacterial drug resistance. However, there are fewer reports on the preparation of antibacterial polyurethanes in combination with polyurethane coatings at present. The present invention not only achieves visible light catalytic sterilization of polyurethane coatings by introducing photosensitizers into polyurethane coatings and grafting them into polyurethane molecular chains, but also introduces flexible hydrophobic groups, thereby achieving film formation, thereby achieving the purpose of sterilization by the visible light emitted by electronic equipment itself, and can be applied to electronic equipment surfaces to isolate bacterial contamination.

[0062] <First Aspect>

[0063] A first aspect of the present invention provides a polyurethane coating capable of visible light catalytic sterilization, wherein the raw materials for preparing the polyurethane coating include functionalized polyol polymers and polyisocyanates.

[0064] In addition, without limitation, various optional functional additive components may be used in the polyurethane coating as long as the technical effects of the present invention are not hindered.

[0065] (Functionalized Polyol Polymer)

[0066] The functionalized polyol polymer of the present invention comprises structural units derived from (A) a photosensitive fungicide containing an unsaturated double bond and (B) a polymerizable monomer. The hydroxyl functionality of the functionalized polyol polymer of the present invention is not particularly limited in principle and can generally be 2 or greater.

[0067] (A) Photosensitive fungicides containing unsaturated double bonds

[0068] The photosensitive fungicide containing unsaturated double bonds can generate reactive oxygen species under visible light excitation. The reactive oxygen species destroy the bacterial cell membrane, leaking cytoplasmic components and damaging DNA in the cell matrix to kill bacteria. Furthermore, the unsaturated double bonds polymerize with polymerizable monomers and are grafted onto polyol polymers, achieving functionalization of the polyol polymer.

[0069] The types of photosensitizers containing unsaturated double bonds include, for example, one or more combinations of porphyrin derivatives, dihydrochlorin compounds, condensed ring quinone compounds, phthalocyanine compounds, and phenothiazine compounds. Among them, from the perspective of absorption wavelength, porphyrin derivatives are preferred. In some specific embodiments, the porphyrin derivatives include, for example, tetraphenylporphyrin chloride as shown in formula (1).

[0070]

[0071] (B) polymerizable monomer

[0072] The polymerizable monomers include at least (meth)acrylate monomers. In order to improve the hydrophobicity of the polyurethane coating, prevent the growth of bacteria in a humid state, further improve the antibacterial effect, and obtain a polyurethane coating that is both bactericidal and hydrophobic, the (meth)acrylate monomers include at least (meth)acrylate monomers modified with hydrophobic substances.

[0073] In some specific embodiments, the hydrophobic substance modified (meth)acrylate monomer includes a combination of one or more of a polysiloxane modified (meth)acrylate monomer or a fluoropolyether alcohol modified (meth)acrylate monomer; wherein the polysiloxane modified (meth)acrylate monomer can be selected from polydimethylsiloxane-(meth)acrylate, etc., and the fluoropolyether alcohol modified (meth)acrylate monomer can be selected from perfluoropolyether alcohol-(meth)acrylate, etc.

[0074] In some preferred embodiments, from the perspective of hydrophobicity and molecular chain flexibility, the hydrophobic substance-modified (meth)acrylate monomer can be selected from polysiloxane-modified (meth)acrylate monomers. By introducing polysiloxane groups, the internal stress caused by the large steric hindrance groups in the above-mentioned reactive photosensitive bactericide can be alleviated during the film formation process, and the final coating can also obtain a satisfactory contact angle.

[0075] In the present invention, at least one polymerizable monomer contains a hydroxyl group. In principle, there is no particular limitation on the polymerizable monomer containing a hydroxyl group, and it can be selected as needed. For example, it can be a (meth)acrylate monomer containing a hydroxyl group, or it can be an olefin monomer containing a hydroxyl group as described below. In some specific embodiments, one or more combinations of hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, etc. can be cited.

[0076] In some more specific embodiments, in addition to the above-mentioned polysiloxane-modified (meth)acrylate monomers and hydroxyl-containing (meth)acrylate monomers, the present invention may also include other (meth)acrylate monomers, which may include one or more combinations of methyl methacrylate, ethyl methacrylate, etc.

[0077] Optionally, from the perspective of improving the strength and flexibility of the polyurethane coating, the polymerizable monomer further includes one or more olefin monomers. As described above, these monomers may further have or not have hydroxyl groups. In some preferred embodiments, they may include one or more aliphatic olefins (without hydroxyl groups) and aromatic olefins. Specifically, the aliphatic olefins may include a combination of one or more of ethylene, isobutylene, isoprene, etc., and the aromatic olefins may include styrene, etc.

[0078] In the present invention, the polyurethane coating layer may be formed in the presence of (C) a photoinitiator.

[0079] (C) Photoinitiator

[0080] The initiator of the present invention is a free radical initiator, which is used to cause the photosensitive bactericide containing unsaturated double bonds and the polymerizable monomer to undergo free radical polymerization.

[0081] The free radical initiator can be an initiator commonly used in the art, such as an azo initiator, an inorganic peroxide initiator, etc., and can include one or more of azobisisobutyronitrile (AIBN), azobisisoheptanenitrile, potassium persulfate, sodium persulfate or ammonium persulfate.

[0082] Composition of functionalized polyol polymers

[0083] The molar ratio of (A) the photosensitive fungicide containing an unsaturated double bond to (B) the polymerizable monomer can be 1:8 to 1:19, for example, 1:9, 1:10, 1:12, 1:14, 1:16, 1:18, etc.

[0084] In the (B) polymerizable monomer, the content of the polysiloxane-modified (meth)acrylate monomer may be 5 mol% to 12 mol%, for example, 6 mol%, 7 mol%, 8 mol%, 9 mol%, 10 mol%, 11 mol%, etc.

[0085] The molar ratio of the photosensitive fungicide (A) containing an unsaturated double bond to the initiator (C) can be 1:1 to 5:1, for example, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, etc. Excessive initiator content may reduce the molecular weight of the functionalized polyol, thereby affecting the surface properties of the coating. Excessive initiator content may fail to achieve the objectives of the present invention.

[0086] (Polyisocyanate)

[0087] There is actually no particular limitation on the type of polyisocyanate of the present invention, and polyisocyanates commonly used in the art can be used, for example, one or more of aliphatic polyisocyanates, alicyclic polyisocyanates and aromatic polyisocyanates.

[0088] The functionality of the polyisocyanate of the present invention may generally be 2 or more, and preferably 2 to 4.

[0089] The aliphatic polyisocyanate may generally be an aliphatic polyisocyanate having a linear or branched structure, such as hexamethylene diisocyanate, polyhexamethylene diisocyanate, and the like.

[0090] The alicyclic polyisocyanate may generally be a polyisocyanate having one or more aliphatic rings with four or more carbon atoms in its molecular structure, such as methylene dicyclohexyl diisocyanate, hydrogenated MDI (HMDI), and isophorone diisocyanate (IPDI).

[0091] The aromatic polyisocyanate may generally be a polyisocyanate having a benzene ring structure, for example, methylene diphenyl diisocyanate (MDI) and toluene diisocyanate (TDI).

[0092] In some preferred embodiments, the polyisocyanate of the present invention may be polyhexamethylene diisocyanate.

[0093] (Composition of polyurethane)

[0094] The polyurethane coating of the present invention can be obtained by reacting the above-mentioned functionalized polyol polymer with polyisocyanate.

[0095] In addition to the functionalized polyol polymer and polyisocyanate described above, the present invention may optionally use other desired components, for example, small molecule polyols, and monoalcohols and monoisocyanates as end-capping agents.

[0096] In principle, there is no particular limitation on the ratio of the functionalized polyol polymer to the polyisocyanate, and the ratio may be 2:1 to 1:2, for example, 1.5:1, 1:1, 1:1.5, and the like.

[0097] <Second Aspect>

[0098] The second aspect of the present invention provides a method for preparing the polyurethane coating capable of visible light catalytic sterilization according to the first aspect, comprising the following steps:

[0099] The (A) photosensitive bactericide containing an unsaturated double bond and the (B) polymerizable monomer are polymerized under the action of the (C) initiator to obtain a functionalized polyol polymer;

[0100] The functionalized polyol polymer, polyisocyanate and organic solvent are mixed and subjected to solvent thermal volatilization to obtain a polyurethane coating.

[0101] The types and amounts of the photosensitive bactericide containing unsaturated double bonds, polymerizable monomers, initiators and polyisocyanates are the same as those in the first aspect and will not be described in detail here.

[0102] The polymerization reaction step may specifically include: dissolving the photosensitive fungicide containing unsaturated double bonds and polymerizable monomers in an organic solvent, and then performing a polymerization reaction in the presence of an initiator.

[0103] The temperature and time of the polymerization reaction are not particularly limited and can be selected based on the temperature and time required for the initiator to initiate the reaction. In some specific embodiments, the polymerization reaction temperature is 70 to 90°C, such as 75°C, 80°C, 85°C, etc.; and the polymerization reaction time is 3 to 24 hours, such as 6 hours, 10 hours, 15 hours, 20 hours, etc.

[0104] In some more specific embodiments, in order to improve the purity of the product, the polymerization reaction can be carried out under nitrogen protection.

[0105] The organic solvent may be selected from one or a combination of tetrahydrofuran, toluene, N,N-dimethylformamide, butanol, acetone and xylene.

[0106] There is no particular limitation on the amount of the organic solvent used in the polymerization reaction and it can be selected as needed. In some specific embodiments, the molar concentration of the photosensitive fungicide containing an unsaturated double bond in the organic solvent can be 0.05 mol / L to 0.1 mol / L.

[0107] In some specific embodiments, after the polymerization reaction, the following steps are further included: removing excess solvent by rotary evaporation and then precipitating to obtain a crude polyol polymer; then dissolving the obtained crude polyol polymer in an organic solvent and then precipitating it in a precipitant; repeating the precipitation 3 to 5 times; and then drying the repeatedly precipitated crude polyol polymer in a vacuum drying oven at 80°C for 12 hours to obtain a functionalized polyol polymer.

[0108] The precipitant is not particularly limited and can be selected as needed. For example, it can be selected from a combination of one or more of petroleum ether, n-hexane, etc.

[0109] In some specific embodiments, the amount of organic solvent used in the solvent thermal volatilization step can be expressed as 30 to 70 g / L based on the mass concentration of the functionalized polyol polymer, for example, 40 g / L, 50 g / L, 60 g / L, etc.

[0110] In some specific embodiments, the temperature of the solvent thermal volatilization is 60-100°C, for example, 70°C, 80°C, 90°C, etc.; the time of the solvent thermal volatilization is 6-12h, for example, 7h, 8h, 9h, 10h, 11h, etc.

[0111] In some more specific embodiments, the solvent volatilization step can be performed by coating a mixture of functionalized polyol polymer, polyisocyanate and organic solvent on the surface of the substrate. There is no particular limitation on the material of the substrate, and specifically, it can be selected from metal, wood, glass, etc.

[0112] <Third Aspect>

[0113] A third aspect of the present invention provides an electronic device, comprising a display device, wherein a surface of a display element of the display device has the polyurethane coating according to the first aspect.

[0114] Example

[0115] The embodiments of the present invention will be described in detail below with reference to the examples, but it will be understood by those skilled in the art that the following examples are merely illustrative of the present invention and should not be construed as limiting the scope of the invention. Where specific conditions are not specified in the examples, the methods were performed according to conventional conditions or the conditions recommended by the manufacturer. Where the manufacturers of the reagents or instruments are not specified, they are all conventional products that can be obtained commercially.

[0116] Example 1

[0117] (1) Preparation of functionalized polyol polymers:

[0118] Hydroxyethyl methacrylate (HEMA, 0.6 mmol), methyl methacrylate (MMA, 0.1 mmol), ethyl methacrylate (BMA, 0.1 mmol), styrene (0.1 mmol), tetraphenylporphyrin chloride (0.05 mmol), and polydimethylsiloxane methacrylate (0.05 mmol) were dissolved in 1 mL of a mixed solvent (toluene / butanol: 1:1). Under a nitrogen atmosphere, AIBN (0.03 mmol) was added as an initiator and stirred at 80°C for 6 h to obtain a mixed solution. After the reaction, the mixture was rotary evaporated to remove residual solvent to obtain a crude polyol solution. The crude polyol solution was then dropwise added to 5 mL of n-hexane for precipitation. The solution was then redissolved in acetone and precipitated in n-hexane. This process was repeated three times before drying to obtain a functionalized polyol polymer.

[0119] (2) Preparation of polyurethane coating:

[0120] 0.2g of a functionalized polyol polymer and 0.1g of polyhexamethylene diisocyanate (HDIT) were weighed and dissolved in 3mL of butanone to create a mixed solution. 0.5mL of the mixed solution was then applied to substrates of various materials and placed in an oven at 60°C for 6 hours to produce a photocatalytically bactericidal polyurethane coating.

[0121] Example 2

[0122] (1) Preparation of functionalized polyol polymers:

[0123] Hydroxyethyl methacrylate (HEMA, 0.5 mmol), methyl methacrylate (MMA, 0.2 mmol), ethyl methacrylate (BMA, 0.1 mmol), styrene (0.1 mmol), tetraphenylporphyrin chloride (0.05 mmol), and polydimethylsiloxane methacrylate (0.05 mmol) were dissolved in 1 mL of a mixed solvent (toluene / butanol: 1:1). AIBN (0.03 mmol) was added as an initiator under a nitrogen atmosphere, and the mixture was stirred at 80°C for 6 h to obtain a mixed solution. After the reaction, the mixture was rotary evaporated to remove residual solvent to obtain a crude polyol solution. The crude polyol solution was then dropwise added to 5 mL of n-hexane for precipitation. The solution was then redissolved in acetone and precipitated in n-hexane. This process was repeated three times, and the functionalized polyol polymer was dried.

[0124] (2) Preparation of polyurethane coating:

[0125] 0.2g of a functionalized polyol polymer and 0.1g of polyhexamethylene diisocyanate (HDIT) were weighed and dissolved in 3mL of butanone to create a mixed solution. 0.5mL of the mixed solution was then applied to substrates of various materials and placed in an oven at 60°C for 6 hours to produce a photocatalytically bactericidal polyurethane coating.

[0126] Example 3

[0127] (1) Preparation of functionalized polyol polymers:

[0128] Hydroxyethyl methacrylate (HEMA, 0.5 mmol), methyl methacrylate (MMA, 0.1 mmol), ethyl methacrylate (BMA, 0.2 mmol), styrene (0.1 mmol), tetraphenylporphyrin chloride (0.05 mmol), and polydimethylsiloxane methacrylate (0.05 mmol) were dissolved in 1 mL of a mixed solvent (toluene / butanol: 1:1). Under a nitrogen atmosphere, AIBN (0.03 mmol) was added as an initiator and stirred at 80°C for 6 h to obtain a mixed solution. After the reaction, the mixture was rotary evaporated to remove residual solvent to obtain a crude polyol solution. The crude polyol solution was then dropwise added to 5 mL of n-hexane for precipitation. The solution was then redissolved in acetone and precipitated in n-hexane. This process was repeated three times before drying to obtain a functionalized polyol polymer.

[0129] (2) Preparation of polyurethane coating:

[0130] 0.2g of a functionalized polyol polymer and 0.1g of polyhexamethylene diisocyanate (HDIT) were weighed and dissolved in 3mL of butanone to create a mixed solution. 0.5mL of the mixed solution was then applied to substrates of various materials and placed in an oven at 60°C for 6 hours to produce a photocatalytically bactericidal polyurethane coating.

[0131] Example 4

[0132] (1) Preparation of functionalized polyol polymers:

[0133] Hydroxyethyl methacrylate (HEMA, 0.5 mmol), methyl methacrylate (MMA, 0.1 mmol), ethyl methacrylate (BMA, 0.1 mmol), styrene (0.2 mmol), tetraphenylporphyrin chloride (0.05 mmol), and polydimethylsiloxane methacrylate (0.05 mmol) were dissolved in 1 mL of a mixed solvent (toluene / butanol: 1:1). Under a nitrogen atmosphere, AIBN (0.03 mmol) was added as an initiator and stirred at 80°C for 6 h to obtain a mixed solution. After the reaction, the mixture was rotary evaporated to remove residual solvent to obtain a crude polyol solution. The crude polyol solution was then added dropwise to 5 mL of n-hexane for precipitation. The solution was then redissolved in acetone and precipitated in n-hexane. This process was repeated three times before drying to obtain a functionalized polyol polymer.

[0134] (2) Preparation of polyurethane coating:

[0135] 0.2g of a functionalized polyol polymer and 0.1g of polyhexamethylene diisocyanate (HDIT) were weighed and dissolved in 3mL of butanone to create a mixed solution. 0.5mL of the mixed solution was then applied to substrates of various materials and placed in an oven at 60°C for 6 hours to produce a photocatalytically bactericidal polyurethane coating.

[0136] Example 5

[0137] (1) Preparation of functionalized polyol polymers:

[0138] Hydroxyethyl methacrylate (HEMA, 0.6 mmol), methyl methacrylate (MMA, 0.05 mmol), ethyl methacrylate (BMA, 0.05 mmol), styrene (0.1 mmol), tetraphenylporphyrin chloride (0.1 mmol), and polydimethylsiloxane methacrylate (0.1 mmol) were dissolved in 1 mL of a mixed solvent (toluene / butanol: 1:1). Under a nitrogen atmosphere, AIBN (0.03 mmol) was added as an initiator and stirred at 80°C for 6 h to obtain a mixed solution. After the reaction, the mixture was rotary evaporated to remove residual solvent to obtain a crude polyol solution. The crude polyol solution was then added dropwise to 5 mL of n-hexane for precipitation. The solution was then redissolved in acetone and precipitated in n-hexane. This process was repeated three times before drying to obtain a functionalized polyol polymer.

[0139] (2) Preparation of polyurethane coating:

[0140] 0.2g of a functionalized polyol polymer and 0.1g of polyhexamethylene diisocyanate (HDIT) were weighed and dissolved in 3mL of butanone to create a mixed solution. 0.5mL of the mixed solution was then applied to substrates of various materials and placed in an oven at 60°C for 6 hours to produce a photocatalytically bactericidal polyurethane coating.

[0141] Example 6

[0142] (1) Preparation of functionalized polyol polymers:

[0143] Hydroxyethyl methacrylate (HEMA, 0.6 mmol), methyl methacrylate (MMA, 0.1 mmol), ethyl methacrylate (BMA, 0.1 mmol), styrene (0.1 mmol), tetraphenylporphyrin chloride (0.05 mmol), and polydimethylsiloxane methacrylate (0.05 mmol) were dissolved in 1 mL of a mixed solvent (toluene / butanol: 1:1). Under a nitrogen atmosphere, AIBN (0.05 mmol) was added as an initiator and stirred at 80°C for 6 h to obtain a mixed solution. After the reaction, the mixture was rotary evaporated to remove residual solvent to obtain a crude polyol solution. The crude polyol solution was then dropwise added to 5 mL of n-hexane for precipitation. The solution was then redissolved in acetone and precipitated in n-hexane. This process was repeated three times before drying to obtain a functionalized polyol polymer.

[0144] (2) Preparation of polyurethane coating:

[0145] 0.2g of a functionalized polyol polymer and 0.1g of polyhexamethylene diisocyanate (HDIT) were weighed and dissolved in 3mL of butanone to create a mixed solution. 0.5mL of the mixed solution was then applied to substrates of various materials and placed in an oven at 60°C for 6 hours to produce a photocatalytically bactericidal polyurethane coating.

[0146] Example 7

[0147] (1) Preparation of functionalized polyol polymers:

[0148] Hydroxyethyl methacrylate (HEMA, 0.6 mmol), methyl methacrylate (MMA, 0.1 mmol), ethyl methacrylate (BMA, 0.1 mmol), styrene (0.1 mmol), tetraphenylporphyrin chloride (0.05 mmol), and polydimethylsiloxane methacrylate (0.05 mmol) were dissolved in 1 mL of a mixed solvent (toluene / butanol: 1:1). Under a nitrogen atmosphere, AIBN (0.03 mmol) was added as an initiator and stirred at 80°C for 6 h to obtain a mixed solution. After the reaction, the mixture was rotary evaporated to remove residual solvent to obtain a crude polyol solution. The crude polyol solution was then dropwise added to 5 mL of n-hexane for precipitation. The solution was then redissolved in acetone and precipitated in n-hexane. This process was repeated three times before drying to obtain a functionalized polyol polymer.

[0149] (2) Preparation of polyurethane coating:

[0150] 0.1g of a functionalized polyol polymer and 0.1g of polyhexamethylene diisocyanate (HDIT) were weighed and dissolved in 3mL of butanone to create a mixed solution. 0.5mL of the mixed solution was then applied to substrates of various materials and placed in an oven at 60°C for 6 hours to produce a photocatalytically bactericidal polyurethane coating.

[0151] Comparative Example 1

[0152] The process is basically the same as Example 1, except that polydimethylsiloxane methacrylate is not used.

[0153] Comparative Example 2

[0154] The process is basically the same as Example 1, except that tetraphenylporphyrin chloride is not included in the polyol, and a non-reactive porphyrin compound is added separately during the preparation of the polyurethane coating to form the polyurethane coating.

[0155] Comparative Example 3

[0156] The process is basically the same as Example 1, except that the amount of tetraphenylporphyrin acyl chloride is reduced to one tenth of that in Example 1.

[0157] Performance Testing

[0158] 1. Sterilization performance

[0159] The polyurethane coating with visible light catalytic sterilization prepared in Example 1 was tested for its sterilization performance against Escherichia coli (E.coil) and Staphylococcus aureus (S.aureus) under conditions of no light and light, respectively. The results are as follows: Figure 2 and Figure 3 shown.

[0160] from Figure 2 and Figure 3 It can be seen that the visible light catalytic sterilization polyurethane coating prepared in Example 1 has no sterilization effect under conditions without light, but has a good sterilization effect under conditions with light. Under the catalytic conditions of visible light, the surface morphology of bacteria on the surface of the experimental coating was damaged, and fluorescent staining showed that all bacteria were inactivated.

[0161] 2. Animal experiments

[0162] Mouse Experiment Procedure: After anesthesia, SD rats were shaved on the back, followed by hair removal and disinfection. A 2.0 cm long skin incision was then made. A 2.5 cm diameter circular blank and a visible light-bacterial polyurethane material (which exhibits excellent bactericidal properties) were used to cover the wound as the sample group. The blank group received no treatment. To prevent death from exposure to high-power xenon lamps, the SD rats were wrapped in tin foil, exposing only the wound area. A hole was punched in the foil beneath the head to provide a breathing hole. The SD rats' wounds, covered with the material, were irradiated with a xenon lamp for 20 minutes. During the experimental observation period, all animals were fed normally, and strict aseptic procedures were followed during the operation. Daily postoperative observations were performed to assess wound infection and healing, with particular attention paid to the presence of ulceration, delayed healing, suppurative infection, and inflammatory exudate. Wound area and healing status were photographed 2, 4, 6, 10, and 12 days after treatment. Animal Experiment Endpoint: The SD rats were terminated 14 days after wound healing.

[0163] The polyurethane material with visible light catalytic sterilization prepared in Example 1 and the blank group were applied to the skin wounds of mice under dark and light conditions, respectively. The results are as follows: Figure 4 shown.

[0164] from Figure 4 It can be seen that the polyurethane material with visible light catalytic sterilization prepared in Example 1 heals the fastest under light conditions, and can be healed in 12 days.

[0165] 3. Hydrophobicity

[0166] The hydrophobicity of the samples was tested by measuring the contact angle. The contact angle was measured by dropping 5 μL of water on the surface of the polyurethane coating prepared in Examples 1 to 7 using a German Dataphysics contact angle meter OCA15EC. The results are shown in Table 1.

[0167] 4. Antibacterial properties

[0168] The antibacterial effects of the polyurethane samples prepared in Examples 1 to 7 on Escherichia coli and Staphylococcus aureus were tested by the plate coating method. The results are shown in Table 1.

[0169] Table 1 Performance test results of visible light catalytic antibacterial polyurethane coatings of Examples 1 to 7

[0170] <![CDATA[Contact angle( o )]]> Antibacterial properties Example 1 112 excellent Example 2 108 excellent Example 3 110 excellent Example 4 105 excellent Example 5 110 excellent Example 6 103 good Example 7 100 good Comparative Example 1 55 Difference Comparative Example 2 110 Difference Comparative Example 3 109 Difference

[0171] It can be seen from Table 1 that the polyurethane coatings capable of photocatalytic sterilization in Examples 1 to 7 of the present invention have good hydrophobicity and antibacterial properties.

[0172] Comparison of Example 1 with Comparative Example 1 shows that when polydimethylsiloxane-methacrylate is not used, the polyurethane coating not only fails to obtain hydrophobicity but also has a poor antibacterial effect.

[0173] Comparison of Example 1 with Comparative Example 2 shows that the addition of the non-reactive porphyrin compound cannot provide the polyurethane coating with good antibacterial properties, and exhibits a poor antibacterial effect.

[0174] Comparison of the embodiment with comparative example 3 shows that the content of tetraphenylporphyrin acyl chloride is too low to provide antibacterial properties for the polyurethane coating, and exhibits a poor antibacterial effect.

[0175] It should be noted that, although the technical solutions of the present invention are described with specific examples, those skilled in the art will appreciate that the present invention should not be limited thereto.

[0176] While various embodiments of the present invention have been described above, the above descriptions are intended to be illustrative, non-exhaustive, and not limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments. The terminology used herein is selected to best explain the principles of the embodiments, their practical applications, or technological improvements in the marketplace, or to enable others skilled in the art to understand the embodiments disclosed herein.

Claims

1. A polyurethane coating for visible light catalytic sterilization, characterized in that: The raw materials for preparing the polyurethane coating include functionalized polyol polymer and polyisocyanate; The functionalized polyol polymer has structural units derived from (A) a photosensitive fungicide containing an unsaturated double bond and (B) a polymerizable monomer, and at least one of the (B) polymerizable monomers contains a hydroxyl group; The (B) polymerizable monomer includes at least a (meth)acrylate monomer, and the (meth)acrylate monomer includes at least a (meth)acrylate monomer modified with a hydrophobic substance; the (meth)acrylate monomer modified with a hydrophobic substance includes a polysiloxane-modified (meth)acrylate monomer, and the polysiloxane-modified (meth)acrylate monomer is selected from polydimethylsiloxane-(meth)acrylate; In the polymerizable monomer (B), the content of the polysiloxane-modified (meth)acrylate monomer is 5 mol% to 12 mol%; Optionally, the (B) polymerizable monomer further comprises one or more olefin monomers; The molar ratio of the (A) photosensitive bactericide containing an unsaturated double bond to the (B) polymerizable monomer is 1:8 to 1:

19.

2. The polyurethane coating according to claim 1, characterized in that The (A) photosensitive fungicide containing an unsaturated double bond includes one or more combinations of porphyrin derivatives, dihydrochlorin compounds, condensed ring quinone compounds, phthalocyanine compounds, and phenothiazine compounds.

3. The polyurethane coating according to claim 1 or 2, characterized in that The (meth)acrylate monomer further includes a (meth)acrylate monomer containing a hydroxyl group.

4. The polyurethane coating according to claim 1 or 2, characterized in that The olefin monomers include one or more of aliphatic olefins and aromatic olefins.

5. The polyurethane coating according to claim 1 or 2, characterized in that The (meth)acrylate monomer modified with a hydrophobic substance further comprises one or more combinations of (meth)acrylate monomers modified with fluoropolyether alcohol.

6. The polyurethane coating according to claim 5, characterized in that The fluoropolyether alcohol-modified (meth)acrylate monomer is selected from perfluoropolyether alcohol-(meth)acrylate.

7. The polyurethane coating according to claim 1 or 2, characterized in that The polyurethane coating is formed in the presence of an initiator (C), and the molar ratio of the photosensitive bactericidal agent (A) containing an unsaturated double bond to the initiator is 1:1 to 5:

1.

8. The polyurethane coating according to claim 1 or 2, characterized in that The molar ratio of the functionalized polyol polymer to the polyisocyanate is 2:1 to 1:

2.

9. The polyurethane coating according to claim 1 or 2, characterized in that The polyisocyanate includes one or more of aliphatic polyisocyanate, alicyclic polyisocyanate and aromatic polyisocyanate.

10. A method for preparing a polyurethane coating according to any one of claims 1 to 9, characterized in that: The following steps are involved: The (A) photosensitive bactericide containing an unsaturated double bond and the (B) polymerizable monomer are polymerized under the action of the (C) initiator to obtain the functionalized polyol polymer; The functionalized polyol polymer, polyisocyanate and organic solvent are mixed and subjected to solvent thermal volatilization to obtain a polyurethane coating.

11. The preparation method according to claim 10, characterized in that: The polymerization reaction temperature is 70-90° C. and the reaction time is 3-24 hours.

12. The preparation method according to claim 10 or 11, characterized in that: The temperature of the solvent thermal volatilization is 60-100° C. and the time is 6-12 hours.

13. An electronic device comprising a display device, characterized in that: A surface of a display element of the display device has the polyurethane coating according to any one of claims 1 to 9.

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